A Practical Guide to Plastics Sustainability: Concept, Solutions, and Implementation (Plastics Design Library) [1 ed.] 0128215399, 9780128215395

Table of contents :
Cover
PLASTICS DESIGN LIBRARY (PDL) PDL HANDBOOK SERIES
A PRACTICAL GUIDE TO PLASTICS
SUSTAINABILITY:
CONCEPT, SOLUTIONS, AND IMPLEMENTATION
Copyright
Contents
Preface
Chapter 1 An Overview of Sustainability and Plastics: A Multifaceted, Relative, and Scalable Concept
Chapter 2 Plastics Overview: Outline of the Current Situation of Plastics
Chapter 3 Metrics of Sustainability in Plastics: Indicators, Standards, Software
Chapter 4 Easy Measures Relating to Improved Plastics Sustainability
Chapter 5 Eco-Design Rules for Plastics Sustainability
Chapter 6 Environmental and Engineering Data to Support Eco-Design for Plastics
Chapter 7 Advanced Environmental and Engineering Properties to Support Eco-Design for Plastics
Chapter 8 Economics Relating to Fossil and Renewable Plastics
Chapter 9 Recycling of Plastics, Advantages, and Limitation of Use
Chapter 10 Transition of Plastics to Renewable Feedstock and Raw Materials
Chapter 11 Plastics Sustainability: Drivers and Obstacles
Chapter 12 Plastics Sustainability: Prospective
Disclaimer
Acronyms and Abbreviations
Glossary
1 An Overview of Sustainability and Plastics: A Multifaceted, Relative, and Scalable Concept
1.1 Sustainability and Circular Economy
1.1.1 Sustainability is a Tripod Based on Environment, Economic, and Social Features
1.1.2 Circular Economy
1.2 Sustainability in the Plastics Field
1.2.1 Sustainable Design
1.2.2 Renewable Polymers
1.2.3 Sustainable Processes or Sustainable Manufacturing
1.2.4 Sustainable Use Phase
1.2.5 Waste Management, Repair, Reuse, Recycling
1.2.6 Economic Involvements
1.3 People’s Perception of Plastics Sustainability
1.3.1 Opinions of Plastics Sector Players
1.3.2 General Public Opinions: Survey Example and Social Network Opinions
1.3.2.1 Plastics Concern Overview
1.3.2.2 Plastics Concern Details
Environment
Applications
Technical Features
Economy
1.4 Drivers of Change
1.4.1 Standards and Reporting
1.4.2 Policies, Directives and Regulations
1.4.3 Examples of Marketing Strategy Based on Sustainability
1.4.4 Cautious Forecast of Major Changes in the Global Environment
1.5 Sustainable Material and Waste Management
1.5.1 Sustainable Materials Management: A New Approach to Material Selection
1.5.2 Sustainable Waste Management
1.5.2.1 Recycling of Production Wastes
1.5.2.2 Treatment of Postconsumer Products
Environment Advantages
Cost Savings
Regulations and Limitations
1.6 Sustainability is Vital to Mitigate Environment Damages Caused by Booming Plastics Consumption
1.6.1 Population Growth
1.6.2 Standard of Living
1.6.3 General Consequences of Population and Gross Domestic Product Growths
1.6.4 Sustainability, the Expected Response to Climate Change
1.6.4.1 Main Greenhouse Gases Overview
Water Vapor
Carbon Dioxide
Methane
Halogenated Gases
Nitrous Oxide (N2O)
Ozone
Sulfur Hexafluoride
Concluding Remarks
Urgency of Decisions
1.6.4.2 Climate Warming and Sea Level Rise: The Major Risks
1.6.4.3 Biological Consequences
1.6.5 Natural and Artificial Sinks
1.7 Overview of Specific Plastics Features
1.7.1 Population and Gross Domestic Product Push the Plastics Demand
1.7.2 The Extent of the Problem: The Worldwide Plastics Demand at a Glance
1.7.3 Plastics: A Generic Name for Very Diverse Materials
1.8 Environmental Issues From a Plastics Point of View
1.8.1 Potential Pollutants
1.8.2 Specific Environmental Issues for Plastics: Visual Pollution, Marine Litter, Single-Use Items
1.8.2.1 Marine Litter
1.8.2.2 Microplastics, Microbeads, Microfibers
1.8.2.3 Single-Use Products: What is the Problem?
1.8.3 High Lifetimes are a Handicap for Waste
1.9 A Major Issue for Sustainability: Plastics Processing Needs (Polluting) Energy
1.9.1 Energy Versus Gross Domestic Product
1.9.2 Overview of Energy Demand Forecast
1.9.3 Potential Energy Sources for the Future
1.9.3.1 Fossil Energy
1.9.3.2 Renewable Energy Resources
Hydropower
Wind power turbine
Solar power
Geothermal Energy
Biofuels and Other Biofeedstocks from Biomass
1.9.3.3 Share Examples of Electricity Sources
1.10 Water Footprint of the Plastics Industry and Water Stress
1.10.1 Overview
1.10.2 Water Consumption for Plastics Production
1.10.3 Best Available Techniques in the Production of Polymers
1.10.4 Polymers From Natural Sources: Not So Green From a Water Point of View
Reference
Further Reading
2 Plastics Overview
2.1 Do Not Confuse Thermoplastics, Thermoplastic Elastomers, Thermosets, Composites, and Hybrids
2.1.1 Thermoplastics
2.1.1.1 Advantages
2.1.1.2 Disadvantages
2.1.2 Thermoplastic Elastomers
2.1.3 Thermosets
2.1.3.1 Advantages
2.1.3.2 Disadvantages
2.1.4 Polymer Composites
2.1.5 Hybrid Materials
2.2 Compound Is Much More than Polymer: Build the Best Balance of Engineering, Cost, and Environmental Requirements Thanks ...
2.2.1 Plastic Alloying
2.2.2 Compounding With Additives
2.2.2.1 Mechanical Property Upgrading and Customization: Toughening, Reinforcement, Plasticization
Reinforcement
Reinforcement With Fibers
Reinforcement and Filling With Mineral Fillers
Reinforcement With Glass Beads
Nanofillers
Impact Modifiers
Plasticization
2.2.2.2 Aging Protection: Additives, Films
2.2.2.3 Sensory Properties
Scratch-Resistance Improvement
Odors
2.2.2.4 Specific Properties: Specific Grades and Additives
Fire Behavior
Conductive Polymers
Antistatic Specialties
Conductive Carbon Blacks
Conductive Fibers
Metal Powders or Flakes
Additives for Antifriction Polymers
Polymers With High Thermal Conductivity
Magnetic Polymers
2.2.2.5 The Cost Cutters
Nonblack Fillers
2.2.2.6 Use of Recycled Plastics
2.2.2.7 Structural Foams
2.3 Understand Particular and Surprising Behavior of Plastics
2.3.1 Elemental Composition Is Essential
2.3.2 Molecular Weight and Chain Architecture Are Also of High Importance
2.3.3 Crystalline and Amorphous Thermoplastics, Glass Transition Temperature
2.3.3.1 Amorphous Polymers
2.3.3.2 Crystalline and Semicrystalline Polymers
The Glass Transition Temperature
Crystallization is Time and Thermal Dependent and Isn’t Homogeneous
2.3.4 Viscoelasticity, Creep, Relaxation
2.3.4.1 Time Dependency
2.3.4.2 Temperature Dependency
2.3.5 Isotropy, Anisotropy
2.3.6 Potential Heterogeneity of Properties
2.3.6.1 Water Uptake Plasticizes Certain Polymers
2.3.6.2 Molecular and Filler Orientation
2.3.6.3 Don’t Confuse Local and Bulk Properties: Take Into Account the Statistical Distribution of Properties
2.3.7 Ambient Humidity Can Plasticize Polymers and Change Their Properties
2.3.8 Often Properties Evolve Abruptly: Glass Transition, Yield, Knees, Frequency-Dependent Properties
2.3.9 Dimensional Stability
2.3.9.1 Shrinkage
2.3.9.2 Warpage
2.3.9.3 Release of Organic Additives
2.3.10 Aging1
2.3.11 Chemical Resistance by Immersion or Contact
2.3.11.1 Exposure Without Constraint
2.3.11.2 Environmental Stress Cracking (ESC)
2.4 Sensory Properties of Plastics: An Outstanding Advantage for Marketing
2.4.1 Optical Properties
2.4.2 Touch
2.4.3 Scratch-Resistance Improvement
2.4.4 Acoustic Comfort
2.4.5 Odors
2.4.6 Taste
2.4.7 Fogging
2.5 Outline of the Technical and Economic Possibilities of Processing
2.5.1 Molding Solid Thermoplastics
2.5.2 Extrusion and Connected Processes
2.5.3 Calendering
2.5.4 Blow Molding
2.5.5 Molding Liquid Thermoplastics
2.5.6 Secondary Processing
2.5.7 Three-Dimensional Printing and Other Additive Manufacturing Methods
2.5.8 Brief Economic Comparison of Some Processing Costs
2.5.9 Repair Possibilities: A Significant Thermoplastic Advantage for Large Parts
Further Reading
3 Metrics of Sustainability in Plastics: Indicators, Standards, Software
3.1 Environment Management Systems
3.2 Life Cycle Accounts: LCI, LCA, LCIA
3.2.1 Life Cycle Overview
3.2.2 Life Cycle Inventory
3.2.3 Life Cycle Assessment
3.2.4 Life Cycle Impact Assessment
3.2.5 Incorporation of Eco-Design or Sustainable Design in the Life Cycle Through ISO 14006
3.2.6 Beware, Life Cycle Costing is Not an Environmental Feature
3.3 General Purpose and Specific Standards Linked to the Environment
3.3.1 Overview
3.3.2 Environmental Management: ISO 14000 Family and a Few Related Standards
3.3.3 Incorporation of Eco-Design or Sustainable Design in the Life Cycle Through ISO 14006
3.3.4 Environmental Assessment of Sites and Organizations
3.3.5 Environmental Labels and Declarations: The ISO 14020 Series of Standards
3.3.6 Environmental Performance Evaluation: ISO 14030 and ISO 14031
3.3.7 Detailed Accounts of LCA, LCI, LCIA: The ISO 14040 Series
3.3.8 Risk Management
3.3.9 Quality Management Systems: ISO 9000 Family Addresses Various Aspects of Quality Management
3.3.10 Environmental Product Declaration
3.4 Environmental Indicators
3.4.1 Overview
3.4.2 Energy Consumption
3.4.3 CO2 and other Greenhouse Gases, Gas Warming Potential
3.4.4 Water Footprint
3.4.5 Toxicity, Unwanted Emissions
3.4.6 Other Common Indicators
3.4.6.1 Ozone Depletion, Photochemical Oxidation
3.4.6.2 Photochemical Smog
3.4.6.3 Acidification
3.4.6.4 Eutrophication
3.4.7 Other Diverse Indicators
3.4.8 Examples of Indicators
3.5 Synthetic Indices Resulting From Environmental Indicator Integration
3.5.1 Overview
3.5.2 Eco-Profiling System—Volvo/Swedish Industry (https://www.iisd.org/pdf/globlgrn.pdf)
3.5.3 CML-IA by CML
3.6 Databases and Software Help in Environmental Management, but Can Lead to Some Discrepancy
3.6.1 Examples of Software Solutions
3.6.2 Software May Lead to Some Discrepancies
3.7 Clarification Concerning Some Terms
Further Reading
4 Easy Measures Relating to Improved Plastics Sustainability
4.1 Overview of Pace of Change in the Plastics Industry
4.2 Decrease the Material Impact on the Product Sustainability
4.2.1 Avoid, Minimize, or Ban Hazardous Materials; Obey Health and Safety Concerns, Regulation Compliance
4.2.2 Optimize Material Consumption Using Simulation and Modeling Tools
4.2.3 Avoid Nonrenewable Natural Resource Depletion Using Renewable Materials
4.2.4 Use Recycled Materials and Waste
4.2.5 Avoid Renewable Material Competing With Food or Causing Deforestation
4.2.6 Design to Facilitate Maintenance, Repair, Reuse, Refurbishment
4.2.7 Use Reliable Materials and Trustworthy Providers
4.3 Minimize Manufacturing Impact on the Environment
4.3.1 Invest in Efficient Machines
4.3.1.1 Injection Machines: A Critical Choice Between Hydraulic, Electric, and Hybrid Models
Hydraulic Injection Molding Machines
Electric Injection Molding Machines
Hybrid Injection Molding Machines
4.3.1.2 Peripherals and Retrofitting Solutions
4.3.2 Favor Less Energy-Demanding Compounds
4.3.3 Digitalization and Software Solutions
4.3.3.1 Smart or Intelligent Machines
4.3.3.2 Manufacturing Execution System Software
4.3.3.3 Enterprise Resource Planning Software
4.3.3.4 Software Solutions Integrated by Plastics Machinery Providers
Energy Monitoring
Troubleshooting
Intelligent Machines
Integrated Production
Interactive Services
4.3.3.5 Target Zero-Defect Manufacturing
Example of Mass-Produced Molded Parts
Example of Zero-Defect Manufacturing of Composite Parts in the Aerospace Industry
4.3.4 Promote Efficient Real-Time Quality Control
4.3.5 Preventive and Predictive Maintenance
4.3.6 Minimize Waste
4.3.7 Use Renewable Energy
4.3.8 Integrate Manufacturing Steps Using Direct Mixing, Comolding, Overmolding, In-Line Process, Workcells
4.3.8.1 Integrated Compounding
4.3.8.2 Coprocessing: Coinjection and Overmolding
4.3.8.3 Fluid-Assisted Injection Molding
4.3.8.4 In-Line Decoration: FIM, IMC, IML, Among Others
4.3.8.5 Printing and Laser Marking
Printing
Laser Marking
4.3.8.6 New Processes, Function Integration
Laser Structuring: Integrate Mechanical and Electrical Functions in MIDs by Laser Direct Structuring
In-Mold Assembly
4.3.8.7 Example of Alternative Processing Methods: Thermoformed Bottles Compete With Blow-Molded Ones
4.3.8.8 Workcells: Automation and Complete Production Cells
4.3.9 Integration of Subparts and Reduction of Raw Material Diversity
4.3.10 Potentially Hazardous Releases Possibly Emitted by Plastics
4.3.11 Think Retrofitting of Machinery
4.4 Reduce Impact of Supply and Distribution Chains
4.5 Reduce Impacts of the Use Phase
4.6 Balancing the Product Durability and Actual Sustainable Benefits
4.7 Optimize the End-of-Life
4.8 Competence Development, Training, e-Learning
References
Further Reading
5 Eco-Design Rules for Plastics Sustainability
5.1 Examples of Environmental Traps
5.1.1 Favorable Example of Automotive Industry: Reduction of Production Impact Matches a Net Impact Reduction Due to the Us...
5.1.2 Counterexample of House Building: Increase of Production Impact Leads to a Final Impact Mitigation due to the Use Phase
5.1.3 Selection of Energy Production Method can Replace a Pollution Type by Another
5.2 Specific Plastics Design Issues
5.3 Overview of Material Sustainability Impact
5.3.1 General Pathway toward Mitigation of Material Impact
5.3.2 Examples of Impact of Material Selection on Other Parameters
5.3.3 Have an Overall View of Sustainability including Late Phases
5.4 Design to Withstand Mechanical Loading
5.4.1 Overview
5.4.2 Temperature Effect
5.4.3 Loading Type Effect
5.4.4 Strain Rate or Time Effect
5.4.5 Impact Behavior
5.4.6 Hardness
5.4.7 Dynamic Fatigue
5.4.8 Dimensional Effects
5.4.9 Combination with other Parameters
5.4.10 Lifetime
5.4.11 Environmental Cost of Reinforcements
5.4.11.1 Fibers
All GFs have in common
Carbon Fibers
Natural Fibers
5.4.11.2 Natural Mineral Fillers
5.4.11.3 Cellulose Nanofibers
5.4.11.4 Carbon Nanotubes and Graphene
5.5 Plastics Behavior Above Ambient Temperature
5.5.1 Average Temperature
5.5.2 Continuous Use Temperature
5.5.3 Underwriter Laboratories Temperature Index
5.5.4 Heat Deflection Temperature
5.5.5 Vicat Softening Temperature
5.5.6 Accelerated Aging
5.5.7 Environmental Cost of Stabilizers and Antioxidants
5.6 Low Temperature Behavior
5.6.1 Low-temperature Tests
5.6.2 Brittle Point
5.6.3 Rigidity in Torsion: “Clash-Berg” and “Gehman” tests
5.6.4 Crystallization Test
5.6.5 Environmental Footprint of Plasticizers
5.7 Design for Dimensional Stability
5.7.1 Thermal Expansion or Retraction
5.7.2 Shrinkage
5.7.3 Warpage
5.7.4 Water or Chemicals Uptake
5.7.5 Aging, Desorption, Bleeding, Releasing of Organic Components
5.8 Electrical Properties
5.8.1 Volume Resistivity: ASTM D257 and IEC 93
5.8.2 Surface Resistivity: ASTM D257 and IEC 93
5.8.3 Dielectric Strength
5.8.4 Arc Resistance
5.8.5 High Voltage Arc Tracking Rate
5.8.6 Frequency, Temperature, Moisture, Physical, and Dynamic Aging Effects
5.8.7 Conductive Polymers: Sustainability Considerations
5.9 Fire Behavior: Some Ins and Outs
5.9.1 UL 94 Fire Ratings
5.9.2 Oxygen Index
5.9.3 Smoke Opacity, Toxicity, and Corrosivity
5.9.4 Cone Calorimeter
5.9.5 Ignition Temperature
5.9.6 Rate of Burning
5.9.7 Glow Wire Test
5.9.8 Fire Resistant Polymers: Sustainability Considerations
5.9.8.1 Inherently FR Polymers
5.9.8.2 FR Additive Solutions
5.9.8.3 The Top Solutions: Halogenated Flame Retardant and Fire, Smoke, and Toxicity Grades
5.9.9 General Collateral Effects from a Sustainability Standpoint
5.9.10 A Glimpse on General Behavior of Biopolymers
5.10 Sensory Issues: Optical Properties, Aesthetics, Odor, Taste, Touch
5.10.1 Complementarity of Instrumental Measurements and Sensory Panel Evaluations
5.10.2 Visual Aspect
5.10.3 Physical Aspect
5.10.4 Touch
5.10.5 Odor and Taste Properties and Transfer
5.10.6 Noise, Vibration, Harshness
5.10.7 General Collateral Effects of Colorants from a Sustainability Standpoint
5.10.7.1 Colorants and Pigments
5.10.7.2 Titanium Oxide
5.11 Design for Aging, Weathering, and Light and UV Behaviors
5.11.1 Overview of Light and Ultra Violet Resistance
5.11.2 Elements of Weathering Appraisal
5.11.2.1 Effect of Color
5.11.2.2 Effect of Anti-UV Additives
5.11.3 Examples of Published Assessments Relating to Light and UV Behavior of Compounds
5.11.3.1 Polyolefins and Derivatives
5.11.3.2 PVC and Other Chlorinated Thermoplastics
5.11.3.3 Styrenics
5.11.3.4 Polyamides
5.11.3.5 Thermoplastic Polyesters
5.11.3.6 Polymethylmethacrylate
5.11.3.7 Polycarbonate
5.11.3.8 Polyacetal
5.11.3.9 Polyphenylene Ether
5.11.3.10 Fluorinated Thermoplastics
5.11.3.11 Cellulosics
5.11.3.12 Polysulfone
5.11.3.13 Polyphenylene Sulfide
5.11.3.14 Polyetherimide
5.11.3.15 Liquid crystal polymer
5.11.3.16 Polybenzimidazole
5.11.3.17 Alloys
5.11.3.18 TPE and Thermoplastic vulcanizate
5.12 Lifetime and End-of-life Criteria
5.12.1 Overview
5.12.2 Accelerated Aging and Modeling
5.12.3 Smart Design and Mitigation of Aggressiveness of Surroundings are Benefiting from a Sustainability Standpoint
5.13 Regulation, Health, and Safety Requirements
Further Reading
6 Environmental and Engineering Data to Support Eco-Design for Plastics
6.1 Overview
6.2 Be Cautious of Some Traps Concerning Standards
6.2.1 General Boundaries of Standards
6.2.2 Real Cases Are Not Ideal Standardized Cases: Take Into Account the Statistical Distribution of Properties
6.2.2.1 Failure Onset: Weak Points and Average Properties
6.2.2.2 Do Not Confuse Local and Bulk Properties: Take into Account the Statistical Distribution of Properties
6.2.2.3 Means are False Friends
6.2.2.4 Standard Deviation Depends on Multiple Factors
6.2.3 Be Cautious of the Real Sense of Common Terms
6.3 Environmental Indicators
6.3.1 Use of Renewable Materials Instead of Fossil Resources
6.3.2 Energy Requirements
6.3.3 Net Carbon Footprint, CO2 and Other Greenhouse Gases, Global Warming Potential
6.3.4 Water Footprint
6.3.5 Examples of Other Environmental Indicators
6.3.6 Variability and Weakness of Environmental Indicators
6.3.7 Do Not Confuse Indicator per Weight and Indicator per Functional Unit
6.4 Usual Indicators for Plastics Design
6.4.1 Thermal Behavior
6.4.1.1 Overview
6.4.1.2 Glass Transition Temperature
6.4.1.3 Thermal Behavior above Room Temperature: HDT, CUT, UL Temperature
Heat Deflection Temperature or Deflection Temperature Under Load
General Assessments Concerning Continuous Use Temperature
Examples of UL Relative Temperature Index
Examples of Impact Strength Above Room Temperature
Examples of Vicat Softening Temperature
6.4.1.4 Low-Temperature Behavior
Expected Minimum Service Temperatures
Low-Temperature Tests
Standardized Impact Tests Processed at Low Temperatures
Brittle Point
Dynamic Torsion Modulus
Crystallization Test
6.4.2 Density
6.4.3 Mechanical Properties
6.4.3.1 Hardness
6.4.3.2 Stress and Strain Under Unidirectional Loading: Tensile, Flexural, and Compression Properties
6.4.3.3 Pay Attention to “Compression Modulus” That Can Hide “Bulk Modulus”
6.4.4 Examples of Water Uptake
6.4.5 Examples of Mold Shrinkage
Further Reading
7 Advanced Environmental and Engineering Properties to Support Eco-Design for Plastics
7.1 Advanced Properties That can Help Eco-Design
7.1.1 Fuel Energy and Feedstock Energy
7.1.2 Gas Warming Potential
7.1.3 Rapid Overview of Examples of Advanced Indicators
7.1.3.1 Examples of Ozone Depletion Potential
7.1.3.2 Photo-Oxidant Creation Potential
7.1.3.3 Acidification Potential
7.1.3.4 Eutrophication Potential
7.1.3.5 Dust/Particulate Matter (≤10μm3)
7.1.3.6 Ecotoxicity Potential
7.1.4 Natural-Sourced Versus Fossil Polymers: A Mixed Bag of Benefits and Drawbacks
7.2 Advanced Engineering Properties
7.2.1 Thermal Dependency of Mechanical Properties
7.2.1.1 Short-Term Effects of High and Low Temperatures
Behavior Above Room Temperature
Behavior Below Room Temperature
7.2.1.2 Long-term Heat Effect on Oxidizing Aging
7.2.2 Time Dependent Mechanical Properties
7.2.2.1 Creep
7.2.2.2 Relaxation
7.2.2.3 Fatigue
7.3 Poisson’s Ratios
7.4 Electrical Properties
7.4.1 Resistivity Examples
7.4.2 Dielectric Strength Examples
7.4.3 Examples of Dielectric Loss Factors
7.5 Flammability: Limiting Oxygen Index examples
7.6 Optical Properties: Examples of Transparent or Translucent Plastics
7.7 Gas Permeability
7.8 Tribological Properties
7.8.1 Coefficient of Friction
7.8.2 Limiting Pressure Velocity
References
Further Reading
8 Economics Relating to Fossil and Renewable Plastics
8.1 Raw Plastics Material Cost: Beware of Unusual “Raw” Materials and Waste Levels
8.1.1 Usual Physical Types of Plastics Raw Materials
8.1.2 Cost of Sophisticated Raw Materials
8.1.3 Examples of Additive Costs
8.1.4 Examples of Reinforcement Costs
8.1.5 Beware of the Actual Consumption of Plastic Compared to the Weight of the Part
8.2 Processing Costs
8.2.1 Capability Proposals for Some Processing Methods
8.2.1.1 Proposals for Thermoplastics
8.2.1.2 Proposals for Composites
8.2.2 Use of Cost Estimator Software
8.2.2.1 Examples of Cost Estimator Software
8.2.2.2 Examples of Cost Estimator Results
Agreement Between Different Cost Estimators
Example of Effect of Run Size
Check the Sensitivity and the Application Window of Variables of Interest
8.3 Examples of Costs
8.3.1 Expected Costs by Market
8.3.2 Expected Cost of Composites
8.4 Economics of Renewable Materials
8.4.1 Plastics Recycling
8.4.2 Biosourced Plastics Consumption
8.4.3 Market Shares by Bioplastic Family
8.4.4 Production Capacities by Bioplastic Family
8.4.5 Bioplastic Capacities by Region
8.4.6 Bioplastic Capacities by Market
8.4.7 Bioadditives Consumption
8.4.7.1 Natural Fiber Composite Market
8.4.7.2 Other Bioadditives
8.4.8 Wood Plastic Composite and Natural Fiber Composite Markets
8.4.9 Biomaterial Costs
8.4.9.1 Bioplastics Costs
8.4.9.2 Natural Fiber Costs
8.5 Survey of Main Bioplastics Markets
8.5.1 Packaging
8.5.2 Consumer Goods
8.5.3 Automotive and Transportation
8.5.4 Building and Construction
8.5.5 Agriculture
8.5.6 Other Markets
Further Reading
Papers and Books
9 Recycling Plastics: Advantages and Limitations of Use
9.1 Recycling Outline
9.1.1 Environmental Benefits of Recycling
9.1.2 Economics of Recycling
9.1.2.1 Market Overview by Region
Overview of Plastic Wastes in United States
Overview of Plastic Wastes in Europe
9.1.2.2 Recovery Costs: A Severe Obstacle to a Self-Growth
Incentive Effect of High Crude Oil Price
9.1.3 Reliability of Recycling
9.1.4 Example of Recycling Loop Effects on Performances
9.1.5 Recycling: Legislation, Standards, and Related Publications
9.1.5.1 EU Waste Legislation Examples
9.1.5.2 Automotive
Schedule
9.1.5.3 Packaging
9.1.5.4 Electrical and Electronic Equipment
9.2 Recycling Methods
9.2.1 Reprocessing of Processing Scraps and Mechanical Recycling
9.2.1.1 Overview
9.2.1.2 Effect of Pollutants
9.2.2 Recycled Material Upgrading by Additives
9.2.2.1 Overview
9.2.2.2 Compatibilizers
9.2.2.3 Impact Modifiers
9.2.2.4 Plasticization
9.2.2.5 Additives for Aging Protection
9.2.2.6 Sensorial Property Enhancers
9.2.2.7 Special Additives and Packages for Recyclate Upgrading
9.2.2.8 The Purity Enhancement
9.2.3 Chemical Recycling
9.2.3.1 Thermoplastic Polyesters
9.2.3.2 Polyurethanes
9.2.4 Solvent Recycling
9.2.4.1 Pretreatment
9.2.4.2 Selective Dissolution
9.2.4.3 Separation
9.2.5 Thermal Recycling
9.2.6 Energy Recovery
9.2.7 Anaerobic Biodegradation of Biodegradable Plastics With Gas Recovery
9.2.8 Enzymatic Depolymerization of Polylactic Acid
9.2.9 The REnescience Process Recovering Plastics and Metals From Municipal Solid Waste Without Sorting
9.3 Sectorial Routes for Recycling
9.3.1 Used Polyethylene Terephthalate Bottles: Realities of Everyday Life
9.3.1.1 Collection of Bottles
9.3.1.2 Sorting of Plastic Bottles
9.3.1.3 Bottle Recycling
9.3.1.4 Bottle-to-Bottle Recycling
9.3.1.5 Bottle to Engineering Thermoplastic Polyester Grades
9.3.2 High-Density Polyethylene Bottles
9.3.3 Electricity and Electronics: Closed- and Open-Loop Recycling
9.3.4 Auto: Closed- and Open-Loop Recycling
9.3.5 Recycling and Reprocessing of Building Products
9.3.6 Recycling of Thermosets
9.3.7 Recycling of Composites
9.3.8 Recycling of Glass and Carbon Fibers, and High-Performance Polymers
9.4 Recycling Advantages: CO2 Emission, Greenhouse Effect, and Carbon Footprint
9.4.1 Some Real Facts and Figures
9.4.2 Statistical Analyses of Some Real Examples
9.5 Recyclate Property Examples
9.5.1 Polyamides Examples
9.5.1.1 Industrially Recycled Polyamides
9.5.2 Polystyrene and Acrylonitrile Butadiene Styrene Examples
9.5.3 Polypropylene Examples
9.5.4 Examples of Polycarbonate, PC/ABS, and PC/PBT Alloys
9.5.5 Examples of Polyetherimide
9.6 Recycled Materials Often Also Bring Cost Saving in Addition to Pollution Savings
9.7 Some Limitations to Recycled Material Use
9.7.1 Underwriters Laboratories’s Recommendations on the Use of Regrind
9.7.2 Producer Recommendations
References
Further Reading
Websites
10 Transition of Plastics to Renewable Feedstock and Raw Materials: Bioplastics and Additives Derived From Natural Resources
10.1 Brief Inventory of Renewable Polymers
10.2 Renewable Additives
10.2.1 Renewable Plasticizers
10.2.2 Natural Reinforcements
10.2.2.1 Natural Fibers
10.2.2.2 Balsa
10.2.2.3 Other Organic Natural Fillers
10.2.2.4 Other Inorganic Renewable Natural Fillers
10.2.3 Processing Aids
10.2.4 Surface Friction Modifiers: Lubricant, Slipping, and Antiblocking Agents
10.2.5 Release Agents
10.2.6 Antistatic Additives
10.2.7 Optical Property Modifiers: Antifogging, Color, Gloss Modifiers
10.2.7.1 Renewable Colorants
10.2.8 Renewable Impact Modifiers and Tougheners
10.2.9 Protective Agents, Stabilizers, Thermal, and Antiaging Additives, Light Stabilizers
10.2.10 Miscellaneous Additives: Fire Retardants, Tackifiers, Nucleating Agent, Waxes, Hardeners, Foaming Agents, etc
10.2.11 Renewable Masterbatches Based on Renewable Matrix or Renewable Additive
10.3 Ready-to-Use Thermoplastic Blends Derived From Starch, a Natural Polymer
10.3.1 Overview
10.3.2 Processing
10.3.3 Environmental Features
10.3.4 Application Sectors
10.3.5 Examples of Producers and Trademarks
10.3.6 Property Tables
10.4 Polylactic Acid Polymerized From a Natural Monomer
10.4.1 Overview
10.4.2 Processing
10.4.3 Environmental Features
10.4.4 Application Sectors
10.4.5 Examples of Producers and Trademarks
10.4.6 Property Tables
10.4.6.1 Melt Strength Enhancement
10.4.6.2 Heat Stabilization
10.5 Natural Linear Polyesters Produced by Bacterial Fermentation—Polyhydroxyalkanoates
10.5.1 Overview
10.5.2 Processing
10.5.3 Environmental Features
10.5.4 Application Sectors
10.5.5 Examples of Producers and Trademarks
10.5.6 Property Tables
10.6 Cellulose Derivatives Based on Natural Cellulose
10.6.1 Overview
10.6.1.1 Advantages
10.6.1.2 Drawbacks
10.6.2 Processing
10.6.3 Environmental Features
10.6.4 Application Sectors
10.6.5 Examples of Producers and Trademarks
10.6.6 Property Tables
10.7 Biopolyethylene and Biosourced Ethylene Vinyl Acetate
10.7.1 Overview
10.7.1.1 Reminder of Advantages of Traditional Polyethylene
10.7.1.2 Reminder of Drawbacks of Traditional Polyethylene
10.7.2 Processing
10.7.3 Polyethylene Environmental Features
10.7.4 Polyethylene Application Sectors
10.7.5 Examples of Producers and Trademarks
10.7.6 Polyethylene Property Tables
10.7.7 Biobased Ethylene Vinyl Acetate Copolymer
10.8 Renewable PET, PBT, PEF, PTT Alternatives to Fossil Thermoplastic Polyesters PET and PBT
10.8.1 Replacement of the Fossil Alcohol by Natural Alcohol
First Step: Plant-Based Mono Ethylene Glycol
10.8.2 Second Step: Paraxylene for 100% Biopolyester
10.8.3 The Third Way: Polyethylene-Furanoate
10.8.4 Recycled Polyethylene Terephthalate
10.8.5 PolyTrimethyleneTerephthalate
10.8.6 Partially Renewable Thermoplastic Elastomer Ester
10.8.7 Polybutylene Succinate
10.8.8 Property Examples of PET, PBT, PTT, TPEE, PBS
10.9 Renewable Polyamides
10.9.1 Polyamides With Long Hydrocarbon Segments: PA11, 1010, 1012
10.9.2 Polyamides Alternating Long and Short Hydrocarbon Segments: PA610, 510, 512, 514, 410
10.9.3 Polyamides With Short Hydrocarbon Segments: PA56
10.9.4 Amorphous Transparent Renewable Polyamides
10.9.5 Polyphthalamide
10.9.6 Renewable Polyether Block Amides
10.9.6.1 Property Tables
10.10 Renewable Polyurethanes
10.10.1 Natural and Renewable Oil Polyols
10.10.2 CO2-Containing Polyols
10.10.3 Bioisocyanate Crosslinker for Polyurethanes
10.10.4 Applications
10.10.4.1 Biopolyurethane Foams
10.10.4.2 Biopolyurethane Sprays
10.10.4.3 Coatings and Adhesives
10.10.4.4 Biothermoplastic Polyurethane
10.10.5 Examples of Environmental Advantages
10.10.6 Examples of Polyurethane Players
10.11 Renewable Unsaturated Polyesters
10.11.1 Overview
10.11.2 Applications
10.11.3 General Properties
10.11.3.1 General Advantages
10.11.3.2 General Drawbacks
10.11.3.3 Special Grades
10.12 Renewable Epoxy Resins
10.12.1 Natural-Sourced Epoxidized Oils and Epichlorhydrin
10.12.2 General Properties of Epoxy Resins
10.12.2.1 General Advantages
10.12.2.2 General Drawbacks
10.12.2.3 Special Grades
10.12.2.4 Applications
10.13 Biosourced Polycarbonates
10.14 Derivatives of Lignin: For Instance the Liquid Wood (Arboform by Tecnaro)
10.15 Example of Self-Reinforced Composite Produced From Cereals
10.16 Renewable Acrylics—Poly(Methyl Methacrylate)
10.16.1 General Advantages
10.16.2 General Drawbacks
10.17 Renewable Phenol Formaldehyde Resins
10.17.1 General Advantages
10.17.2 General Drawbacks
10.18 Renewable Polypropylene
10.19 Renewable Polyvinyl Chloride
10.19.1 General Advantages
10.19.2 General Drawbacks
10.20 Thermosetting Cyanate Ester Resins
10.21 Thermosetting Furanic Resins
10.22 An Endless List of Alloys
10.22.1 Alloys of Renewable Polymers
10.22.2 Hybrid Alloys of Renewable and Fossil Polymers
10.22.3 Others
10.22.3.1 Examples of Algae and Fossil Polymer Compounds
10.22.3.2 Various Bioplastics Derived From Renewable Raw Materials
References
Further Reading
11 Plastics Sustainability: Drivers and Obstacles
11.1 The Vast Range of Waste Strategies: From Waste Minimization to Landfilling
11.2 Waste Minimization
11.3 Repair and Reuse
11.3.1 Overview
11.3.2 High-Tech Repairs: Example of Aircraft Structural Repair
11.3.3 Benefits of Reused Drums
11.3.4 Refillable Bottles: May Be a Counterexample
11.3.5 Refurbishing and Upgrading Machinery: Benefits of Industry 4.0
11.3.5.1 Overview
11.3.5.2 Industry 4.0: A Modern Way to Inspire an Efficient Retrofitting
11.4 Recycling and Actual Reuse
11.4.1 Environmental Benefits of Recycling
11.4.2 Closed-Loop Recycling Overview
11.4.3 Recycling of High-Performance Materials: Example of Carbon Fiber
11.4.4 Global Warming Potential of Specific Recycled Polymers
11.4.5 Global Warming Potential of End Products Incorporating Recycled Polymers
11.4.6 Examples of Fossil Energy Gains Due to the Use of Recycled Resins
11.4.7 Fossil Energy Demand of End Products Based on Reused Materials and/or Recycled Polymers
11.4.8 Example of Inconsistency Between Indicators Relating to a Recycled Polymer Family
11.4.9 Examples of Cost Savings Due to Recycling
11.4.10 Example of Environmental Benefits of Recycling a Commodity Plastic: rPVC
11.4.11 Recycling, Reuse, or Use Virgin Polymer: The Right Answer Depends on the Actual Context
11.5 Policy, Legislation, Fees, Taxes, Bans, Deposit and Bill Strategies, and the Green Wave Are Real Game-changers
11.5.1 Incentive Legislation Example: Extended Producer Responsibility
11.5.2 Example of Regulation Restraining the Use of Plastics: Carrier Bags
11.5.3 Example of Regulation Boosting Recycling: End-of-Life Vehicles
11.5.4 Example of Recycled Plastics Limitations
11.5.5 Example of “Deposit and Bill” Approach: Beverage Bottles
11.6 Renewable Materials: Alternative to Oil Becoming Scarcer and Use of Natural-Sourced Materials
11.6.1 Success Story Examples
11.6.2 A Questionable Case
11.6.3 A Textbook Case: Replacement of ABS for Lego Bricks
11.6.3.1 Drop-in Solutions for Green ABS
11.6.3.2 Substitute Biobased Polymers for ABS
11.7 Ecological Features Boosting the Growth of Plastics
11.7.1 Functionality Integration Due to Design Freedom
11.7.2 Lightweighting: Energy and Resource Savings, Pollution Mitigation
11.7.2.1 Overview of General Plastics Solutions
11.7.2.2 Environment-Friendly Structural Solutions
11.7.2.3 The Main Potential Boosters and Brakes for Natural Fiber–Reinforced Composites
11.7.2.4 Fully Renewable Solutions: Natural Fibers and Biosourced Polymers
11.7.2.5 Hybrid Solutions Combine Renewable and Fossil Components
11.7.2.6 Sustainable Solutions Based on “Unsustainable” Composites
11.7.2.7 Automotive: A Promising Domain for Traditional Fossil Plastics
11.7.2.8 Composites Save Weight and Mitigate Pollution
Organosandwich
Traditional Composites
11.7.2.9 Mobility Solution Examples
Aircraft
Road Transportation
Marine
Railway
11.7.3 Take Advantage of the Unique Insulation Efficiency of Plastics Foams: “Zero Energy” Housing Examples and Others
11.8 Examples of Bottlenecks for the Growth of Plastics
11.8.1 Fire Behavior
11.8.2 Nanomaterials
11.8.3 3D Printing and Other Additive Manufacturing Techniques
11.9 Where We Stand Today: Global, Regional, Sectorial Inequalities
11.9.1 Global Landscape
11.9.2 Plastics Waste Treatment: Promising Results of Advanced Countries
11.9.3 Brief Jumble of Facts and Figures
References
Further Reading
12 Plastics Sustainability: Prospective
12.1 Demand and Growth Potential of Plastics
12.1.1 Overview of the Future Global Plastics Industry
12.1.2 Effects of Demography and Standard of Living
12.1.3 Rethinking Time Management
12.1.4 Authoritarian Restrictions, Bans, and Incentive Actions
12.1.5 Emerging Technologies: Example of Vehicles
12.1.5.1 Electric Vehicles
12.1.5.2 Autonomous Vehicles
12.1.6 The Dream of Almost Perfect Polymers
12.1.7 Alternative Fuels
12.1.8 Plastics Brand Image
12.1.9 Specificities Linked to Sustainable Plastics
12.2 Economics of Renewable Plastics and Bio-additives: Quantified Expectations
12.2.1 Renewable Plastics Consumption and Capacity Forecasts
12.2.1.1 Renewable Plastics Consumption Overview at Mid- and Long-Term
Recovery Volume
Bio-sourced Plastics Consumption
12.2.1.2 Market Shares by Bioplastic Family
12.2.1.3 Production Capacities by Bioplastic Family
12.2.1.4 Bioplastic Capacities by Region
12.2.1.5 Bioplastic Capacities by Market
12.2.1.6 Composites Consumption
12.2.2 Bio-additives Consumption
12.2.3 Bio-material Costs
12.2.3.1 Crude Oil: Shortage or Not?
12.2.3.2 Bioplastics Costs
12.2.3.3 Long-term Costs of Bioplastics Compared to Fossil Plastics
Modeling From Historical Prices
Crude Oil Price Expectations
Modeling Plastics Prices Thanks to Crude Oil Prices
12.3 Sustainability: The Problem Is at a System Level
12.3.1 Sustainability Game Changers: Smart Factories, Circularity, and Environmental Compliance
12.3.2 Emergence and Rapid Advance of Prescriptive Techniques
12.3.3 Examples of Strategies Aiming at a Better Sustainability
12.4 Wastes: Collection and Financing Schemes
12.4.1 Collection Systems: Separate or Commingled Waste
12.4.2 “Polluter Pays” Principle
12.4.3 Polymers Incompatible With Existing Recycling Streams
12.5 Recycling Management
12.5.1 Examples of Direct Involvement of Plastics Producers
12.5.2 Example of Associations of Plastics Industry
12.5.3 Example of Difficult-to-Recycle Hi-Tech Carbon Fiber Reinforced Plastic Composite for Aeronautics
12.5.4 Example of Industrial-Scale PS Recycling Channel
12.5.5 Better Reliability and Availability of Recycled Plastic Are Unavoidable Issues
12.6 Waste Sorting
12.7 Suppress the Pitfall of Waste Sorting: Process Plastics Waste Without Sophisticated Sorting
12.7.1 Depolymerization by Enzymes
12.7.2 Depolymerization by Microwaves
12.7.3 Other Methods
12.8 Municipal Solid Waste: A Mine of Plastics (and Other Materials) or an Environmental Calamity?
12.9 Ocean Litter: Calamity or Untapped Feedstock?
12.10 Examples of Sustainable Renewable Sources Used or Proposed by Resin Producers
12.11 Supramolecular, Vitrimers, and Other Self-Healing Polymers
12.12 Conclusion
Reference
Index
Back Cover

Citation preview

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

PLASTICS DESIGN LIBRARY (PDL) PDL HANDBOOK SERIES Series Editor: Sina Ebnesajjad, PhD ([email protected]) President, FluoroConsultants Group, LLC Chadds Ford, PA, USA http://www.FluoroConsultants.com The PDL Handbook Series is aimed at a wide range of engineers and other professionals working in the plastics industry, and related sectors using plastics and adhesives. PDL is a series of data books, reference works and practical guides covering plastics engineering, applications, processing, and manufacturing, and applied aspects of polymer science, elastomers and adhesives. Recent titles in the series Recycling of Flexible Plastic Packaging 1, Niaounakis, Michael (ISBN: 9780128163351) Plasticizers Derived from Post-Consumer PET 1, Langer, Ewa (ISBN: 9780323462006) Polylactic Acid 2, Sin, Lee Tin (ISBN: 9780128144725) Durability and Reliability of Polymers and Other Materials in Photovoltaic Modules 1, Yang, Hsinjin; French, Roger; Bruckman, Laura (ISBN: 9780128115459) Fluoropolymer Additives 2, Ebnesajjad, Sina; Morgan, Richard (ISBN: 9780128137840) The Effect of UV Light and Weather on Plastics and Elastomers 4, McKeen, Larry (ISBN: 9780128164570) PEEK Biomaterials Handbook 2, Kurtz, Steven (ISBN: 9780128125243) Hydraulic Rubber Dam, Thomas et al. (ISBN: 9780128122105) Electrical Conductivity in Polymer-based Composites, Taherian & Kausar (ISBN: 9780128125410) Plastics to Energy, Al-Salem (ISBN: 9780128131404) Recycling of Polyethylene Terephthalate Bottles, Thomas et al. (ISBN: 9780128113615) Dielectric Polymer Materials for High-Density Energy Storage, Dang (ISBN: 9780128132159) Thermoplastics and Thermoplastic Composites, Biron (ISBN: 9780081025017) Recycling of Polyurethane Foams, Thomas et al. (ISBN: 9780323511339) Introduction to Plastics Engineering, Shrivastava (ISBN: 9780323395007) Chemical Resistance of Thermosets, Baur, Ruhrberg & Woishnis (ISBN: 9780128144800) Phthalonitrile Resins and Composites, Derradji, Jun & Wenbin (ISBN: 9780128129661) The Effect of Sterilization Methods on Plastics and Elastomers, 4e, McKeen (ISBN: 9780128145111) Polymeric Foams Structure-Property-Performance, Obi (ISBN: 9781455777556) Technology and Applications of Polymers Derived from Biomass, Ashter (ISBN: 9780323511155) Fluoropolymer Applications in the Chemical Processing Industries, 2e, Ebnesajjad & Khaladkar (ISBN: 9780323447164) Reactive Polymers, 3e, Fink (ISBN: 9780128145098) Service Life Prediction of Polymers and Plastics Exposed to Outdoor Weathering, White, White & Pickett, (ISBN:9780323497763) Polylactide Foams, Nofar & Park (ISBN: 9780128139912) Designing Successful Products with Plastics, Maclean-Blevins (ISBN: 9780323445016) Waste Management of Marine Plastics Debris, Niaounakis, (ISBN: 9780323443548) Film Properties of Plastics and Elastomers, 4e, McKeen, (ISBN: 9780128132920) Anticorrosive Rubber Lining, Chandrasekaran (ISBN: 9780323443715) Shape-Memory Polymer Device Design Safranski & Griffis, (ISBN: 9780323377973) A Guide to the Manufacture, Performance, and Potential of Plastics in Agriculture, Orzolek, (ISBN: 9780081021705) Plastics in Medical Devices for Cardiovascular Applications, Padsalgikar, (ISBN: 9780323358859) Industrial Applications of Renewable Plastics, Biron (ISBN: 9780323480659) Permeability Properties of Plastics and Elastomers, 4e, McKeen, (ISBN: 9780323508599) Expanded PTFE Applications Handbook, Ebnesajjad (ISBN: 9781437778557) Applied Plastics Engineering Handbook, 2e, Kutz (ISBN: 9780323390408) Modification of Polymer Properties, Jasso-Gastinel & Kenny (ISBN: 9780323443531) The Science and Technology of Flexible Packaging, Morris (ISBN: 9780323242738) Stretch Blow Molding, 3e, Brandau (ISBN: 9780323461771) Chemical Resistance of Engineering Thermoplastics, Baur, Ruhrberg & Woishnis (ISBN: 9780323473576) Chemical Resistance of Commodity Thermoplastics, Baur, Ruhrberg & Woishnis (ISBN: 9780323473583) To submit a new book proposal for the series, or place an order, please contact Edward Payne, Acquisitions Editor at edward. [email protected]

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY CONCEPT, SOLUTIONS, AND IMPLEMENTATION

Michel Biron

William Andrew is an imprint of Elsevier The Boulevard, Langford Lane, Kidlington, Oxford, OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2020 Elsevier Ltd. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-12-821539-5 For Information on all William Andrew publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Matthew Deans Acquisitions Editor: Edward Payne Editorial Project Manager: Ana Claudia Garcia Production Project Manager: Poulouse Joseph Cover Designer: Victoria Pearson Typeset by MPS Limited, Chennai, India

Contents

Preface ................................................................................................................................................................. xix Disclaimer......................................................................................................................................................... xxvii Acronyms and Abbreviations ............................................................................................................................ xxix Glossary ............................................................................................................................................................ xxxv 1

An Overview of Sustainability and Plastics: A Multifaceted, Relative, and Scalable Concept............. 1 1.1 Sustainability and Circular Economy ..................................................................................................... 1 1.1.1 Sustainability is a Tripod Based on Environment, Economic, and Social Features ................... 1 1.1.2 Circular Economy ......................................................................................................................... 1 1.2 Sustainability in the Plastics Field.......................................................................................................... 3 1.2.1 Sustainable Design ........................................................................................................................ 3 1.2.2 Renewable Polymers ..................................................................................................................... 4 1.2.3 Sustainable Processes or Sustainable Manufacturing................................................................... 4 1.2.4 Sustainable Use Phase................................................................................................................... 4 1.2.5 Waste Management, Repair, Reuse, Recycling............................................................................ 4 1.2.6 Economic Involvements................................................................................................................ 4 1.3 People’s Perception of Plastics Sustainability........................................................................................ 5 1.3.1 Opinions of Plastics Sector Players .............................................................................................. 5 1.3.2 General Public Opinions: Survey Example and Social Network Opinions................................. 6 1.4 Drivers of Change ................................................................................................................................... 8 1.4.1 Standards and Reporting ............................................................................................................... 8 1.4.2 Policies, Directives and Regulations .......................................................................................... 10 1.4.3 Examples of Marketing Strategy Based on Sustainability......................................................... 11 1.4.4 Cautious Forecast of Major Changes in the Global Environment............................................. 12 1.5 Sustainable Material and Waste Management ..................................................................................... 12 1.5.1 Sustainable Materials Management: A New Approach to Material Selection.......................... 12 1.5.2 Sustainable Waste Management ................................................................................................. 13 1.6 Sustainability is Vital to Mitigate Environment Damages Caused by Booming Plastics Consumption ............................................................................................................................ 17 1.6.1 Population Growth ...................................................................................................................... 17 1.6.2 Standard of Living ...................................................................................................................... 18 1.6.3 General Consequences of Population and Gross Domestic Product Growths........................... 18 1.6.4 Sustainability, the Expected Response to Climate Change........................................................ 18 1.6.5 Natural and Artificial Sinks ........................................................................................................ 23 1.7 Overview of Specific Plastics Features ................................................................................................ 24 1.7.1 Population and Gross Domestic Product Push the Plastics Demand......................................... 24 1.7.2 The Extent of the Problem: The Worldwide Plastics Demand at a Glance .............................. 24

v

vi

CONTENTS

1.7.3 Plastics: A Generic Name for Very Diverse Materials.............................................................. 25 1.8 Environmental Issues From a Plastics Point of View .......................................................................... 26 1.8.1 Potential Pollutants...................................................................................................................... 26 1.8.2 Specific Environmental Issues for Plastics: Visual Pollution, Marine Litter, Single-Use Items ......................................................................................................................... 29 1.8.3 High Lifetimes are a Handicap for Waste.................................................................................. 32 1.9 A Major Issue for Sustainability: Plastics Processing Needs (Polluting) Energy ............................... 32 1.9.1 Energy Versus Gross Domestic Product..................................................................................... 32 1.9.2 Overview of Energy Demand Forecast ...................................................................................... 32 1.9.3 Potential Energy Sources for the Future..................................................................................... 33 1.10 Water Footprint of the Plastics Industry and Water Stress.................................................................. 39 1.10.1 Overview ................................................................................................................................... 39 1.10.2 Water Consumption for Plastics Production ............................................................................ 39 1.10.3 Best Available Techniques in the Production of Polymers ..................................................... 41 1.10.4 Polymers From Natural Sources: Not So Green From a Water Point of View ...................... 42 Reference ........................................................................................................................................................ 43 Further Reading .............................................................................................................................................. 43 2

Plastics Overview.......................................................................................................................................... 45 2.1 Do Not Confuse Thermoplastics, Thermoplastic Elastomers, Thermosets, Composites, and Hybrids .................................................................................................................................................... 45 2.1.1 Thermoplastics .............................................................................................................................. 45 2.1.2 Thermoplastic Elastomers............................................................................................................. 46 2.1.3 Thermosets .................................................................................................................................... 48 2.1.4 Polymer Composites ..................................................................................................................... 49 2.1.5 Hybrid Materials ........................................................................................................................... 49 2.2 Compound Is Much More than Polymer: Build the Best Balance of Engineering, Cost, and Environmental Requirements Thanks to Formulation........................................................... 50 2.2.1 Plastic Alloying ............................................................................................................................. 51 2.2.2 Compounding With Additives ...................................................................................................... 51 2.3 Understand Particular and Surprising Behavior of Plastics ................................................................... 66 2.3.1 Elemental Composition Is Essential ........................................................................................... 66 2.3.2 Molecular Weight and Chain Architecture Are Also of High Importance ............................... 66 2.3.3 Crystalline and Amorphous Thermoplastics, Glass Transition Temperature ............................ 67 2.3.4 Viscoelasticity, Creep, Relaxation.............................................................................................. 71 2.3.5 Isotropy, Anisotropy.................................................................................................................... 72 2.3.6 Potential Heterogeneity of Properties ......................................................................................... 73 2.3.7 Ambient Humidity Can Plasticize Polymers and Change Their Properties .............................. 75 2.3.8 Often Properties Evolve Abruptly: Glass Transition, Yield, Knees, Frequency-Dependent Properties ................................................................................................ 75 2.3.9 Dimensional Stability.................................................................................................................. 75 2.3.10 Aging ........................................................................................................................................... 76 2.3.11 Chemical Resistance by Immersion or Contact ......................................................................... 77 2.4 Sensory Properties of Plastics: An Outstanding Advantage for Marketing .......................................... 78 2.4.1 Optical Properties.......................................................................................................................... 78 2.4.2 Touch............................................................................................................................................. 78 2.4.3 Scratch-Resistance Improvement.................................................................................................. 78

CONTENTS

vii

2.4.4 Acoustic Comfort .......................................................................................................................... 79 2.4.5 Odors ............................................................................................................................................. 79 2.4.6 Taste .............................................................................................................................................. 79 2.4.7 Fogging.......................................................................................................................................... 79 2.5 Outline of the Technical and Economic Possibilities of Processing ..................................................... 79 2.5.1 Molding Solid Thermoplastics...................................................................................................... 80 2.5.2 Extrusion and Connected Processes ............................................................................................. 81 2.5.3 Calendering.................................................................................................................................... 81 2.5.4 Blow Molding ............................................................................................................................... 81 2.5.5 Molding Liquid Thermoplastics ................................................................................................... 81 2.5.6 Secondary Processing.................................................................................................................... 82 2.5.7 Three-Dimensional Printing and Other Additive Manufacturing Methods ................................. 82 2.5.8 Brief Economic Comparison of Some Processing Costs ............................................................. 83 2.5.9 Repair Possibilities: A Significant Thermoplastic Advantage for Large Parts ........................... 84 Further Reading .............................................................................................................................................. 84 3

Metrics of Sustainability in Plastics: Indicators, Standards, Software .................................................. 85 3.1 Environment Management Systems ....................................................................................................... 85 3.2 Life Cycle Accounts: LCI, LCA, LCIA ................................................................................................. 86 3.2.1 Life Cycle Overview..................................................................................................................... 86 3.2.2 Life Cycle Inventory ..................................................................................................................... 87 3.2.3 Life Cycle Assessment.................................................................................................................. 87 3.2.4 Life Cycle Impact Assessment ..................................................................................................... 88 3.2.5 Incorporation of Eco-Design or Sustainable Design in the Life Cycle Through ISO 14006 ..... 88 3.2.6 Beware, Life Cycle Costing is Not an Environmental Feature ................................................... 88 3.3 General Purpose and Specific Standards Linked to the Environment................................................... 88 3.3.1 Overview ..................................................................................................................................... 89 3.3.2 Environmental Management: ISO 14000 Family and a Few Related Standards ...................... 89 3.3.3 Incorporation of Eco-Design or Sustainable Design in the Life Cycle Through ISO 14006 ... 91 3.3.4 Environmental Assessment of Sites and Organizations ............................................................. 91 3.3.5 Environmental Labels and Declarations: The ISO 14020 Series of Standards ......................... 92 3.3.6 Environmental Performance Evaluation: ISO 14030 and ISO 14031 ....................................... 92 3.3.7 Detailed Accounts of LCA, LCI, LCIA: The ISO 14040 Series............................................... 92 3.3.8 Risk Management........................................................................................................................ 93 3.3.9 Quality Management Systems: ISO 9000 Family Addresses Various Aspects of Quality Management ................................................................................................................... 94 3.3.10 Environmental Product Declaration............................................................................................ 94 3.4 Environmental Indicators ........................................................................................................................ 95 3.4.1 Overview ....................................................................................................................................... 95 3.4.2 Energy Consumption..................................................................................................................... 95 3.4.3 CO2 and other Greenhouse Gases, Gas Warming Potential ........................................................ 96 3.4.4 Water Footprint ............................................................................................................................. 96 3.4.5 Toxicity, Unwanted Emissions ..................................................................................................... 97 3.4.6 Other Common Indicators............................................................................................................. 97 3.4.7 Other Diverse Indicators ............................................................................................................... 97 3.4.8 Examples of Indicators.................................................................................................................. 98 3.5 Synthetic Indices Resulting From Environmental Indicator Integration ............................................... 98

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CONTENTS

3.5.1 Overview ....................................................................................................................................... 98 3.5.2 Eco-Profiling System—Volvo/Swedish Industry (https://www.iisd.org/pdf/globlgrn.pdf)....... 100 3.5.3 CML-IA by CML........................................................................................................................ 100 3.6 Databases and Software Help in Environmental Management, but Can Lead to Some Discrepancy ........................................................................................................................................... 100 3.6.1 Examples of Software Solutions................................................................................................. 101 3.6.2 Software May Lead to Some Discrepancies............................................................................... 105 3.7 Clarification Concerning Some Terms ................................................................................................. 111 Further Reading ............................................................................................................................................ 111 4

Easy Measures Relating to Improved Plastics Sustainability................................................................ 113 4.1 Overview of Pace of Change in the Plastics Industry.......................................................................... 113 4.2 Decrease the Material Impact on the Product Sustainability............................................................... 115 4.2.1 Avoid, Minimize, or Ban Hazardous Materials; Obey Health and Safety Concerns, Regulation Compliance............................................................................................................... 115 4.2.2 Optimize Material Consumption Using Simulation and Modeling Tools................................. 116 4.2.3 Avoid Nonrenewable Natural Resource Depletion Using Renewable Materials ...................... 118 4.2.4 Use Recycled Materials and Waste ............................................................................................ 118 4.2.5 Avoid Renewable Material Competing With Food or Causing Deforestation.......................... 120 4.2.6 Design to Facilitate Maintenance, Repair, Reuse, Refurbishment ............................................ 121 4.2.7 Use Reliable Materials and Trustworthy Providers ................................................................... 124 4.3 Minimize Manufacturing Impact on the Environment......................................................................... 124 4.3.1 Invest in Efficient Machines ..................................................................................................... 125 4.3.2 Favor Less Energy-Demanding Compounds............................................................................ 129 4.3.3 Digitalization and Software Solutions ...................................................................................... 130 4.3.4 Promote Efficient Real-Time Quality Control ......................................................................... 142 4.3.5 Preventive and Predictive Maintenance.................................................................................... 143 4.3.6 Minimize Waste ........................................................................................................................ 144 4.3.7 Use Renewable Energy ............................................................................................................. 144 4.3.8 Integrate Manufacturing Steps Using Direct Mixing, Comolding, Overmolding, In-Line Process, Workcells ....................................................................................................... 146 4.3.9 Integration of Subparts and Reduction of Raw Material Diversity ......................................... 153 4.3.10 Potentially Hazardous Releases Possibly Emitted by Plastics................................................. 153 4.3.11 Think Retrofitting of Machinery .............................................................................................. 155 4.4 Reduce Impact of Supply and Distribution Chains.............................................................................. 156 4.5 Reduce Impacts of the Use Phase......................................................................................................... 156 4.6 Balancing the Product Durability and Actual Sustainable Benefits .................................................... 156 4.7 Optimize the End-of-Life...................................................................................................................... 157 4.8 Competence Development, Training, e-Learning ................................................................................ 157 References..................................................................................................................................................... 157 Further Reading ............................................................................................................................................ 157

5

Eco-Design Rules for Plastics Sustainability ........................................................................................... 159 5.1 Examples of Environmental Traps ..................................................................................................... 160 5.1.1 Favorable Example of Automotive Industry: Reduction of Production Impact Matches a Net Impact Reduction Due to the Use Phase ......................................................... 160 5.1.2 Counterexample of House Building: Increase of Production Impact Leads to a Final Impact Mitigation due to the Use Phase ......................................................................... 161

CONTENTS

5.2 5.3

5.4

5.5

5.6

5.7

5.8

5.9

ix

5.1.3 Selection of Energy Production Method can Replace a Pollution Type by Another.............. 162 Specific Plastics Design Issues ........................................................................................................... 163 Overview of Material Sustainability Impact ...................................................................................... 163 5.3.1 General Pathway toward Mitigation of Material Impact ......................................................... 164 5.3.2 Examples of Impact of Material Selection on Other Parameters ............................................ 164 5.3.3 Have an Overall View of Sustainability including Late Phases .............................................. 165 Design to Withstand Mechanical Loading ......................................................................................... 165 5.4.1 Overview ................................................................................................................................. 166 5.4.2 Temperature Effect.................................................................................................................. 166 5.4.3 Loading Type Effect ............................................................................................................... 166 5.4.4 Strain Rate or Time Effect...................................................................................................... 166 5.4.5 Impact Behavior ...................................................................................................................... 167 5.4.6 Hardness .................................................................................................................................. 167 5.4.7 Dynamic Fatigue ..................................................................................................................... 167 5.4.8 Dimensional Effects ................................................................................................................ 168 5.4.9 Combination with other Parameters ....................................................................................... 168 5.4.10 Lifetime ................................................................................................................................... 168 5.4.11 Environmental Cost of Reinforcements.................................................................................. 168 Plastics Behavior Above Ambient Temperature ................................................................................ 171 5.5.1 Average Temperature................................................................................................................ 172 5.5.2 Continuous Use Temperature.................................................................................................... 172 5.5.3 Underwriter Laboratories Temperature Index .......................................................................... 172 5.5.4 Heat Deflection Temperature.................................................................................................... 173 5.5.5 Vicat Softening Temperature .................................................................................................... 173 5.5.6 Accelerated Aging..................................................................................................................... 173 5.5.7 Environmental Cost of Stabilizers and Antioxidants ............................................................... 173 Low Temperature Behavior ................................................................................................................ 174 5.6.1 Low-temperature Tests.............................................................................................................. 174 5.6.2 Brittle Point ............................................................................................................................... 174 5.6.3 Rigidity in Torsion: “Clash-Berg” and “Gehman” tests .......................................................... 175 5.6.4 Crystallization Test ................................................................................................................... 175 5.6.5 Environmental Footprint of Plasticizers ................................................................................... 175 Design for Dimensional Stability ....................................................................................................... 176 5.7.1 Thermal Expansion or Retraction............................................................................................. 176 5.7.2 Shrinkage................................................................................................................................... 177 5.7.3 Warpage..................................................................................................................................... 177 5.7.4 Water or Chemicals Uptake...................................................................................................... 177 5.7.5 Aging, Desorption, Bleeding, Releasing of Organic Components .......................................... 177 Electrical Properties ............................................................................................................................ 178 5.8.1 Volume Resistivity: ASTM D257 and IEC 93......................................................................... 178 5.8.2 Surface Resistivity: ASTM D257 and IEC 93 ......................................................................... 178 5.8.3 Dielectric Strength .................................................................................................................... 179 5.8.4 Arc Resistance........................................................................................................................... 179 5.8.5 High Voltage Arc Tracking Rate.............................................................................................. 179 5.8.6 Frequency, Temperature, Moisture, Physical, and Dynamic Aging Effects ........................... 179 5.8.7 Conductive Polymers: Sustainability Considerations............................................................... 179 Fire Behavior: Some Ins and Outs...................................................................................................... 180

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CONTENTS

5.9.1 UL 94 Fire Ratings ................................................................................................................. 181 5.9.2 Oxygen Index .......................................................................................................................... 182 5.9.3 Smoke Opacity, Toxicity, and Corrosivity............................................................................. 182 5.9.4 Cone Calorimeter .................................................................................................................... 182 5.9.5 Ignition Temperature............................................................................................................... 182 5.9.6 Rate of Burning....................................................................................................................... 182 5.9.7 Glow Wire Test....................................................................................................................... 183 5.9.8 Fire Resistant Polymers: Sustainability Considerations......................................................... 183 5.9.9 General Collateral Effects from a Sustainability Standpoint ................................................. 186 5.9.10 A Glimpse on General Behavior of Biopolymers .................................................................. 187 5.10 Sensory Issues: Optical Properties, Aesthetics, Odor, Taste, Touch ................................................. 187 5.10.1 Complementarity of Instrumental Measurements and Sensory Panel Evaluations ............... 188 5.10.2 Visual Aspect .......................................................................................................................... 189 5.10.3 Physical Aspect ....................................................................................................................... 189 5.10.4 Touch....................................................................................................................................... 189 5.10.5 Odor and Taste Properties and Transfer................................................................................. 191 5.10.6 Noise, Vibration, Harshness.................................................................................................... 191 5.10.7 General Collateral Effects of Colorants from a Sustainability Standpoint............................ 191 5.11 Design for Aging, Weathering, and Light and UV Behaviors .......................................................... 195 5.11.1 Overview of Light and Ultra Violet Resistance..................................................................... 196 5.11.2 Elements of Weathering Appraisal......................................................................................... 197 5.11.3 Examples of Published Assessments Relating to Light and UV Behavior of Compounds .. 198 5.12 Lifetime and End-of-life Criteria........................................................................................................ 203 5.12.1 Overview ................................................................................................................................. 203 5.12.2 Accelerated Aging and Modeling ........................................................................................... 205 5.12.3 Smart Design and Mitigation of Aggressiveness of Surroundings are Benefiting from a Sustainability Standpoint ............................................................................................ 205 5.13 Regulation, Health, and Safety Requirements.................................................................................... 206 Further Reading ............................................................................................................................................ 207 6

Environmental and Engineering Data to Support Eco-Design for Plastics......................................... 209 6.1 Overview ............................................................................................................................................... 209 6.2 Be Cautious of Some Traps Concerning Standards ............................................................................. 209 6.2.1 General Boundaries of Standards ............................................................................................... 209 6.2.2 Real Cases Are Not Ideal Standardized Cases: Take Into Account the Statistical Distribution of Properties............................................................................................................ 210 6.2.3 Be Cautious of the Real Sense of Common Terms ................................................................... 211 6.3 Environmental Indicators ...................................................................................................................... 212 6.3.1 Use of Renewable Materials Instead of Fossil Resources ......................................................... 214 6.3.2 Energy Requirements .................................................................................................................. 214 6.3.3 Net Carbon Footprint, CO2 and Other Greenhouse Gases, Global Warming Potential............ 216 6.3.4 Water Footprint ........................................................................................................................... 216 6.3.5 Examples of Other Environmental Indicators ............................................................................ 216 6.3.6 Variability and Weakness of Environmental Indicators ............................................................ 217 6.3.7 Do Not Confuse Indicator per Weight and Indicator per Functional Unit................................ 220 6.4 Usual Indicators for Plastics Design..................................................................................................... 221 6.4.1 Thermal Behavior........................................................................................................................ 221

CONTENTS

xi

6.4.2 Density......................................................................................................................................... 249 6.4.3 Mechanical Properties ................................................................................................................. 260 6.4.4 Examples of Water Uptake ......................................................................................................... 304 6.4.5 Examples of Mold Shrinkage ..................................................................................................... 306 Further Reading ............................................................................................................................................ 307 7

Advanced Environmental and Engineering Properties to Support Eco-Design for Plastics ............. 309 7.1 Advanced Properties That can Help Eco-Design ................................................................................. 309 7.1.1 Fuel Energy and Feedstock Energy ............................................................................................ 309 7.1.2 Gas Warming Potential ............................................................................................................... 309 7.1.3 Rapid Overview of Examples of Advanced Indicators.............................................................. 310 7.1.4 Natural-Sourced Versus Fossil Polymers: A Mixed Bag of Benefits and Drawbacks ............. 312 7.2 Advanced Engineering Properties......................................................................................................... 314 7.2.1 Thermal Dependency of Mechanical Properties ........................................................................ 314 7.2.2 Time Dependent Mechanical Properties..................................................................................... 321 7.3 Poisson’s Ratios .................................................................................................................................... 349 7.4 Electrical Properties .............................................................................................................................. 352 7.4.1 Resistivity Examples ................................................................................................................... 354 7.4.2 Dielectric Strength Examples ..................................................................................................... 354 7.4.3 Examples of Dielectric Loss Factors .......................................................................................... 354 7.5 Flammability: Limiting Oxygen Index examples ................................................................................ 355 7.6 Optical Properties: Examples of Transparent or Translucent Plastics................................................. 365 7.7 Gas Permeability ................................................................................................................................... 365 7.8 Tribological Properties.......................................................................................................................... 367 7.8.1 Coefficient of Friction................................................................................................................. 368 7.8.2 Limiting Pressure Velocity ......................................................................................................... 368 References..................................................................................................................................................... 369 Further Reading ............................................................................................................................................ 369

8

Economics Relating to Fossil and Renewable Plastics ........................................................................... 371 8.1 Raw Plastics Material Cost: Beware of Unusual “Raw” Materials and Waste Levels....................... 371 8.1.1 Usual Physical Types of Plastics Raw Materials ....................................................................... 371 8.1.2 Cost of Sophisticated Raw Materials.......................................................................................... 372 8.1.3 Examples of Additive Costs ....................................................................................................... 372 8.1.4 Examples of Reinforcement Costs.............................................................................................. 372 8.1.5 Beware of the Actual Consumption of Plastic Compared to the Weight of the Part ............... 373 8.2 Processing Costs.................................................................................................................................... 374 8.2.1 Capability Proposals for Some Processing Methods.................................................................. 376 8.2.2 Use of Cost Estimator Software ................................................................................................. 378 8.3 Examples of Costs................................................................................................................................. 380 8.3.1 Expected Costs by Market .......................................................................................................... 380 8.3.2 Expected Cost of Composites ..................................................................................................... 380 8.4 Economics of Renewable Materials ..................................................................................................... 381 8.4.1 Plastics Recycling ....................................................................................................................... 383 8.4.2 Biosourced Plastics Consumption............................................................................................... 383 8.4.3 Market Shares by Bioplastic Family .......................................................................................... 385 8.4.4 Production Capacities by Bioplastic Family .............................................................................. 385

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CONTENTS

8.4.5 Bioplastic Capacities by Region................................................................................................. 387 8.4.6 Bioplastic Capacities by Market................................................................................................. 387 8.4.7 Bioadditives Consumption .......................................................................................................... 387 8.4.8 Wood Plastic Composite and Natural Fiber Composite Markets .............................................. 389 8.4.9 Biomaterial Costs ........................................................................................................................ 390 8.5 Survey of Main Bioplastics Markets .................................................................................................... 391 8.5.1 Packaging .................................................................................................................................... 392 8.5.2 Consumer Goods ......................................................................................................................... 392 8.5.3 Automotive and Transportation .................................................................................................. 392 8.5.4 Building and Construction .......................................................................................................... 399 8.5.5 Agriculture................................................................................................................................... 404 8.5.6 Other Markets.............................................................................................................................. 404 Further Reading ............................................................................................................................................ 409 Papers and Books ......................................................................................................................................... 409 9

Recycling Plastics: Advantages and Limitations of Use......................................................................... 411 9.1 Recycling Outline.................................................................................................................................. 411 9.1.1 Environmental Benefits of Recycling......................................................................................... 414 9.1.2 Economics of Recycling ............................................................................................................. 416 9.1.3 Reliability of Recycling .............................................................................................................. 420 9.1.4 Example of Recycling Loop Effects on Performances .............................................................. 423 9.1.5 Recycling: Legislation, Standards, and Related Publications.................................................... 425 9.2 Recycling Methods................................................................................................................................ 435 9.2.1 Reprocessing of Processing Scraps and Mechanical Recycling ................................................ 437 9.2.2 Recycled Material Upgrading by Additives ............................................................................... 439 9.2.3 Chemical Recycling .................................................................................................................... 447 9.2.4 Solvent Recycling ....................................................................................................................... 449 9.2.5 Thermal Recycling ...................................................................................................................... 450 9.2.6 Energy Recovery ......................................................................................................................... 451 9.2.7 Anaerobic Biodegradation of Biodegradable Plastics With Gas Recovery............................... 452 9.2.8 Enzymatic Depolymerization of Polylactic Acid ....................................................................... 452 9.2.9 The REnescience Process Recovering Plastics and Metals From Municipal Solid Waste Without Sorting................................................................................................................ 452 9.3 Sectorial Routes for Recycling ............................................................................................................. 452 9.3.1 Used Polyethylene Terephthalate Bottles: Realities of Everyday Life ..................................... 453 9.3.2 High-Density Polyethylene Bottles............................................................................................. 454 9.3.3 Electricity and Electronics: Closed- and Open-Loop Recycling ............................................... 454 9.3.4 Auto: Closed- and Open-Loop Recycling .................................................................................. 455 9.3.5 Recycling and Reprocessing of Building Products .................................................................... 456 9.3.6 Recycling of Thermosets ............................................................................................................ 457 9.3.7 Recycling of Composites ............................................................................................................ 457 9.3.8 Recycling of Glass and Carbon Fibers, and High-Performance Polymers................................ 458 9.4 Recycling Advantages: CO2 Emission, Greenhouse Effect, and Carbon Footprint............................ 458 9.4.1 Some Real Facts and Figures...................................................................................................... 460 9.4.2 Statistical Analyses of Some Real Examples ............................................................................. 460 9.5 Recyclate Property Examples ............................................................................................................... 461 9.5.1 Polyamides Examples ................................................................................................................. 461

CONTENTS

xiii

9.5.2 Polystyrene and Acrylonitrile Butadiene Styrene Examples ..................................................... 461 9.5.3 Polypropylene Examples............................................................................................................. 461 9.5.4 Examples of Polycarbonate, PC/ABS, and PC/PBT Alloys ...................................................... 461 9.5.5 Examples of Polyetherimide ....................................................................................................... 462 9.6 Recycled Materials Often Also Bring Cost Saving in Addition to Pollution Savings........................ 466 9.7 Some Limitations to Recycled Material Use........................................................................................ 466 9.7.1 Underwriters Laboratories’s Recommendations on the Use of Regrind ................................... 466 9.7.2 Producer Recommendations........................................................................................................ 466 References..................................................................................................................................................... 466 Further Reading ............................................................................................................................................ 467 10 Transition of Plastics to Renewable Feedstock and Raw Materials: Bioplastics and Additives Derived From Natural Resources ........................................................................................................... 469 10.1 Brief Inventory of Renewable Polymers ........................................................................................ 469 10.2 Renewable Additives....................................................................................................................... 471 10.2.1 Renewable Plasticizers...................................................................................................... 472 10.2.2 Natural Reinforcements .................................................................................................... 474 10.2.3 Processing Aids ................................................................................................................. 482 10.2.4 Surface Friction Modifiers: Lubricant, Slipping, and Antiblocking Agents ................... 482 10.2.5 Release Agents .................................................................................................................. 482 10.2.6 Antistatic Additives........................................................................................................... 482 10.2.7 Optical Property Modifiers: Antifogging, Color, Gloss Modifiers.................................. 483 10.2.8 Renewable Impact Modifiers and Tougheners................................................................. 486 10.2.9 Protective Agents, Stabilizers, Thermal, and Antiaging Additives, Light Stabilizers .... 489 10.2.10 Miscellaneous Additives: Fire Retardants, Tackifiers, Nucleating Agent, Waxes, Hardeners, Foaming Agents, etc.......................................................................... 490 10.2.11 Renewable Masterbatches Based on Renewable Matrix or Renewable Additive........... 491 10.3 Ready-to-Use Thermoplastic Blends Derived From Starch, a Natural Polymer........................... 491 10.3.1 Overview ............................................................................................................................. 491 10.3.2 Processing............................................................................................................................ 491 10.3.3 Environmental Features ...................................................................................................... 494 10.3.4 Application Sectors ............................................................................................................. 494 10.3.5 Examples of Producers and Trademarks ............................................................................ 495 10.3.6 Property Tables ................................................................................................................... 495 10.4 Polylactic Acid Polymerized From a Natural Monomer ............................................................... 495 10.4.1 Overview ............................................................................................................................. 495 10.4.2 Processing............................................................................................................................ 497 10.4.3 Environmental Features ...................................................................................................... 497 10.4.4 Application Sectors ............................................................................................................. 498 10.4.5 Examples of Producers and Trademarks ............................................................................ 498 10.4.6 Property Tables ................................................................................................................... 499 10.5 Natural Linear Polyesters Produced by Bacterial Fermentation—Polyhydroxyalkanoates .......... 499 10.5.1 Overview ............................................................................................................................. 499 10.5.2 Processing............................................................................................................................ 502 10.5.3 Environmental Features ...................................................................................................... 502 10.5.4 Application Sectors ............................................................................................................. 502 10.5.5 Examples of Producers and Trademarks ............................................................................ 503 10.5.6 Property Tables ................................................................................................................... 503

xiv

CONTENTS

10.6 Cellulose Derivatives Based on Natural Cellulose ........................................................................ 503 10.6.1 Overview ............................................................................................................................. 506 10.6.2 Processing............................................................................................................................ 506 10.6.3 Environmental Features ...................................................................................................... 506 10.6.4 Application Sectors ............................................................................................................. 506 10.6.5 Examples of Producers and Trademarks ............................................................................ 507 10.6.6 Property Tables ................................................................................................................... 507 10.7 Biopolyethylene and Biosourced Ethylene Vinyl Acetate............................................................. 507 10.7.1 Overview ............................................................................................................................. 507 10.7.2 Processing............................................................................................................................ 510 10.7.3 Polyethylene Environmental Features ................................................................................ 510 10.7.4 Polyethylene Application Sectors ....................................................................................... 510 10.7.5 Examples of Producers and Trademarks ............................................................................ 512 10.7.6 Polyethylene Property Tables ............................................................................................. 513 10.7.7 Biobased Ethylene Vinyl Acetate Copolymer.................................................................... 513 10.8 Renewable PET, PBT, PEF, PTT Alternatives to Fossil Thermoplastic Polyesters PET and PBT .................................................................................................................................. 513 10.8.1 Replacement of the Fossil Alcohol by Natural Alcohol .................................................... 513 10.8.2 Second Step: Paraxylene for 100% Biopolyester............................................................... 515 10.8.3 The Third Way: Polyethylene-Furanoate ........................................................................... 516 10.8.4 Recycled Polyethylene Terephthalate................................................................................. 516 10.8.5 PolyTrimethyleneTerephthalate .......................................................................................... 517 10.8.6 Partially Renewable Thermoplastic Elastomer Ester ......................................................... 517 10.8.7 Polybutylene Succinate ....................................................................................................... 517 10.8.8 Property Examples of PET, PBT, PTT, TPEE, PBS.......................................................... 518 10.9 Renewable Polyamides ................................................................................................................... 518 10.9.1 Polyamides With Long Hydrocarbon Segments: PA11, 1010, 1012................................. 524 10.9.2 Polyamides Alternating Long and Short Hydrocarbon Segments: PA610, 510, 512, 514, 410 ................................................................................................. 526 10.9.3 Polyamides With Short Hydrocarbon Segments: PA56..................................................... 526 10.9.4 Amorphous Transparent Renewable Polyamides ............................................................... 526 10.9.5 Polyphthalamide .................................................................................................................. 528 10.9.6 Renewable Polyether Block Amides .................................................................................. 528 10.10 Renewable Polyurethanes ............................................................................................................... 530 10.10.1 Natural and Renewable Oil Polyols.................................................................................. 530 10.10.2 CO2-Containing Polyols.................................................................................................... 531 10.10.3 Bioisocyanate Crosslinker for Polyurethanes ................................................................... 532 10.10.4 Applications....................................................................................................................... 532 10.10.5 Examples of Environmental Advantages.......................................................................... 533 10.10.6 Examples of Polyurethane Players ................................................................................... 534 10.11 Renewable Unsaturated Polyesters ................................................................................................. 535 10.11.1 Overview ........................................................................................................................... 535 10.11.2 Applications....................................................................................................................... 537 10.11.3 General Properties ............................................................................................................. 537 10.12 Renewable Epoxy Resins................................................................................................................ 538 10.12.1 Natural-Sourced Epoxidized Oils and Epichlorhydrin..................................................... 538 10.12.2 General Properties of Epoxy Resins ................................................................................. 541 10.13 Biosourced Polycarbonates ............................................................................................................. 542

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xv

10.14 Derivatives of Lignin: For Instance the Liquid Wood (Arboform by Tecnaro) ........................... 542 10.15 Example of Self-Reinforced Composite Produced From Cereals ................................................. 543 10.16 Renewable Acrylics—Poly(Methyl Methacrylate)......................................................................... 543 10.16.1 General Advantages .......................................................................................................... 544 10.16.2 General Drawbacks ........................................................................................................... 544 10.17 Renewable Phenol Formaldehyde Resins....................................................................................... 544 10.17.1 General Advantages .......................................................................................................... 546 10.17.2 General Drawbacks ........................................................................................................... 546 10.18 Renewable Polypropylene............................................................................................................... 547 10.19 Renewable Polyvinyl Chloride ....................................................................................................... 548 10.19.1 General Advantages .......................................................................................................... 548 10.19.2 General Drawbacks ........................................................................................................... 548 10.20 Thermosetting Cyanate Ester Resins .............................................................................................. 548 10.21 Thermosetting Furanic Resins ........................................................................................................ 549 10.22 An Endless List of Alloys............................................................................................................... 549 10.22.1 Alloys of Renewable Polymers......................................................................................... 549 10.22.2 Hybrid Alloys of Renewable and Fossil Polymers .......................................................... 549 10.22.3 Others ................................................................................................................................ 550 References................................................................................................................................................... 554 Further Reading .......................................................................................................................................... 555 11 Plastics Sustainability: Drivers and Obstacles ...................................................................................... 557 11.1 The Vast Range of Waste Strategies: From Waste Minimization to Landfilling ........................... 557 11.2 Waste Minimization .......................................................................................................................... 558 11.3 Repair and Reuse .............................................................................................................................. 558 11.3.1 Overview ............................................................................................................................... 559 11.3.2 High-Tech Repairs: Example of Aircraft Structural Repair ................................................ 559 11.3.3 Benefits of Reused Drums .................................................................................................... 560 11.3.4 Refillable Bottles: May Be a Counterexample..................................................................... 560 11.3.5 Refurbishing and Upgrading Machinery: Benefits of Industry 4.0 ..................................... 560 11.4 Recycling and Actual Reuse ............................................................................................................. 562 11.4.1 Environmental Benefits of Recycling................................................................................. 562 11.4.2 Closed-Loop Recycling Overview...................................................................................... 563 11.4.3 Recycling of High-Performance Materials: Example of Carbon Fiber ............................. 564 11.4.4 Global Warming Potential of Specific Recycled Polymers ............................................... 564 11.4.5 Global Warming Potential of End Products Incorporating Recycled Polymers ............... 565 11.4.6 Examples of Fossil Energy Gains Due to the Use of Recycled Resins ............................ 565 11.4.7 Fossil Energy Demand of End Products Based on Reused Materials and/or Recycled Polymers.............................................................................................................. 566 11.4.8 Example of Inconsistency Between Indicators Relating to a Recycled Polymer Family.................................................................................................................................. 567 11.4.9 Examples of Cost Savings Due to Recycling..................................................................... 568 11.4.10 Example of Environmental Benefits of Recycling a Commodity Plastic: rPVC .............. 568 11.4.11 Recycling, Reuse, or Use Virgin Polymer: The Right Answer Depends on the Actual Context..................................................................................................................... 568 11.5 Policy, Legislation, Fees, Taxes, Bans, Deposit and Bill Strategies, and the Green Wave Are Real Game-changers .................................................................................................................. 569

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11.5.1 Incentive Legislation Example: Extended Producer Responsibility.................................... 569 11.5.2 Example of Regulation Restraining the Use of Plastics: Carrier Bags ............................... 569 11.5.3 Example of Regulation Boosting Recycling: End-of-Life Vehicles.................................... 570 11.5.4 Example of Recycled Plastics Limitations ........................................................................... 571 11.5.5 Example of “Deposit and Bill” Approach: Beverage Bottles.............................................. 571 11.6 Renewable Materials: Alternative to Oil Becoming Scarcer and Use of Natural-Sourced Materials ................................................................................................................ 571 11.6.1 Success Story Examples........................................................................................................ 572 11.6.2 A Questionable Case............................................................................................................. 573 11.6.3 A Textbook Case: Replacement of ABS for Lego Bricks................................................... 573 11.7 Ecological Features Boosting the Growth of Plastics ...................................................................... 574 11.7.1 Functionality Integration Due to Design Freedom............................................................... 574 11.7.2 Lightweighting: Energy and Resource Savings, Pollution Mitigation ................................ 575 11.7.3 Take Advantage of the Unique Insulation Efficiency of Plastics Foams: “Zero Energy” Housing Examples and Others..................................................................... 585 11.8 Examples of Bottlenecks for the Growth of Plastics ....................................................................... 587 11.8.1 Fire Behavior......................................................................................................................... 587 11.8.2 Nanomaterials........................................................................................................................ 588 11.8.3 3D Printing and Other Additive Manufacturing Techniques............................................... 589 11.9 Where We Stand Today: Global, Regional, Sectorial Inequalities ................................................. 589 11.9.1 Global Landscape.................................................................................................................. 589 11.9.2 Plastics Waste Treatment: Promising Results of Advanced Countries ............................... 590 11.9.3 Brief Jumble of Facts and Figures........................................................................................ 592 References................................................................................................................................................... 592 Further Reading .......................................................................................................................................... 593 12 Plastics Sustainability: Prospective ........................................................................................................ 595 12.1 Demand and Growth Potential of Plastics...................................................................................... 595 12.1.1 Overview of the Future Global Plastics Industry ............................................................... 595 12.1.2 Effects of Demography and Standard of Living ................................................................ 596 12.1.3 Rethinking Time Management ........................................................................................... 597 12.1.4 Authoritarian Restrictions, Bans, and Incentive Actions ................................................... 597 12.1.5 Emerging Technologies: Example of Vehicles .................................................................. 600 12.1.6 The Dream of Almost Perfect Polymers ............................................................................ 601 12.1.7 Alternative Fuels ................................................................................................................. 601 12.1.8 Plastics Brand Image........................................................................................................... 601 12.1.9 Specificities Linked to Sustainable Plastics ....................................................................... 602 12.2 Economics of Renewable Plastics and Bio-additives: Quantified Expectations ........................... 602 12.2.1 Renewable Plastics Consumption and Capacity Forecasts ................................................ 603 12.2.2 Bio-additives Consumption................................................................................................. 606 12.2.3 Bio-material Costs............................................................................................................... 606 12.3 Sustainability: The Problem Is at a System Level ......................................................................... 609 12.3.1 Sustainability Game Changers: Smart Factories, Circularity, and Environmental Compliance................................................................................................. 609 12.3.2 Emergence and Rapid Advance of Prescriptive Techniques ............................................. 611 12.3.3 Examples of Strategies Aiming at a Better Sustainability................................................. 611 12.4 Wastes: Collection and Financing Schemes................................................................................... 612 12.4.1 Collection Systems: Separate or Commingled Waste........................................................ 612

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12.4.2 “Polluter Pays” Principle .................................................................................................... 613 12.4.3 Polymers Incompatible With Existing Recycling Streams ................................................ 613 12.5 Recycling Management................................................................................................................... 613 12.5.1 Examples of Direct Involvement of Plastics Producers..................................................... 614 12.5.2 Example of Associations of Plastics Industry .................................................................... 614 12.5.3 Example of Difficult-to-Recycle Hi-Tech Carbon Fiber Reinforced Plastic Composite for Aeronautics ................................................................................................. 615 12.5.4 Example of Industrial-Scale PS Recycling Channel .......................................................... 615 12.5.5 Better Reliability and Availability of Recycled Plastic Are Unavoidable Issues ............. 615 12.6 Waste Sorting .................................................................................................................................. 616 12.7 Suppress the Pitfall of Waste Sorting: Process Plastics Waste Without Sophisticated Sorting ... 619 12.7.1 Depolymerization by Enzymes ........................................................................................... 619 12.7.2 Depolymerization by Microwaves ...................................................................................... 620 12.7.3 Other Methods..................................................................................................................... 620 12.8 Municipal Solid Waste: A Mine of Plastics (and Other Materials) or an Environmental Calamity?......................................................................................................................................... 620 12.9 Ocean Litter: Calamity or Untapped Feedstock? ........................................................................... 621 12.10 Examples of Sustainable Renewable Sources Used or Proposed by Resin Producers ................. 624 12.11 Supramolecular, Vitrimers, and Other Self-Healing Polymers...................................................... 625 12.12 Conclusion....................................................................................................................................... 626 Reference .................................................................................................................................................... 627 Index ................................................................................................................................................................... 629

Preface Plastics are often suspected of being a poor material from a sustainability point of view. Sustainability being a relative feature, that is false and true. It is false because the plastics industry already applies a significant batch of guidelines of sustainability. It is true because the plastics industry does not take advantage of many other ways that are emerging thanks to the general transition of our world toward better sustainability. We are at the right time to accelerate the expansion of sustainability trends: governments increase sustainability requirements, and average person is increasingly aware of the scale and urgency of the problem, even accepting the idea that sustainability deserves an extra cost. This book is not theoretical, but is intended to provide general ways workable for plastics, rules of thumb, or sophisticated methods as well as examples of pitfalls relating to sustainability from a plastics point of view. Of course those considerations do not cover a multitude of real cases, the legal requirements and the context continuously evolve, allowing the reader to complete this information thanks to further intensive investigations using other suitable tools. The scheme of this book is as follows: 1. An overview of sustainability and plastics: A multifaceted, relative, and scalable concept 2. Plastics overview: Outline of the current situation of plastics 3. Metrics of sustainability in plastics: Indicators, standards, and software 4. Easy measures relating to improved plastics sustainability 5. Eco-design rules for plastics sustainability 6. Environmental and engineering data to support eco-design for plastics

7. Advanced environmental and engineering properties to support eco-design for plastics 8. Economics relating to fossil and renewable plastics 9. Recycling of plastics, advantages and limitation of use 10. Transition of plastics to renewable feedstock and raw materials 11. Plastics sustainability: Drivers and obstacles 12. Plastics sustainability: Prospective Subjectively, plastics are often disparaged although their consumption steadily grows for many reasons including, in a jumble, the infinite design opportunities, cost-effective and value-added solutions, the possibility to make possible unsolvable problems. In a few words, plastics solve a lot of problems at the lowest cost, leading to the highest benefit for the designer, manufacturer, device integrator, as well as the end customer. On the one hand, users love affordable plastic pipes, safe electric cables, dielectric films, household appliances, smartphones, computers, home electronics, cars, packaging, aircraft, and other piles of plastics parts. On the other hand, the ordinary mortal perceives plastics as pollutants for land and sea, sources of toxic and polluting leakages over hundreds of years. Objectively, the current situation is not so differentiated but can be upgraded by taking advantage of the current and innovative strategies and conversely by banning bad habits contrary to sustainability. Sustainable solutions include ways of good sense using known paths such as smart design or the use of recycled matter, and innovative routes such as naturalsourced polymers that still need a lot of research, change of habits, and money for the transition even if sustainability can be profitable in the medium or long term. To give a rough idea, patent inflation relating to plastics sustainability during the past 20 years leads to an average coefficient in the order of 5.5 times (from 4 up to 9 according to the topic).

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Today more than 95% of plastics are from fossil origin making that renewable polymers and ingredients could be a major way toward a better sustainability. Natural-sourced plastics and recycled polymers avoid the use of crude oil as feedstock and provide agricultural employment. Solutions must be considered very early, the more so as the issue is complex and requires intensive upstream research along with the implementation of important logistical measures. Time frames for industrial development are in the order of decades, from 10 up to more than 60 years according to the magnitude of the problem. Today, researchers are working for 2050 and beyond. This book aims to provide practical information helping designers to situate the sustainability problematic from a plastics point of view. The designer’s main problems are examined bringing together some basic reminders dealing with plastics, basics of sustainability, eco-design, economics that can help designers, generally familiar to metals, to be more sensitive to plastics features. It is one of the tools aiming to quickly clarify the uses, possibilities, and problems of renewable plastics and composites allowing to make first raw selections and rejections. This work considers as renewable materials recycled plastics, bioplastics derived from natural polymers, bioplastics derived from biobricks (drop-in solutions), biocompounds containing renewable reinforcements and/or bioadditives. Often, the level of renewable material is limited for technical or economic reasons, or legal requirements. So, the renewable carbon content can be as low as a few tens of percent. However, the decision to use a new renewable material has technical, economic, and environmental consequences needing extensive research and trials. The selected examples and information bring to mind some aspects of the problem without claiming to be exhaustive and cannot be directly used by the reader, who must work deeper on the subject to choose the suitable grade in the selected subfamilies and use the actual data measured on the selected grade processed with the actual processing method for final computing, designing, economic study, and so forth. The advice of plastics specialists is irreplaceable, and obviously, prototypes and tests under operating conditions are essential. Obviously, this book cannot cover all cases but it gives some starting points for innovative thinking on the part of the reader to select information

PREFACE

relating to his/her own case and to search elsewhere for complementary and corroborating information.

Chapter 1 An Overview of Sustainability and Plastics: A Multifaceted, Relative, and Scalable Concept Sustainability is a relatively recent concern integrating environmental, economic, and societal worries. First and foremost, sustainable plastics must obey the general sustainability criteria and then specific criteria linked to their specific features. The goal of this chapter is to help define sustainability, examine main drivers of change and propose some hypotheses of changes in the overall environment. The booming consumption due to population growth and improvement of standard of living increase problems of sustainability and lead to new approaches of material selection taking into account more sustainable materials and better management of waste generation, reuse, and recycling. Environment damages and risks induced by climate change, greenhouse gases (GHG), sea-level rise, and biological concerns are examined as well as benefits coming from natural and artificial GHG sinks. An overview of specific plastics features, demand, diversity, potential pollutants, specific environmental issues, visual pollution and marine litter, and high lifetimes of waste alert the reader and help to reach a more accurate opinion on the extent of the problem. Lastly this chapter examines two aspects of sustainability that are of prime importance for the plastics industry: the preferential use of renewable energy (demand forecast, potential energy sources, survival of traditional sources) and the water footprint.

Chapter 2 Plastics Overview: Outline of the Current Situation of Plastics After some basic reminders concerning thermoplastics, thermosets, composites, thermoplastic elastomers, hybrids, formulation, alloying, compounding,

PREFACE

and related processing methods, the designer’s main problems are examined, taking into account the technical and environmental requirements. Some particular and surprising behaviors of plastics are examined such as, for example molecular weight, chain architecture, crystallinity, glass transition temperature, viscoelasticity, creep, and relaxation that are time and temperature dependent. Anisotropy of the matter can induce heterogeneity of properties, water uptake plasticizes certain polymers, among others, making local and bulk properties that are different and lead to statistical distribution of properties in a same part. Often properties can evolve abruptly when temperature or frequency gradually evolve: glass transition, yield, knees, induction time, and some frequency-dependent properties. In addition to temperature, dimensional stability depends on shrinkage, warpage, releasing of organic additives, and water uptake. Aging and chemical resistance are affected by simultaneous exposure to loading. The sensory properties such as optical features, fogging, touch, scratch resistance, acoustic comfort, odors, and taste complete the property panel. 27 Tables and 15 figures illustrate this chapter.

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Examined specific tools for sustainability management include indicators, standards, and software concerning environment management systems, life cycle inventory, life cycle assessment, life cycle impact assessment, incorporation of eco-design, or sustainable design in the life cycle. This chapter also broaches general purpose and specific standards linked to the environment, environmental assessment of sites and organizations, environmental labels and declarations, environmental performance, risk management, quality management systems, and environmental product declaration. Environmental indicators are examined more or less in depth such as energy consumption, CO2 and other GHG, gas warming potential (GWP), water footprint, toxicity, unwanted emissions, ozone depletion, photochemical oxidation, acidification, eutrophication, and other diverse indicators. Synthetic indexes (Eco-Profiling System (EPS)— Volvo, CML-IA) resulting in environmental indicator integration are also discussed. Clarification concerning some terms, databases, and software helping in environmental management complete this brief landscape of sustainability tools. Social and societal aspects, as well as regulatory requirements are not taken into account.

Chapter 3 Metrics of Sustainability in Plastics: Indicators, Standards, Software

Chapter 4 Easy Measures Relating to Improved Plastics Sustainability

Plastics synthesis, processing, use, and disposal as all the human activities consume resources and energy, pollute, and compromise the future of the planet by global warming, atmospheric ozone depletion, and accumulation of pollutants often under organic forms and particularly harmful for human, animal, vegetal, and aquatic life. It is essential to evaluate different solutions with efficient and unbiased methods, preferably standardized allowing to compare the whole life from resource use up to waste disposal. Methods are very diverse and may be globally or regionally applied, from general purpose or detailed level, from voluntary or mandatory application. Laws, regulations, and trends are rapidly evolving and the information presented is only a quick glance needing a deeper study before application to the problem of the reader.

After an overview of the pace of change in the plastics industry, this chapter deals with the minimization of material impact using more or less traditional methods including a ban of hazardous materials; health and safety precautions, regulation compliance, and basic principles of sustainability. Material consumption and impact can be optimized using simulation and modeling tools, shifting, if suitable, from fossil to natural resources noncompeting with food, using recyclates and selecting reliable materials and trustworthy providers. Design must be orientated to facilitate maintenance, repair, reuse, refurbishment, among others. Manufacturing impact on the environment can be mitigated thanks to efficient machines, peripherals and retrofitting solutions, less energydemanding compounds, and use of dedicated software solutions (MES, ERP, etc.), leading to a

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rigorous management, efficient real-time quality control, and preventive and predictive maintenance that minimize waste and misuse of resources. Zero-defect manufacturing (ZDM) strategies can optimize environmental and economic costs. Energy must shift to renewable sources, and inline integration of manufacturing steps using direct mixing, coprocessing, inline process, workcells, and so forth generally lead to a better sustainability. Mitigation of environmental impact deals with all steps of the lifetime (including, supply, and distribution chains), use phase, machinery investment, and end of life. Hazardous releases must be minimized or suppressed. At each step, and at the end, the designer must balance the product features and the actual sustainable benefits in real conditions. The development of competences thanks to training and e-Learning contributes to sustainability improvement. 7 Tables and 7 figures illustrate this chapter.

Chapter 5 Eco-Design Rules for Plastics Sustainability Eco-design, green design, sustainable design, environmental design, and so on are new ways of designing aiming to comply with the principles of social, economic, and ecological sustainability. They are based on principles concerning the natural resource preservation, renewable source uses avoiding competition with food crops, energy saving, ban of toxic elements and molecules, carbon footprint reduction, effectiveness of recycling, and end cost optimization, among others. After a few examples, this chapter deals with principles of well-established routes related to longlasting parts, design optimization, weight and cost savings, reuse, repairing, and real reuse of recycled plastics saving energy, resources, and minimizing pollution. Of course, products must satisfy technical requirements and comply with specific rules. After a brief overview of material sustainability impact, specific behaviors of plastics that can surprise designers familiar with metals are briefly examined. The target is to alert the reader on the basic plastics behavior with mechanical loading, reinforcement of compounds, the effect of temperatures above and below ambient temperature, dimensional stability, electrical properties, fire, sensory

PREFACE

issues, optical properties, aesthetics, odor, taste, and touch. Aging takes several forms mainly weathering, light and UV radiations, and chemicals contact. Actual lifetime is not an intrinsic feature, but depends on the essential properties required for the targeted applications and varies according to the set level of properties retained as end-of-life criteria. Of course, plastics must obey regulations, health, and safety requirements. Ranges of data and information on sustainability, renewable materials; engineering properties and economics are examined in the following chapters. 16 Tables and 15 figures illustrate this chapter.

Chapter 6 Environmental and Engineering Data to Support Eco-Design for Plastics Sustainability is a new mode of thinking integrating environmental worries to the design step, in addition to traditional engineering and economical requirements. This chapter targets helping designers to clarify, on the one hand, the environmental issues and, on the other hand, to remind engineering considerations from a plastics point of view. Examined environmental indicators include:

• Energy requirements • Net carbon footprint, CO2 and other GHG, and GWP

• Water footprint • Some other environmental indicators Some pitfalls induced by environmental indicator uses are examined. On the other hand, usual engineering indicators for plastics design are noted. They deal with thermal behavior, glass transition temperature, heat deflection temperature (HDT), Continuous Use Temperature under unstressed state (CUT), Underwriters Laboratories (UL) temperature, and low temperature behavior. Numerous data deal with density, mechanical properties, hardness, stress and strain under unidirectional loading (tensile, flexural and compression properties), water uptake, and shrinkage. 25 Tables gather data related to neat, reinforced, and modified grade examples allowing to position subfamilies and grades with respect to each other. After a first rough screening, designers must

PREFACE

cooperate with chosen producers and processors to fix the final choice.

Chapter 7 Advanced Environmental and Engineering Properties to Support Eco-Design for Plastics Among other criteria, sustainable products must be efficient, competitive, and cost effective. Designers must know that plastics have specific environmental and engineering properties often time and temperature dependent. The goal of this chapter is to provide the basics and many examples (27 tables) for those advanced property data. Advanced environmental properties include fuel and feedstock energy, special aspects of GWP, ozone depletion potential, photo-oxidant creation potential, acidification potential, eutrophication potential, dust/ particulate matter, and ecotoxicity potential. Compared to usual fossil polymers, natural-sourced plastics bring benefits and also possible drawbacks. Advanced engineering properties are thermal and time-dependent with physical consequences (at short term) and aging (at long term) effects including creep, relaxation and fatigue damages. Low temperatures lead to hardening and brittleness, but slow the damages of aging. Several tables deal with electrical properties including resistivity, dielectric strength, and dielectric loss factors. Flammability through the oxygen index examples quickly alerts to the risks of fire. Optical properties (examples of transparent or translucent plastics), gas permeability, Poisson’s ratios, and tribological properties (coefficient of friction and PV: limiting pressure velocity) complete this landscape. 27 Tables and 12 figures illustrate this chapter.

Chapter 8 Economics Relating to Fossil and Renewable Plastics The goal of this chapter is to provide some economic information helping clarify quickly costs and market features concerning a panel of fossil and renewable plastics, composites, reinforcements, and additives.

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The range of costs is vast dependent on the selected polymer and additives, the geometry of the part, the selected processing method and, of course, the run size. Online cost estimator software solutions are examined and examples of costs (without guarantee) of parts by market conclude this topic. After an overview of recycled plastics costs and production capacities, natural-sourced materials are examined by family, countries (United States, EU, Asia) and by application markets. Some forecasts are proposed up to 2022, and even beyond for longer term. The market shares of the various renewable plastics families, the main application sectors, the natural fibers (NF), the NF composites and wood plastic composite are also reviewed. The main markets (packaging; consumer goods; automotive and transportation; building and civil engineering; agriculture; electrical and electronics equipment including household, entertainment, and office appliances; furniture and bedding; mechanical engineering; sports, and leisure; medical) are examined (7 tables reviewing more than 1000 examples) according to specific applications and used plastics families and trademarks. 20 Tables and 9 figures illustrate this chapter.

Chapter 9 Recycling of Plastics, Advantages, and Limitation of Use Today, recycling is the first source of renewable plastics ahead of natural-sourced polymers. After a brief outline relating to environmental benefits, involvements in economy, legislation, reliability, and performance concerns, the various methods of recycling are examined from mechanical to thermal recycling through chemical, solvent technologies, and enzymatic depolymerization. Rheology, mechanical performances, aging resistance, flammability, and color can be improved thanks to upgrading formulations with traditional or special additives. The most used sectorial routes concerning the recycling—polyEthylene terephthalate (PET) and polyEthylene (PE) bottles, E&E products, automotive and building devices—are discussed. Recycling of thermosets, composites, fibers, and highperformance polymers are approached.

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PREFACE

Special attention on environmental advantages of recycling is paid to CO2 emission, GHG effects, and carbon footprints. Several examples of industrially recycled plastic performances include polyamides, polystyrene, acrylonitrile-butadiene-styrene (ABS), polypropylene (PP), polycarbonate (PC) and its alloys PC/ABS and PC/polybutyleneterephthalate (PBT), and polyetherimide. Cost and pollution savings are also pointed out before an examination of some limitations. 26 Tables and 24 figures illustrate this chapter.

polyesters, acrylics, phenolic resins, epoxies, PCs, PP, and PVC. When published properties are limited or unavailable, facts and figures related to fossil counterparts are noted to help the reader, but the true properties of renewable grades can be somewhat different even if they are claimed to be “similar.” 55 Tables and 2 figures illustrate this chapter.

Chapter 10 Transition of Plastics to Renewable Feedstock and Raw Materials

Main bottlenecks, potential boosters, and brakes for the growth of plastics are examined in this chapter. Waste strategies range from waste minimization (the best solution) to landfilling through recycling and less known repairing and reuse. Hi-tech as well as common applications are concerned without forgetting in a different way, refurbishing, and upgrading of processing machinery benefiting of industry 4.0. Recycling and reuse in close or open loop offer environmental benefits for commodity or hi-tech materials (up to carbon fibers). Examples of GWP, energy, and other environment or economic indicators display benefits, but also some drawbacks of plastics recycling, pointing out inconsistency between indicators. In fact, the right answer depends on the actual context. Of course, policy, legislation, taxes, bans, and the green wave restrain use of plastics (carrier bags) or boost recycling (end-of-life vehicles). Some technical reasons are also limiting recyclate consumption. Success story examples of natural-sourced materials display alternative to oil scarcity, but the replacement of a fossil polymer can remain temporarily an unsolvable problem (e.g., ABS for Lego bricks). Ecological boosters of plastics include function integration, design freedom, lightweighting, and related energy and resource savings, as well as pollution mitigation. Sustainable systems include full or hybrid solutions based on biosourced polymers, natural fibers, and also “unsustainable” composites saving weight, fuel, and pollution in promising mobility fields from automotive to aircraft through railway and others. Insulation efficiency of plastics foams for “zero-energy” houses are other examples. 16 Tables and 11 figures illustrate this chapter.

After an inventory of renewable plastics derived from natural polymers, this chapter deals with properties, processing, and uses of natural-sourced additives, thermoplastic resins, thermosetting polymers, and composites. Please keep in mind that marketed products are often partially derived from renewable sources. Thermoplastic blends and derivatives of starch (TPS) include Mater-Bi (Novamont), and other compounds from BIOPAR (Biop) up to Solanyl (Rodenburg). For neat or reinforced polylactic acid derivatives, specific information put emphasis on formulation with additives (melt-strength enhancers, stabilizers, impact modifiers, plasticizers etc.), and alloying with other plastics. Properties of cellulose esters cellulose acetobutyrate [(CAB), cellulose acetate (CA), cellulose propionate (CP), and biograde] are detailed. Aliphatic polyesters include polyhydroxyalkanoate, polyhydroxybutyrate, polyhydroxybutyrate-cohydroxyvalerate, and others. Liquid wood based on lignin (arboform) and self-reinforced composite produced from cereals (VEGEMAT) conclude this chapter. A broad panel of biomonomers and bioblocks “similar” to those used for fossil resins lead to special advantages, but also possible limitations, allowing to synthetize a variety of plastics using traditional polymerization equipment. Physical, mechanical, and chemical properties, aging, processing, applications, and producers are examined for renewable polyethylene, thermoplastic polyesters, polyamides, polyurethanes, unsaturated

Chapter 11 Plastics Sustainability: Drivers and Obstacles

PREFACE

Chapter 12 Plastics Sustainability: Prospective In fact, the future has already begun and should be a mix of continuity (sustainable solutions proposed by resin producers, designers, etc.) and disruptive technologies thanks to innovative ways. The prospective depends on multiple and heterogeneous factors linked to expected demand and growth potential of plastics, demography, and standard of living, rethinking of time management, mandatory restrictions, bans or on the contrary incentive actions, oil shortage, and so forth. Emerging technologies can lead to a disruption of today’s landscape. For example, electric vehicles and autonomous vehicles may significantly change the use of plastics. Alternative fuels can boost the start of renewable polymers and help to speed up the dream of almost-perfect and self-healing polymers. Of course, sustainable plastics also bear their specific features including incompatibility with fossil polymers for some of them. Economics of renewable plastics and bioadditives include quantified expectations, consumption and capacity forecasts, recycling volume, biosourced plastic demand, market shares by family,

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region, and market. Composites and bioadditives are examined before propositions of long-term costs resulting from modeling based on historical prices, crude oil prices, and agricultural index expectations. In fact, sustainability depends on both individual and collective behavior regarding waste management (collection, financing, etc.), recycling management (e.g., reliability, bulk depolymerization suppressing the pitfall of waste sorting). Municipal solid wastes (MSW) and ocean litter, today considered as an environmental calamity, may become a mine of plastics and feedstock. 6 Tables and 14 figures illustrate this chapter. Once again, please note that this book is not an encyclopedia for a definitive selection of sustainable solutions based on plastics, but is only one of the tools aiming to help stakeholders implied in plastics device design. Generally speaking, a single book cannot cover all situations and cannot replace the intelligence of a team of designers and specialists of plastics, which is the ultimate decision maker and solely responsible for the final selection.

Disclaimer This book is not a basic theoretical study of sustainability, but suggests some potential ways for a transition to a better sustainability of plastic parts and devices. Each proposal is not suitable for all cases and therefore must be tested before application. Sustainability of plastics is a multifaceted, relative, and scalable concept that must be considered on the whole life cycle, according to the arbitration between the various pollutions and other damages to the environment, the relative importance dedicated to the various pillars of sustainability. In addition, designers cannot manage the actual conditions of the use phase making that actual sustainability can differ from the expected sustainability. Of course, a single book cannot solve this harsh and extensively stretched problem, and a solution for a given case may be inefficient or damaging for other cases. Sustainability requires skilled staff integrated into the design team in addition to engineers, manufacturing cost specialists, and marketing managers. This book is not an encyclopedia for a definitive selection of plastics sustainability, but suggests some examples of traditional or emerging solutions more or less easy to apply. Sustainability depends on time; local, national, and global requirements make that actual solutions can vary with time, location, and policy streams. More generally speaking, the reader must be aware of some traps in the literature such as, but not limited to:

• Property data claimed by producers or researchers are measured under specific conditions and, therefore, must be checked under real conditions before use for the design of plastics parts.

• It is the responsibility of the reader to select information relating to his/her own case and to search elsewhere for complementary and corroborating information.

• A book is only one of the tools aiming to help the preselection of solution systems. The reader is the only responsible for his/her

selection and, of course, he/she must absolutely cooperate with specialists for the selection of the definitive solution system.

• The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice. All the information contained in this book, collected from reliable documentation and verified as far as possible, is aimed at experienced, professional readers. We cannot accept responsibility for the accuracy, availability, timeliness, content, or completeness of data, processing methods, machinery, information, and ideas. The characteristic data, economic figures, general assessments, and indications concerning all the properties are not guaranteed and cannot be used for calculations, computations, or other operations to determine design, sustainability, cost-effectiveness, or profitability. The author is not responsible for possible technical, economic, typographical, or other errors. This book gives no warranties either expressed or implied. Design, processing, and application of plastics and composites are professional activities needing specific skills and involving industrial and financial risks, health hazards, toxicity, fire hazards, regulation conformity, and so forth. Readers must verify the technical data and information, economic figures, possible suitability for the targeted application with their own suppliers of raw materials or parts, machinery makers, and other current technical and economic sources. Prototypes and tests under operating conditions are essential. The reader is solely responsible for their chosen solutions. New materials and processes such as, for example, nanomaterials and 3D printing are emerging and their behaviors concerning humans and the environment are poorly known. Regulations depend on the countries involved, and are rapidly evolving. Consequently, designers, employers, users, and other players must continuously study regulations

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and the risks arising from the application of new technologies. Risks include among others, but are not limited to, inhalation of the material and emitted produces, absorption through the skin, contact with the skin or eyes, ingestion, fire and/or explosion (ultrafine dust), hazardous chemical reactions, and damaging of installations by nanomaterials (corrosion, etc.). It is the responsibility of the reader to determine the appropriate use of each product, processing

DISCLAIMER

method, machinery and ideas, and compliance with processing rules, safety precautions, health hazards, and existing national laws and regulations required by the countries regarding processing, commercialization, use, application, and disposal. The safety data, facts, and figures herein are provided for information only and are no substitute for the content of material safety data sheets and other information from producers, compounders, converters, and other suppliers.

Acronyms and Abbreviations 3D printing additive manufacturing techniques 5V UL fire rating AAGR average annual growth rate ABS acrylonitrile butadiene styrene ACM-V vulcanized acrylate rubber ACS acrylonitrile chlorinated polyethylene styrene Aeq acidification potential AES or AEPDS acrylonitrile EPDM styrene AM additive manufacturing AMC alkyd molding compound AP acidification potential APP ammonium polyphosphate ArF or AF aramid fiber ASA acrylonitrile styrene acrylate ASR auto shredder residues ASTM American Society for Testing and Materials ATBC acetyltributyl citrate ATH aluminum trihydrate BDO butanediol BF boron fiber BIR Bureau of International Recycling BMC bulk molding compound BMI bismaleimide BOD biochemical oxygen demand BOPLA bi-axially oriented polylactic acid BOPP bi-axially oriented polypropylene BPA bisphenol A BPI Biodegradable Products Institute BRIC Brazil Russia India China BTX aromatics, principally benzene, toluenes and xylenes CA cellulose acetate CAB cellulose acetobutyrate CAD computer aided design CAGR compound annual growth rate CBT cyclic polybutadiene terephthalate CE cyanate ester CF carbon fiber CFC chlorofluorocarbon CFRP carbon fiber reinforced plastic CFRTP carbon fiber reinforced thermoplastic CIC continuous impregnated compound

CM or CPE chlorinated polyethylene CNSL cashew nut shell liquid CNT carbon nanotube CO2 carbon dioxide CoBot(s) collaborative robots COC or COP cyclic olefin copolymers or cyclic olefin polymers COD chemical oxygen demand CONC concentrated solution COP or COC cyclic olefin polymers or cyclic olefin copolymers COPE or TPEE copolyester TPE CP cellulose propionate CPE or CM chlorinated polyethylene CPVC or PVC-C chlorinated PVC CS compression set CTI comparative tracking index CTLE coefficient of thermal linear expansion CUT continuous use temperature under unstressed state Cy polycyanate DAP diallyl phthalate DCPD poly(dicyclopentadiene) DCS dicaprylsebacate DIN CERTCO product conformity assessment DMC dough molding compound DMTA dynamic mechanical thermal analysis DRIV direct resin injection and venting DSC differential scanning calorimeter DTA differential thermal analysis DWNT double-wall nanotubes EB elongation at break EBA, EGMA, EMAH, EEA, EAA ethylene acid and ethylene ester copolymers (e.g., ethylene butylacrylate) ECO prefix concerning ecology or the environment (e.g., eco-profile) ECTFE ethylene monochlorotrifluoroethylene EE, E&E, EEE electrical & electronics equipment EFSA European Food Safety Agency ELV end of life vehicle EMA ethylene-methacrylate ionomers EMI electromagnetic interference xxix

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EMS environment management system EOAT end-of-arm tooling EP epoxy EP eutrophication potential EPA environmental protection agency EPD environmental product declaration EPDM rubber terpolymer ethylene, propylene, diene EPE environmental performance evaluation EPEAT electronic product environmental assessment tool EPS expandable (or expanded) polystyrene EPS eco-profiling system ERP enterprise resource planning ESBO epoxidized soybean oil ESC environmental stress cracking ESD electrostatic discharge ETFE ethylene tetrafluoroethylene ETP engineering thermoplastics EU European Union EVA, E/VAC, EVAC, VAE, EVM ethylene vinylacetate copolymers EVOH ethylene vinyl alcohol copolymers FAO Food and Agriculture Organization FDA Food and Drug Administration FEP fluorinated ethylene propylene FIM film insert molding F-PVC flexible PVC FR fire retardant FST flame, smoke, and toxicity GB glass bead GDP gross domestic product GF glass fiber GFRP glass fiber reinforced plastic GFRTP glass fiber reinforced thermoplastic GHG greenhouse gas GMT glass mat thermoplastic GWI glow wire ignition GWP global warming potential HB UL fire rating HDPE or PE HD high density polyethylene HDT heat deflection temperature HFC hydrofluorocarbon HFFR halogen free fire retardant HIPS high impact PS HPGF high-performance short glass fiber reinforced polypropylene HSCT high-speed civil transport (aircraft) HTPC hybrid thermoplastic composite HTV high temperature vulcanization HVAC heating, ventilation and air-conditioning

ACRONYMS

AND

ABBREVIATIONS

HWI hot wire ignition ICIS information provider for the petrochemical, oil, and energy industries. ICP inherently conductive polymer IDP inherently dissipative polymer IEEE Institute of Electrical and Electronic Engineers ILSS interlaminar shear strength IMC in-mold coating IMD in-mold decoration IML in-mold labeling IoT Internet of Things IPN interpenetrating polymer network IRHD International Rubber Hardness IRM International Referee Material ISO International Standardization Organization JBPA Japan BioPlastics Association LCA life cycle assessment LCC life cycle costing LCI life cycle inventory LCP liquid crystal polymer LCTC low cost tooling for composites LDPE or PE LD low density polyethylene LED light-emitting diode LEFM linear elastic fracture mechanics LFRT long fiber reinforced thermoplastic LFT long fiber reinforced thermoplastic LGF long glass fiber LIM liquid injection molding LLDPE linear low density polyethylene LOI limiting oxygen index LRI liquid resin infusion LRTM light RTM LSR liquid silicone rubber LWRT light weight reinforced thermoplastic MABS methylmethacrylate acrylonitrile butadiene styrene MAH maleic anhydride MBS methyl methacrylate butadiene styrene MDPE medium density polyethylene MEG monoethylene glycol MES manufacturing execution system MF melamine MFC microfibrillated cellulose MMT modified montmorillonite MPR melt processable rubber (TPE) MSW municipal solid waste MVTR moisture vapor transmission rate MWNT multiwalled carbon nanotubes NB no break NCC nanocrystalline cellulose

ACRONYMS

AND

ABBREVIATIONS

NF natural fiber NFC natural fiber composite NOx nitrous oxides NPO natural oil polyols NVH noise vibration harshness O&M Organization & Methods Department ODP ozone depletion potential OIT oxygen induction time OLED organic light-emitting diode OPET oriented PET OPP oriented PP OPS oriented PS ORNL Oak Ridge National Laboratory OTR oxygen transmission rate PA polyamide PAA polyarylamide PAEK polyaryletherketone PAI polyamide imide PAN polyacrylonitrile PAS polyarylsulfone PA-T transparent amorphous polyamide PB polybutene-1 or polybutylene-1 PBB polybrominated biphenyls PBDE polybrominated diphenyl ethers PBI polybenzimidazole PBO polyphenylenebenzooxazole PBS polybutylene succinate PBSA polybutylene succinate-adipate PBT or PBTP polybutyleneterephthalate PC polycarbonate PCB polychlorinated biphenyls PCB printed circuit board PC-HT polycarbonate-high temperature PCL polycaprolactone PCR postconsumer recycled PCT polycyclohexylene-dimethylene terephthalate PCTA terephthalate/isophthalate PCTFE polychlorotrifluoroethylene PCTG polycyclohexylene-dimethylenediol/ ethyleneglycol terephthalate PDLA poly-D-lactide PDMS polydimethylsiloxane PE polyethylene PEAA polyethylene acrylic acid PEAR polyetheramide resin PEBA polyether block amide PECVD plasma-enhanced chemical vapor deposition PEEK polyetherether ketone PEF polyethylene furanoate PEG polyethylene glycol

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PEI polyetherimide PEK polyetherketone PEKK polyether ketone ketone PEN polyethylene naphthalenedicarboxylate PEO polyethylene oxide PES or PESU polyethersulfone PET or PETP polyethylene terephthalate PETG polyethylene glycol modified PETI phenylethynyl with imide terminations PEX cross-linked polyethylene PF phenolic resin PF1Ax PF general purpose, ammonia free PF2Cx PF heat resistant, glass fiber reinforced PF2Dx PF impact resistant, cotton filled PF2E1 PF mica filled PFA perfluoroalkoxy PGA polyglycolic acid PHA polyhydroxyalkanoate PHB polyhydroxybutyrate PHBH polyhydroxybutyrate-hexanoate PHBV polyhydroxybutyrate-co-hydroxyvalerate PHV polyhydroxyvalerate PI polyimide PIR polyisocyanurate PK polyketone PLA polylactic acid PLLA poly-L-lactide PLM product life cycle management PMI polymethacrylimide PMMA polymethylmethacrylate PMP polymethylpentene PO polyolefin POCP photo-oxidant creation potential POE polyolefin elastomer POM polyoxymethylene or polyacetal POP polyolefin plastomer POSS polyhedral oligomeric silsesquioxane PP polypropylene PP/EPDM unvulcanized EPDM blended with polypropylene or block copolymerized PPEPDM (reactor TPO)— (TPE) (TPO) PP/EPDM-V vulcanized EPDM dispersed in polypropylene (TPE) (TPV) PP/IIR-V vulcanized butyl rubber dispersed in polypropylene (TPE) (TPV) PP/NBR-V vulcanized nitrile rubber dispersed in polypropylene (TPE) (TPV) PPA polyphthalamide PPC polypropylene carbonate PPE polyphenylene ether PPO polyphenylene oxide

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PPS polyphenylene sulfide PPSU polyphenylenesulfone PPT or PTMT or PTT polypropylene terephthalate Prepreg preimpregnated PS polystyrene PSU polysulfone PS-X or XPS cross-linked polystyrene PTFE polytetrafluoroethylene PTMT or PBT polytetramethylene terephthalate or polybutyleneterephthalate PTMT or PPT or PTT poly(trimethylene terephthalate) PTT polytrimethylene terephthalate PUR polyurethane PV pressure velocity factor PV photovoltaic PVA or PVAL or PVOH polyvinyl alcohol PVAC polyvinyl acetate PVAL or PVA or PVOH polyvinyl alcohol PVB polyvinyl butyrate PVC polyvinyl chloride PVC-C or CPVC chlorinated PVC PVC-U unplasticized PVC PVDC polyvinylidene chloride PVDF polyvinylidene fluoride PVF polyvinyl fluoride PVOH or PVAL or PVA polyvinyl alcohol QA quality assurance r recycled (i.e., rPET, rPP) REACH Registration Evaluation Authorization and Restriction of CHemicals RF radio frequency RFI resin film impregnation RH relative humidity or hygrometry RIM reaction injection molding RIRM resin injection recirculation molding RoHS restriction of hazardous substances ROI return on investment RP reinforced plastic RRIM reinforced reaction injection molding RT room temperature RTI relative thermal index RTM resin transfer molding RTP reinforced thermoplastic RTV room temperature vulcanization SAN styrene acrylonitrile SAP super absorbent polymer SATUR saturated solution SB styrene butadiene SBC styrenic block copolymer

ACRONYMS

AND

ABBREVIATIONS

SBS styrene butadiene styrene (TPE) SCRIMP Seeman’s composite resin infusion molding process SEBS styrene ethylene/butylene styrene (TPE) SEPS styrene ethylene/propylene styrene (TPE) SFRT short fiber reinforced thermoplastic SGF short glass fiber Si Silicium Si silicone SiOx silicon oxide SIS styrene isoprene styrene (TPE) SLA stereolithography SLS selective laser sintering SMA styrene maleic anhydride SMC sheet molding compound SMMA styrene methyl methacrylate SN curve plot of stress or strain (S) leading to failure after N cycles of repeated loading SOL solution SPC statistical process control SPDF super plastic diaphragm forming SPE society of plastics engineers SPI society of the plastics industry SP-polyimides condensation polyimides SR self-reinforced SRRIM structural (reinforced) resin injection molding SWNT single-walled carbon nanotubes TAC triallyl cyanurate TDI toluene-2,4-diisocyanate TFE tetrafluoroethylene Tg glass transition temperature TGA thermogravimetric analysis TGV high-speed train TMC thick molding compound TOE or toe tonne of oil equivalent TP thermoplastic TP/Si-V TPV of a vulcanized silicone rubber dispersed in a thermoplastic phase TPE thermoplastic elastomer TPE/PVC PVC-based TPE, alloys of PVC and rubber (TPE) (TPO or TPV) TPEE or COPE thermoplastic elastomer ester TPI thermoplastic imide TPO thermoplastic olefin TPR thermoplastic rubber TPS thermoplastic starch TPU thermoplastic polyurethane TPV thermoplastic vulcanizate TR temperature-retraction procedure TS tensile strength

ACRONYMS

AND

ABBREVIATIONS

UD unidirectional composite UF urea formaldehyde UHMWPE or PE-UHMW ultrahigh molecular weight PE UL Underwriters Laboratories Unkn. unknown UP unsaturated polyester USB United Soybean Board UV ultraviolet V0 to V2 UL fire rating VAE ethylene vinylacetate copolymers VARI vacuum assisted resin injection VARTM vacuum assisted RTM VE vinylester VGCNF vapor grown carbon nanofibers

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VIP vacuum infusion process VOC volatile organic compounds VOP vegetable oil polymer VST vicat softening temperature VTT Technical Research Centre of Finland Ltd WEEE waste electrical and electronic equipment WPC wood plastic composite WRAP Waste and Resources Action Program XLPE cross-linked LDPE XPE or PEX cross-linked polyethylene XPS or PS-X cross-linked polystyrene ZDM zero-defect manufacturing ZMC a highly automated process using molding compounds

Glossary 3D printing initially “3D printing” used inkjet printer heads to deposit a material layer by layer. Today this term covers various additive manufacturing (AM) techniques. AM techniques build up objects from 3D data generated from 3D computer-aided design (CAD) or 3D scanning systems. AM builds the object layer by layer from liquid, powder, filament, or sheet material and consolidates successive layers by joining, melting, or curing. Each layer corresponds to the virtual cross section from the CAD model Abiotic depletion abiotic depletion refers to the depletion of nonliving (abiotic) resources such as fossil fuels, minerals, clay, and peat. Abiotic depletion is measured in kilograms of antimony (Sb) equivalents Accelerated heat aging conventional accelerated heat aging tests consist of exposing defined samples to controlled temperature air in ovens protected from light, ozone, and chemicals, for one or more given times. The degradation is measured by the variation at room temperature of one or several physical, mechanical, or esthetic characteristics during the aging. The variations of impact resistance, hardness, or tensile or flexural strength are the most frequently studied. Accelerated aging is an arbitrary measurement that must be interpreted and must constitute only one of the elements used in making a judgment Acidification acidification results from the emission of acids by industrial, agricultural, or other activities, which leads to a decrease in pH and an increase of potentially toxic elements. The major acidifying pollutants are SO2, NOx, HCl, CO2, etc. Acidification is measured in terms of SO2 equivalents Acoustic emission sound generated by defects such as crack initiation or crack growth when a sample or part is mechanically stressed

Additive adding additives to raw polymer(s) optimizes durability, reinforcement, plasticity, processing, esthetics, impact resistance, optical or electrical properties, fire resistance, etc. Reinforcement uses glass, Aramid, carbon fibers, natural fibers, textile fibers, mineral fillers, glass beads, nanofillers, carbon nanotubes, etc. Other mineral or organic additives are as diverse as plasticizers, colorants and pigments, impact modifiers, processing stabilizers, antioxidants, light stabilizers, hydrolysis stabilizers, tribological agents, nucleators, antirodents, microbicides, low cost fillers, matting agents, foaming additives, etc. Additive manufacturing or AM AM techniques build up objects from 3D data generated from 3D computer-aided design (CAD) or 3D scanning systems. AM builds the object layer by layer from liquid, powder, filament, or sheet material and consolidates successive layers by joining, melting, or curing. Each layer corresponds to the virtual cross section from the CAD model Alloy thermoplastic families are diverse, but their number is limited and often there are wide gaps between the properties of two basic polymer types. To bridge the gap, two polymer families can be mixed if they are compatible or if it is possible to compatibilize them with the use of a third material. For a suitable mixing of two components, the properties of an alloy including the cost are generally intermediate between those of each component Amorphous chains of an amorphous polymer are randomly arranged. Amorphous polymers slowly soften when heated above their glass transition temperature Generally, amorphous polymers have lower chemical resistance than semicrystalline ones, but may be transparent Anaerobic digestion anaerobic digestion consists of a series of biological processes in which microorganisms break down biodegradable

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plastics (and other biodegradable materials) in the absence of oxygen Anisotropic a polymer or composite is anisotropic if its properties depend on the test direction. When measured along different axes, physical and/or mechanical properties (modulus, refractive index, conductivity, etc.,) are different. Unidirectional tapes are highly anisotropic Annealing heating and keeping a polymer part at a temperature near, but below, its melting point to relax internal stresses without distortion of its shape Antifogging additive this helps to avoid the condensation of water vapor on cold plastic surfaces resulting in the formation of water droplets and loss of transparency Aspect ratio the ratio of length to diameter of a fiber or the ratio of the thickness to the planar sizes of a particle American Society for Testing and Materials (ASTM) standards ASTM International, formerly known as the ASTM, is a globally recognized leader in the development and delivery of international voluntary consensus standards. Today, some 12,000 ASTM standards are used around the world to improve product quality, enhance safety, facilitate market access and trade, and build consumer confidence The main technical committee (TC) dealing with plastics is the D20—plastics, but other standards can be classified into C03—chemical-resistant nonmetallic materials; D07—wood; D08—roofing and waterproofing; D09—electrical and electronic insulating materials; D13—textiles; D14—adhesives and others Balanced laminate all plies of a balanced laminate are placed in plus/minus pairs, for example, 6 45 degrees, symmetrically about the layup centerline Biobased derived from living matter or biomass. Please note that products labeled as “Biobased” are not necessarily compostable unless specified as such Biobased carbon content the biobased carbon content of a plastic is the amount of biobased carbon in the material or product as fraction weight or percent weight of the total organic carbon in the material or product Biobased content biobased content by weight percentage can be different to the biobased carbon content because it takes into account

GLOSSARY

oxygen from natural sources. For instance, a 50% starch content inserted into a polyolefin may show only a 20% 25% biobased carbon content while the weight approach might show a higher result Bioblock, biomonomer, biooligomer a biosourced chemical block, monomer, or oligomer is used to synthetize polymers or oligomers Biochemical oxygen demand (BOD) BOD measures the amount of dissolved oxygen needed by aerobic biological organisms present in water to break down organic material. The BOD value is most commonly expressed in milligrams of oxygen consumed per liter of sample during 5 days of incubation at 20°C Biodegradation biodegradation is the chemical decomposition of polymers by bacteria or other biological means in the presence of oxygen (aerobic biodegradation) or in the absence of oxygen (anaerobic biodegradation) For nonbiodegradable polymers, degradation can be obtained using high levels of biodegradable additives. These are sources of nutrients for microorganisms, but conventional polymers, polyethylene particularly, are not biodegraded; only biodegradable additives are completely biodegraded, but:

• The skeleton of conventional polymer becomes weak and brittle and can disappear more easily.

• The surface area is highly increased and promotes chemical and bacterial attacks. It is possible to degrade polymers by:

• Photodegradation obtained by the addition of small levels of UV degradation promoters or photoinitiators.

• Oxydo-degradation: prooxidants accelerate the thermo-oxidation of polymers.

• Hydrolysis: polyesters are sensitive to hydrolysis, which cuts the macromolecules. The fragments are more or less biodegradable.

• Water solubility: the polymer disappears from view, but the chemical species can pollute the environment. Generally, final uses are specific because of the solubility. Bioplastics from renewable sources bioplastics are not a single class of polymer, but rather a

GLOSSARY

series of products that can vary considerably one from to the other. Generally, they are directly or indirectly based on renewable biomass sources such as ethanol, vegetable oil, cornstarch, pea starch, sugar, etc. The natural content can be, for example, as low as 20%. Beware, sometimes biocompatible synthetic plastics are quoted as bioplastics. They are not included in this book Brittle plastic when mechanically stressed, the break point of brittle plastics arises immediately after the yield point or coincides with it Carbon footprint carbon footprint can be featured by the total amount of carbon dioxide (CO2) and methane (CH4), directly or indirectly emitted by a defined system or activity. Carbon footprint is calculated as carbon dioxide equivalent (CO2e) The carbon footprint (CO2e) of various forms of energy generation can be, for example:

• • • •

Coal 900 1050 g/kWh Gas 450 600 g/kWh Photovoltaic 50 100 g/kWh Wind, nuclear, and hydro less than 50 g/kWh

Cast film film made by casting a layer of plastic onto a surface. After solidification, the film is removed for use. The plastic can be in molten state, in solution, or dispersion Chemical oxygen demand (COD) COD measures the number of organic compounds in water. COD measures everything that can be chemically oxidized Circular economy alternative economic model that proposes new criteria including:

• Reuse efficiently recovered materials from previous uses. • Keep resources in use for as long as possible. • Extract the maximum value from resources while in use, which may require an optimization of the design.

• Satisfactorily recover and regenerate products and materials at the end of each service life, which closes the loop. Please note that “sending back to carbon cycle” option can be understood in several ways, for example, composting, the ultimate step, or chemical recycling providing new chemical blocks for the polymerization of new virgin plastics. These are not conflicting; recycling can be

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used for some loops and then composting or chemical recycling for a deeper regenerative step, leading to a virgin polymer ready for a new life. This limits the accumulation of contaminants. Today the common economic scheme is a linear economy that can be shortly summarized by:

• Produce and manufacture from all available resources

• Use through the easiest way • Dispose after use through the easiest way Collaborative robots or cobots collaborative robots do not need a fence around the work area because they know where humans are and stop gently if a human touches them. Humans can work side by side with collaborative robots that do all the strenuous repetitive work, freeing humans up to use their brains and manual dexterity to do the lighter, more intricate jobs Composites composites combine a polymer matrix, thermoset, or thermoplastic and a nonmiscible reinforcement closely linked with the matrix such as fibers of significant length compared to the diameter, yarns, mats, fabrics, foams, honeycombs, etc. The matrix (or binder) ensures the cohesion of the composite, and distributes and dampens the impacts or stresses to protect the composite from the environment. The cohesion of the matrix and the reinforcement is of vital importance. The reinforcement bears the stresses. When these reinforcements are not randomly distributed, the properties are anisotropic, being enhanced in the reinforcement direction Compound compounds are obtained by mixing of raw polymer(s) with additives, leading to a broad range of characteristics for the same raw polymer Consolidation compression of a heated composite to reduce voids and achieve a better cohesion and strength Copolymer or heteropolymer copolymers (or heteropolymers) are polymerized from two or more monomers arranged in various structures, for instance, statistical copolymers with a random arrangement of comonomers, alternating copolymers with a regular distribution of comonomers, block copolymers alternating blocks of each monomer. Copolymers can be

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linear, branched, or hyperbranched. Branched copolymers include star copolymers, brush copolymers, and comb copolymers Cradle-to-factory gate cycle beginning with raw material extraction from the Earth and ending with the product leaving the factory Cradle-to-grave complete cycle beginning with raw material extraction and ending with the final disposal of the product or part (recycling, composting, landfilling, etc.) Crazing tiny cracks near or on the surface of plastic materials Creep Creep is the time-dependent strain induced by a constant mechanical loading. The strain is a function of the stress level, the time for which the stress is applied, and the temperature. The results can be presented graphically in various ways by combining these three parameters or in quantified forms such as creep modulus and creep strength, for example. Creep can lead to breaking for levels of stress much lower than ultimate stresses measured by dynamometry Crosslinking or curing building of a 3D network due to chemical reactions linking several polymer chains. Crosslinking can be achieved by heating or UV or electron beam irradiation, etc. Some thermoplastics are crosslinkable and are industrially used in their two forms, namely thermoplastic and thermoset Crystallinity polymers can be amorphous, crystalline, or semicrystalline. Semicrystalline polymers contain regions of three-dimensional ordering and amorphous regions without any order; the degree of crystallinity is the weight fraction or the volume fraction of crystalline material. It ranges from zero for a completely amorphous polymer to one for a completely crystalline polymer. Semicrystalline polymers are generally tougher than totally amorphous polymers, but are opaque while some amorphous polymers are transparent. The crystallinity of a polymer can be measured by differential scanning calorimetry or density or X-ray diffraction Drop-in solutions the use of natural-sourced components that can directly enter, pure or possibly mixed with fossil components, into polymerization plants, replacing a portion or the totality of fossil raw materials. No extra capital or no basic processing step modification is required Ductile plastic a plastic is ductile when the break point is far from the yield point

GLOSSARY

Eco-balance see life-cycle assessment or life-cycle analysis Eco-design or environment conscious design (ECD) or sustainable design eco-design or ECD or sustainable design targets the reduction of adverse environmental impacts of a product throughout its entire life-cycle. This can involve balancing the environmental aspects of the product with its intended use, performance, cost, marketability and quality, and choosing methods to meet legal and regulatory requirements in the most environment-friendly way Eco-profile eco-profile assessment of the total energy use, raw material use, air and water emissions, and the total solid waste produced from the cradle to the factory gate. An ecoprofile always ends with the production of the considered part or product Eco-profiling system (EPS) EPSs use different environmental indices and ecological scores to compare the sustainability of different solutions Indices may be divided, for example, into:

• • • •

Natural resource index Substance effect index Material index and Process index

The criteria may include:

• Type and extent of environmental impact or problem

• • • •

Intensity and frequency of occurrence of impact Real distribution of impact Durability of problem Contribution to problem by emission of 1 kg of a given substance

• Possibility and associated costs of remedying problem Ecosystem association of populations of different species of living organisms and nonliving components occupying the same geographical area at a defined time Plants, animals, biomass, energy, water, nitrogen, minerals, residues from the decomposition of organic matter, and toxic materials are, among others, essential parameters of an ecosystem.

GLOSSARY

Ecotoxicity detrimental effects of natural or synthetic parameters potentially toxic for ecosystems. Concentrated by human activities, they might occur in the environment at densities, concentrations, or levels high enough to disrupt the natural biochemistry, physiology, behavior, and interactions of the living organisms that comprise of that ecosystem e-Manufacturing polymer parts can be produced by e-manufacturing, an additive manufacturing technique building up objects from 3D data generated from 3D computer-aided design or 3D scanning systems. e-Manufacturing or direct digital manufacturing is suitable for the limitedrun production of certain parts, being a costeffective alternative to traditional manufacturing methods for low production volumes, high design complexities, and the probability of nearterm design changes End cost the end cost includes processing, assembling, delivery, set up, operating, and endof-life costs, taking into account durability, savings in maintenance, and operating costs, etc. End costs must be taken into account when deciding whether to design with plastics or conventional materials End-of-arm tooling (EOAT) or endeffectors robots for the plastics industry use common and specific EOAT, also called end-effectors. Applications are as diverse as transporting, sorting, inspecting, machining, assembling, painting, soldering, palletizing, etc. Energy: primary and secondary primary energy is found in nature and has not been subjected to any conversion process. It is the energy contained in raw fuels, and other forms of energy received as inputs into a system. Primary energy can be nonrenewable or renewable. Examples include crude oil, natural gas, coal, hydroelectric, geothermal, photovoltaic, wind, nuclear, and biomass Secondary energy refers to the more convenient forms of energy, which are transformed from other, primary energy sources through energy conversion processes. Examples include electricity, refined fuels, gasoline, and hydrogen fuels Environmental impact possible effects caused on the environment by a development, industrial, or infrastructural project or by the

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release or concentration of substances in the local environment. For example, naturalsourced polyethylene production has beneficial environmental impacts such as fuel savings and agricultural labor development, but it also has detrimental effects such as deforestation and pollution by fertilizers, insecticides, etc. Environmental stress cracking (ESC) when a plastic exposed to air is subjected to a stress or a strain below its yield point, cracking can occur after a long duration. The simultaneous exposure to a chemical environment under the same stress or strain can lead to a spectacular reduction of the failure time. The accelerated cracking in this way corresponds to “ESC.” Environment conscious design (ECD) or ecodesign or sustainable design ECD, eco-design, or sustainable design targets the reduction of adverse environmental impacts of a product throughout its entire life-cycle. This can involve balancing the environmental aspects of the product with its intended use, performance, cost, marketability and quality, and choosing methods to meet legal and regulatory requirements in the most environment-friendly way Eutrophication eutrophication is caused by the addition of nutrients to a soil or water system that leads to an increase in biomass, thereby damaging other life forms. Water acquires a high concentration of nutrients, especially phosphates and nitrates, promoting the excessive growth of algae. Eutrophication is measured in terms of phosphate (PO432) equivalents Extended producer responsibility (EPR) EPR places the responsibility for the postconsumer phase of certain goods on producers, which assume significant responsibility—financial and/ or physical—for the treatment or disposal of postconsumer products Face sheet or skin surface material of sandwich structures Fatigue the repeated mechanical loading of a polymer leads to a speedier failure than an instantaneous loading under identical strain or identical stress Fire behavior polymers are based on organic matter that are more or less combustible. They emit smoke and drip. Fire behavior depends on the nature of the polymer and the use of

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GLOSSARY

fire-proofing agents, special plasticizers, and specific fillers. Tests relate to:

• the tendency for combustion based on underwriter laboratories (UL) 94 ratings and oxygen index • the smoke opacity • the toxicity and corrosivity of the smoke The main categories of UL ratings are:

• V-0: the most difficult to burn, extinguished after 10 seconds, no drips

• V-1: extinguished after 30 seconds, no drips • V-2: extinguished after 30 seconds, flaming particles or drips permitted

• 5V: extinguished after 60 seconds, flaming particles or drips permitted

• HB: burning horizontally at a 76 mm/min maximum rate The UL rating depends on the exact grade and the sample thickness. The oxygen index is the minimum percentage of oxygen in an atmosphere of oxygen and nitrogen that sustains the flame of an ignited polymer sample. Fire retardant (FR) substance or method that reduces the flammability of materials or delays their combustion. This includes chemical additives, charcoal generating agents, and coatings. Finally, FR additives do not prevent combustion; it is a question of oxygen access, temperature, and time. In the event of a lack of oxygen, plastics are destroyed by pyrolysis if the temperature is high enough Flame smoke toxicity (FST) flame, smoke, and toxicity requirements for mass transport vehicles Flow line or weld line a flow line is a mark on a molded part resulting from the meeting of two flow fronts during molding. Generally, this spot has weaker properties Fogging the word relates to two different phenomena:

• Condensation of the air moisture on a cold material, the formation of tiny droplets on the surface, and light scattering and the obscuring of the material.

• Desorption of additives or low molecular weight polymers from plastic parts and their condensation on other cold parts, for example, glazing of cars, particularly windscreens, optical lenses, or electronic devices where the deposit of additives can also create electrical insulation. Fossil energy demand (MJ/kg polymer) fossil energy demand represents a depletion of finite reserves including fossil feedstocks that are converted into polymer (or other product) itself as well as fossil energy process usage for this conversion Fossil plastics plastics originated from fossil fuels formed by natural processes such as the anaerobic decomposition of buried, dead organisms. The age of fossil fuels including petroleum, coal, and natural gas is typically between millions and hundreds of millions of years Glass transition temperature (Tg) for amorphous polymers or amorphous domains of semicrystalline polymers, the Tg is a reversible transition from a hard and brittle state into a molten or rubber-like state. There are sudden and significant changes in the physical properties including the coefficient of thermal expansion and specific heat. The transition temperature value depends on the testing conditions, notably the cooling or heating rate and the frequency of the measured parameter Global warming potential (GWP) GWP is an appraisal of greenhouse gas (e.g., CO2, CH4, nitrous oxide) contribution to global warming. Global warming comes from an increase in the atmospheric concentration of greenhouse gases, which changes the absorption of infra-red radiation in the atmosphere leading to changes in climatic patterns and higher global average temperatures. GWP is measured in terms of CO2 equivalents, comparing the amount of heat trapped by a certain mass of the studied gas to the amount of heat trapped by a similar mass of CO2 Genetically modified organism (GMO) GMO is any organism whose genetic material has been altered using genetic engineering techniques Greenhouse gases (GHGs) GHGs are often expressed in terms of the amount of CO2, or its equivalent of other GHGs, emitted through

GLOSSARY

transport, land clearance, and the production and consumption of food, fuels, manufactured goods, materials, wood, roads, buildings, and services Haze haze refers to the cloudy appearance of a transparent polymer caused by light scattering. Haze may appear after long exposure to moisture Heavy metals heavy metals, concentrated as a result of human activities, are harmful to the environment. They include, but are not limited to, mercury, zinc, copper, cadmium, vanadium, and lead Heteropolymer or copolymer heteropolymers or copolymers are polymerized from two or more monomers arranged in various structures, for instance, statistical copolymers with a random arrangement of comonomers, alternating copolymers with a regular distribution of comonomers, block copolymers alternating blocks of each monomer Copolymers can be linear, branched, or hyperbranched. Branched copolymers include star copolymers, brush copolymers, and comb copolymers Homopolymer homopolymers are based on a single monomer. They can be linear (a single chain) or branched (with side chains) Hybrid materials hybrid materials are not really a clearly defined material category but result from a design method that associates, by integrating them closely, one or more polymers on the one hand and, generally, one or more other materials, which provide one or more functionalities difficult or impossible to obtain with only one polymer Impact behavior impact tests measure the energy absorbed during a specified impact of a standard weight striking, at a given speed, a test sample clamped with a suitable system. The hammer can be a falling weight or, more often, a pendulum. In this case, the samples can be smooth or notched. The results depend on the molecular orientation and the degree of crystallization of the material in the sample, its size, the clamping system, the possible notch and its form, the mass, and the strike speed. The values found in the literature, even for instrumented multiaxial impact (International Organization for Standardization 6603-2:2000), can only be used to help in decision making and do not replace tests on real parts

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The Izod and Charpy impact tests are mostly used Industry 4.0 industry 4.0 is building on the digital revolution toward creating a continuous and smooth flow of information along the entire value chain. Industry 4.0 is based on software dealing in information from humans, sensors, robots, etc., to detect, quantify, and analyze just about all properties linked to raw materials, machines, processing, quality, products, failures, traceability, etc. The goal is to improve sustainability, customer satisfaction, costeffectiveness, resource optimization, efficient collaboration between stakeholders from providers to customers, to enhance productivity, quality, waste management, affordability, and timeous delivery International Organization for Standardization (ISO) standards ISO is the world’s largest developer and publisher of international standards. ISO is a network of the national standards institutes of 163 countries with a Central Secretariat in Geneva, Switzerland, that coordinates the system. ISO is a nongovernmental organization that forms a bridge between the public and private sectors Two main technical committees (TCs) deal with plastics and rubbers, namely TC 61 for plastics and TC 45 for rubber and rubber products. Standards can be also emitted by other TCs such as, for example, TC 138 for plastics pipes, fittings, and valves for the transport of fluids or TC 20 for aircraft and space vehicles Isomer isomers have the same molecular formula, but different atom and function arrangements. Structural isomers have different monomer arrangements Stereoisomers have the same monomer arrangement, but different spatial distributions of chemical functions Polymers can be cis- or trans-according to the relative position of substituent on either side of a double bond Isotropic isotropic polymers have equal properties in all directions. Carefully molded glass bead filled thermoplastics are isotropic Laminate a laminate is made of several stacked plies (or laminae) with diverse orientations chosen to achieve given required properties. These plies are held together by to resin. Among other parameters, laminate performance depends on the properties of each ply, the orientations of

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the reinforcements, the order in which the plies are stacked, and the cohesion between the plies Life-cycle assessment or life-cycle analysis (LCA) LCA assesses environmental impacts resulting from all the stages of a product or part life including raw material extraction, material processing, manufacture, distribution, use, repair and maintenance, and disposal or recycling. LCA is also known as eco-balance or cradle-tograve analysis Life cycle inventory (LCI) LCI is the inventory of the total energy use, raw material use, air and water emissions, and the total solid waste produced from the cradle-to-grave (grave being the ultimate disposal). The LCI gives the basic data for life-cycle analyses. It is equivalent to the eco-profile, covering the complete life-cycle. In the strictest sense of the term, the LCI of resins, pellets, new films, or tubes, etc. does not exist because the pellets and new parts or products aren’t usually thrown away Light and UV resistance polymers are based on organic materials and are sensitive to natural or artificial UV sources. This is of primary importance for outdoor exposure of unprotected parts and for some industrial applications such as electrical welding, photocopier light exposure devices, etc. UV resistance can be tested by specific devices including irradiation by artificial UV light of various UV sources or by direct sunlight exposure The interpretation of the test results is difficult because of climate diversity, risks of industrial or domestic pollution in real life, lack of correlation between artificial and natural aging, and the different degradation kinetics of the various properties Lignin one of the most abundant organic polymers on Earth, exceeded only by cellulose. Lignin constitutes 30% of nonfossil organic carbon and 20% 35% of the dry mass of wood. Lignins are crosslinked phenolic polymers having the approximate formula: (C31H34O11)n Linear economy currently the common economic scheme is a linear economy that can be shortly summarized as:

• Produce and manufacture from all available resources

• Use through the easiest way • Dispose after use through the easiest way

GLOSSARY

Alternatively, the circular economy proposes new criteria including:

• Reuse efficiently recovered materials from previous uses.

• Keep resources in use for as long as possible. • Extract the maximum value from resources while in use, which may require an optimization of the design.

• Satisfactorily recover and regenerate products and materials at the end of each service life, which closes the loop. Please note that “sending back to carbon cycle” option can be understood in several ways, for example, composting, the ultimate step, or chemical recycling providing new chemical blocks for the polymerization of new virgin plastics. These are not conflicting, recycling can be used for some loops and then composting or chemical recycling for a deeper regenerative step, leading to a virgin polymer ready for a new life. This limits the accumulation of contaminants. Today the common economic scheme is a linear economy that can be shortly summarized by:

• Produce and manufacture from all available resources

• Use through the easiest way • Dispose after use through the easiest way. Marine litter plastics that end up in the oceans commingled with other solids form marine litter with local “islands,” particularly shocking from a visual point of view. It is estimated that plastic accounts for over 80% of marine litter Manufacturing execution system software controlling the activities occurring on a shop floor, from orders up to delivery to customers Microplastics microplastics result from:

• Leakage of plastic resin pellets during preprocessing operations such as polymerization, compounding, etc. • Unwanted loss of plastics products waterbodies. By erosion and wear the size is reduced to micron level.

in

• Intentional use of microbeads in personal care products.

GLOSSARY

Microplastics (usually less than 5 mm), can be ingested by aquatic wildlife leading to potential risks, injuries, poisoning, and other damages. Molecular weight molecular weight can be expressed in:

• Number average molecular weight (Mn) • Weight average molecular weight (Mw) The ratio of the weight average to the number average (Mw/Mn) is the polydispersity index giving an indication on the molecular weight distribution. Molecular weight distribution (MWD) most polymers have a unimodal distribution, but for specific purposes some have a bimodal distribution. The MWD influences the strength of solid plastics and the rheology of molten polymers Municipal solid waste (MSW) MSW consists of everyday items that are discarded by the public Orthotropic the properties of orthotropic polymers are different along two orthogonal directions. For example, balanced laminates having the same properties along the X- and Y-axis but different properties along the Z-axis (thickness) Ozone depletion (ozone hole) destruction of the ozone stratospheric layer by reactions with chlorine and bromine derivatives Depletion of the ozone layer increases UV radiations at ground level and affects the prevalence of skin cancer and other disorders. International conventions and national laws prohibit the production, use, and release of ozone-depleting substances Photochemical oxidation the formation of photochemical oxidant smog is the result of complex reactions between NOx and volatile organic compounds under the action of sunlight (UV radiation), which leads to the formation of ozone in the troposphere. The smog phenomenon is highly dependent on meteorological conditions and the background concentrations of pollutants. Photochemical oxidation is measured using photo-oxidant creation potential, which is normally expressed in ethylene equivalents Placement process to set reinforcements in a composite part to maximize given required properties. For example, fiber placement or tape placement Ply or lamina a ply (or lamina) is a flat or curved elementary arrangement of unidirectional or

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woven fibers embedded in a polymer matrix. Its thickness depends on the used reinforcement. For example, a carbon fiber ply may be on the order of 0.127 mm thick. Usually several plies are stacked to build a laminate “Polluter pays” principle directly or indirectly, the polluter pays for the collection, sorting, processing, or decontamination of a produced or consumed product, device, etc. There are not common rules and only a few examples are given showing their diversity. Many other systems may be set up by some nations Polymer a polymer is a long chain or macromolecule built by the polymerization of one or several monomer(s). Homopolymers are made from only one monomer and comonomers from two or more monomers Polymers can be linear or branched. Branched copolymers include star copolymers, brush copolymers, and comb copolymers Post cure additional curing achieved by heating or UV or electron beam irradiation, etc., to optimize a 3D network. Some thermoplastics are crosslinkable and are industrially used in their two forms, namely thermoplastic and thermoset Pot life period of time a paint or an adhesive stays useable Preform blow molding: preform or parison is the crude part molded or extruded before blowing Composites: reinforcements shaped before the addition of a resin or before molding Prepreg reinforcements of all forms such as fabrics, rovings, tapes, ribbons, etc., (made of aramid, glass, or carbon fibers) are impregnated with thermoplastic or thermoset resins to give prepregs. The resin level can be as high as 85%. After or during shaping, part consolidation is achieved by heating under pressure Product life-cycle management (PLM) software PLM software solutions help with the management of the entire life-cycle of a product from origin, through engineering design and manufacture, to service and disposal. People, data, processes, and business systems are factored REACH (Registration Evaluation Authorization and Restriction of Chemicals) REACH is an European Directive but it is also a Chinese regulation dealing with new chemical substance notification to the Chemical Registration Centre of the Ministry of Environmental Protection for new chemicals irrespective of annual tonnage,

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that is, chemicals other than the approximately 45,000 substances currently listed on the Inventory of Existing Chemical Substances Produced or Imported in China Failure to register will mean the substance cannot be manufactured or imported into the EU market. Recycling three main methods can be used:

• reuse used material in the same or another application • conversion into basic chemicals by chemolysis or thermolysis • energy production by combustion Relaxation relaxation is the time-dependent stress resulting from a constant strain. The stress is a function of the strain level, the application time, and the temperature. The results of tests at a defined temperature can be presented as a load versus time curve or a stress retention versus time curve The stress retention for a defined time and temperature is the actual measured stress divided by the original stress at time zero Renewable this work considers as renewable materials: recycled plastics, bioplastics derived from natural polymers, bioplastics derived from biobricks (drop-in solutions), biocompounds containing renewable reinforcements and/or bioadditives. Often, the level of renewable material is limited for technical or economic reasons or legal requirements Residual internal stresses thermoplastic injectionmoldings may contain residual stresses that are the consequence of differential cooling rates through the molded parts. They depend upon a wide range of variables including the mold design, material, and processing parameters. These stresses can significantly reduce the lifetime of parts and can reduce the dimensional stability by warpage. They also contribute to environmental stress cracking damages Residual monomer residual monomers are the nonreacted monomers remaining after polymerization. There is an obligation to comply with the limits of residual monomer levels Restriction of hazardous substances (RoHS) the RoHS directive restricts certain hazardous

GLOSSARY

substances commonly used in electrical and electronic equipment. Do not confuse EU RoHS and China RoHS; both target similar goals, but their approaches are different concerning the product categories, the restrictions, and the application schedule Rheology rheology studies the flow and deformation of materials in both solid and fluid states applying the laws of elasticity and viscosity initially proposed by Hooke and Newton. Currently, there are many mathematical models Molten thermoplastics are pseudoplastic fluids with a viscosity decreasing when shearing increases, which is an advantage in injection molding when the material flows through small cross section gates. Processing temperature, rate of flow, and residence time, etc., affect the rheology The rheology of thermosetting resins is more complex, the crosslinking or curing affecting more or less abruptly the rheology during processing Sandwich structure a sandwich structure is fabricated by firmly linking a thick core and two thin and stiff outer skins or faces. Often, the core material is foam, honeycomb, or balsa with a low density Foams are prefabricated or cast in place Normally sandwich composites are lightweight and stiff depending on the type and thickness of core, stiffness of the faces, and the binding performance. If the adhesive bond between the various elements is too weak there are risks of delamination Skin or face sheet surface material (composites, plastics, metals) of sandwich structures. Generally, the thickness of the two faces is inferior to the core thickness Smart factory the smart factory and business is a flexible system that can self-optimize performance across a broader network, selfadapt to and learn from new conditions in real or near-real time, and autonomously run entire production processes Starch carbohydrate consisting of a large number of glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants as an energy store Stress concentration stress concentration is the increase of stress near a notch, void, hole, inclusion, or other discontinuity of a plastic part

GLOSSARY

Sustainability the concept of sustainability was developed and then normalized (ISO 14,000) to help economic and industrial players to think about ways to improve or minimize the degradation of the Earth. Sustainability can be schematized as a tripod based on: 1. Environmental requirements: the basis axiom can be simplified as “Today acts mustn’t compromise the environment of the planet for tomorrow” or “present acts mustn’t compromise the needs of future generations.” 2. Economic growth: sustainable products must be efficient, competitive, cost effective, and beneficial for everybody. 3. Social progress: this includes fair labor standards and the equal treatment of women and minorities. Sustainable design, eco-design, or environmentally conscious design (ECD) sustainable design, eco-design, or ECD targets the reduction of adverse environmental impacts of a product throughout its entire lifecycle. This can involve balancing the environmental aspects of the product with its intended use, performance, cost, marketability and quality, and choosing methods to meet legal and regulatory requirements in the most environment-friendly way Tape unidirectional prepreg, generally of limited width Thermal behavior polymers are temperature sensitive A fall in temperature has only physical effects, namely an increase in the modulus and rigidity, a reduction in the impact resistance, and the material can become brittle. Semicrystalline polymers crystallize A temperature rise causes immediate and longterm effects:

• Immediate physical effects including the decay of the modulus and other mechanical and physical properties, softening, reversible thermal expansion, and, eventually, irreversible shrinkage and warpage.

• Long-term effects include irreversible creep and relaxation, irreversible chemical degradation of the material, decrease in mechanical

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properties, even after a return to the ambient temperature. Thermoplastic elastomer (TPE) thermoplastics having elastic properties in a defined range of temperatures. TPEs combine the ease of thermoplastic processing without curing and the ease of recycling, but their mechanical properties decrease as temperatures rise because of their thermoplasticity Thermoplastics thermoplastics have the simplest molecular structure with chemically independent macromolecules. Upon heating, they are softened or melted, which allows for their shaping, molding, extrusion, thermoforming, or welding. After cooling they solidify again Multiple cycles of heating and cooling can be repeated without severe damage, allowing for reprocessing and recycling Thermosets thermosets before hardening, like thermoplastics, are independent macromolecules. But in their final state, after hardening, they have a three-dimensional structure obtained by chemical crosslinking produced after (spray-up molding or filament winding) or during processing (compression or injection molding, for example) Ton of oil equivalent (toe) toe is defined as the amount of energy released by burning one ton of crude oil. It is approximately 42 GJ Tow a tow is an untwisted bundle of continuous filaments. The number of filaments is expressed in thousands followed by a k (for kilo). For example, an xyk tow has 1000xy filaments Toxicity toxicity is the degree to which something is able to produce illness or damage an exposed organism. There are four different types of toxicity, namely human toxicity, terrestrial ecotoxicity, marine aquatic ecotoxicity, and fresh water aquatic ecotoxicity. Toxicity is measured in terms of dichlorobenzene equivalents TPV thermoplastic elastomer having a vulcanized phase Underwriter laboratories (UL) fire rating the UL 94 fire rating provides basic information on a material’s ability to extinguish a flame, once ignited. Samples can be tested horizontally (H) or vertically (V) and the burning rate, the extinguishing time, and dripping are considered. The main categories are:

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• V-0: the most difficult to burn, extinguished after 10 seconds, neither dripping nor flaming particles permitted. • V-1: extinguished after 30 seconds, neither dripping nor flaming particles permitted. • V-2: extinguished after 30 seconds, flaming particles or drips permitted.

• 5V: extinguished after 60 seconds, flaming particles or drips permitted. • HB: burning horizontally at a 76 mm/min maximum rate. The UL rating depends on the sample thickness. For the same grade of polyethylene, the UL ratings are:

• V-2 for a 1.6 mm thickness • V-0 for a 6 mm thickness Underwriter laboratories (UL) temperature index the temperature index is the maximum temperature that causes a 50% decay of the studied characteristics in the long term. It is derived from long-term oven-aging test runs. The UL temperature index depends on the properties considered:

• electrical only • electrical and mechanical, impact excluded • electrical and mechanical, impact included

GLOSSARY

UL temperature indices increase with the thickness of the samples. Like all laboratory methods, the temperature index is an arbitrary measurement that must be interpreted and must constitute only one of the elements by which judgment is made Volatile organic compounds (VOCs) VOCs form a broad category of volatile chemical compounds, some of which pose a health hazard. The presence of VOCs in the atmosphere can also lead to the greenhouse effect, ozone layer depletion, and acidification Water footprint the water footprint measures the amount of water used to produce each of the goods and services used. It can be measured for a single process such as growing rice or for a product such as a pair of jeans Weld line or flow line a weld line is a mark on a molded part resulting from the meeting of two flow fronts during molding. Generally, this spot has weaker properties Wood plastic composite composite materials made of a thermoplastic heavily filled with wood fiber, wood flour, pulp fibers, peanut hulls, bamboo, straw, etc. Yield point the yield point is the first point of the stress/strain curve for which there is an increase in the strain without an increase in the stress. Parts must always operate well below this stress/ strain level during service Zero-defect manufacturing (ZDM) ZDM is often a shortcut meaning “lowest possible level of defects”

1 An Overview of Sustainability and Plastics: A Multifaceted, Relative, and Scalable Concept 1.1 Sustainability and Circular Economy 1.1.1 Sustainability is a Tripod Based on Environment, Economic, and Social Features • Environmental requirements: the basis axiom can be simplified as “To-day acts mustn’t compromise the environment of the planet for to-morrow” or “present acts mustn’t compromise the needs of future generations.” This aspect is the main purpose of this book.

• Economic growth: sustainable products must be efficient, competitive, cost effective, and beneficial for everybody.

• Social progress including fair labor standards, equal treatment of women and minorities, and so forth. This aspect is not included into the framework of this book. Please note that sustainability for a company must include:

• Direct activities that are under its direct control (e.g., manufacturing operations).

• Indirect activities from sources upstream and downstream in the supply chain, for example, energy production, freight transportation, or purchases. Indirect footprint may be very significant, and possibly greater than the direct footprint.

so forth, while consuming energy, materials, and resources as well as emitting pollution.

• Renewable polyethylene (PE) from ethanol produced from sugarcane entails growing sugarcane using fertilizers, agricultural machines, land occupation, disposal at the end-of-life, and so forth, while consuming energy, materials and resources as well as emitting pollution. Sugarcane for ethanol production used for PE synthesis can compete with food crops. In pure theory, there are no plastics or metals and other traditional materials that are sustainable and finally sustainability is a very simple dilemma, namely the choice of the lesser of possible evils and the minimization of the resulting parameters. The main obstacles are consumption of raw materials, energy, and water, the production of waste and emission of toxic elements, and, more generally, pollution. More realistically a material can be more sustainable than another or can have a different sustainability balance. In addition, ranking can evolve with time. Generally, the designer must arbitrate between two or more solutions choosing the best balance between advantages and drawbacks. A solution may be more interesting in one location than in another because of social and economic features, such as the use of agricultural means instead of industrial ones.

1.1.2 Circular Economy Sustainability is a relative concept making that a solution can be more sustainable (or less) than another. For example:

• Green electricity is more sustainable than fossil electricity, but needs manufacturing of photovoltaic cells, land occupation for setup, maintenance, disposal at the end-of-life, and

Today the common economic scheme is a linear economy that can be briefly summarized as:

• Produce and manufacture from all available resources.

• Use through the easiest way. • Dispose after use through the easiest way.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00001-X © 2020 Elsevier Ltd. All rights reserved.

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That leads, among others, to overconsumption of natural and fossil resources, and pollution. As an alternative, the circular economy (see Fig. 1.1B) proposes new criteria, including:

• Satisfactorily recover and regenerate products and materials at the end of each service life, which closes the loop. Note that the “sending back to carbon cycle” option can be understood in several ways, for example composting, the ultimate step, or chemical recycling providing new chemical blocks for the polymerization of new virgin plastics. These options are not conflicting, with recycling being used for some loops and then composting or chemical recycling being used for a deeper regenerative step leading to a virgin polymer ready for a new life. That limits the accumulation of contaminants.

• Reuse efficiently recovered materials from previous uses. Please in keep mind that in the real life there is anyway a more or less high loss.

• Keep resources in use for as long as possible. • Extract the maximum value from resources while in use, which may require an optimization of the design. (A)

Sustainable design New life new device Renewable polymers Sustainability Repair reuse recycling

Sustainable process Sustainable use phase

(B)

Low resource depletion

Low resource depletion

Sustainable manufacturing Recycling and reuse as plastics

Sustainable manufacturing

Long lasting use

Short circle of circular economy

Sending back to carbon cycle

Recycling and reuse as plastics

Long lasting and sustainable use

Extended circle of circular economy

Figure 1.1 Diagram of Sustainability and Circular economy of plastics (A) Sustainable option examples. (B) Circular economy option examples.

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We can remark the similarities between Fig. 1.1A and B. From a sustainable point of view, a circular economy is a major and essential step for better sustainability, but additional requirements included as part of sustainability must be taken into account such as:

• Create and make viable an effective after-use plastics economy.

• Decouple plastics from fossil feedstocks. • Use the best compromise (amount

of

resources/actual properties).

• Reduce the leakage of plastics into natural systems and other externalities.

• Ban and avoid accumulation of substances of concern, particularly when closing the plastic material loops.

1.2 Sustainability in the Plastics Field In the framework of the plastics industry, the environmental requirements may be expressed as follows:

• Renewable resources shall be used efficiently and their consumption at long term does not exceed their natural regeneration.

• Nonrenewable resources shall be used efficiently and their use must be limited to levels compatible with their forecasted substitution by renewable resources.

• Releases of hazardous or polluting substances to the environment shall not exceed its assimilative capacity; pollutant concentrations must be below the known critical levels of preservation of human health and the environment.

• For hazardous substances, persistent and/or bioaccumulative, a zero release is required to avoid their accumulation in the environment.

• Irreversible adverse effects of human activities on ecosystems and environment shall be avoided. Of course, products, manufacturing, use, and disposal must comply with regulations, directives, and other global or local requirements.

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Fig. 1.1 shows examples of ways of progress toward a better sustainability including the design, source of raw materials, processing methods, use phase, and disposal. Obviously, all the steps may not be suitable for a defined product; for example, renewable polymers may be not performing enough or are too expensive, actual process may be inevitably energy intensive, sustainable energy may be unavailable on site, use phase cannot be improved, recycling may be too expensive or unusable, and so forth. Being realistic, all products (new and old) more or less disturb our environment and the sustainability concept must not be understood strictly speaking, but must be considered as a relative concept of progress toward the best possible sustainability. Moreover, it is also necessary to take into account the positive aspects of “imperfect” polymers (or other materials). PE packaging pollutes, but is economical, light to carry, resilient, waterproof, and efficiently preserves food. Fig. 1.1 deserves some explanations and examples.

1.2.1 Sustainable Design Ecodesign or sustainable design and so on are new headaches for designers, needing much innovative thinking to make the decision between new sustainable systems and traditional solutions, finding the best balance between performances, durability, native resource preservation, energy saving, pollution, and carbon footprint reduction, recycling (and actual reuse), end-cost optimization, and so forth. Well-established routes mainly relate to design optimization by modeling, longer lasting parts, weight, and cost savings. Repairing and real reuse of recycled plastics save money, energy, resources, and pollution provided they comply with the technical requirements and conform to specific rules. Design thinking must take into consideration all the steps of the product life and must make arbitration between very different consequences. For example, is it wise using a higher weight of polymer, which increases environment damage, to extend the lifetime of the part to be designed? Or what is the less damaging: natural-source polymers consuming water and fertilizer or fossil polymers consuming crude oil?

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

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1.2.2 Renewable Polymers

• Damping foams decreasing damages due to

Sustainable plastics address the needs of consumers with minimum damages for the environment, land, oceans, water, health, and other environmental parameters. In addition, they must be affordable and improve social features. The feedstocks can come from the biomass or from recycling of used parts and products. Compared to their traditional counterparts, the sustainable raw materials must obey other rules, including:

• Lightweighting: automotive and other transport

• not compete the existing applications particularly food and feed

• • • • • •

use less net water be energy efficient favor renewable energy emit less greenhouse gases (GHGs) be less polluting lead to a smaller carbon footprint during the whole life cycle

1.2.3 Sustainable Processes or Sustainable Manufacturing Compared to their traditional counterparts, the sustainable processes must:

• favor step integration saving energy • preserve the chemical structure of polymers avoiding oxidation, mitigating residence times, and high temperatures

• • • • • •

be energy efficient favor renewable energy emit less GHGs use less net water be less polluting lead to a smaller carbon footprint

unexpected impacts. vehicles, and lighter packaging saving fuel for transport.

• Packaging lengthening lifetime of fresh food.

1.2.5 Waste Management, Repair, Reuse, Recycling Of course, the prime solution is the mitigation (or cutting) of waste generation. In the other cases, waste must be reused or suitably treated. Reuse, if conducted under good conditions, is the best recovery solution, particularly when targeting the same purpose for which the original parts were conceived. The possibility of repairing must be taken into account before the choice between reuse or waste treatment. In the other cases, waste management must be taken into account, including:

• The actual repairing methods of the part or device and the actual outlets.

• The possibility to integrate an existing stream of plastic wastes at end-of-life.

• The existence of a recycling method. • The possibility to really use the recycled material. Reprocessing in the production for the original purpose is the best recycling solution. Other solutions include, in descending order of interest:

• Energy recovery using used parts as fuel. • Incineration under good conditions without energy recovery.

• Landfilling of wastes, the worst solution.

1.2.4 Sustainable Use Phase

Of course, the used method must comply with laws, directives, and other regulations.

Plastics can save energy and, consequently, pollution during the use phase. For example:

1.2.6 Economic Involvements

• Insulation foams saving energy for heating and cooling devices, warehouses, houses etc. Among emerging goals, let us consider the construction of zero-energy houses and buildings.

According to the context, sustainability may induce economic advantages or overspending coming from, for example the use of renewable polymers, consumption of expensive additive lengthening the part lifetime, use of specific waste

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collection streams and recycling process, among others. In that case, the designer should ask the question, “Who pays the extra cost?” Often the end user does not agree, willing a better sustainability but at the same price as the traditional part.

1.3 People’s Perception of Plastics Sustainability Of course, the perception of sustainability differs according to the polled people—plastics sector stakeholders or general public.

1.3.1 Opinions of Plastics Sector Players Bonnie J. BACHMAN, Shristy BASHYAL, and Margaret BAUMANN (Missouri University of Science & Technology,  GHA Associates) led a survey, “Sustainability in the plastics industry: concerns, issues, and strategies.” For more than 200 players of the plastics industry, 15 subjects are ranked from very high to low concern (see Table 1.1). Plastics stakeholders already apply specific methods (see Table 1.1) to improve sustainability, primarily in descending order:

Table 1.1 Sustainability in the Plastics Industry: Main Concerns. Nonrenewable resource depletion (e.g., crude oil) Government legislation in regards to sustainability Increasing consumer concern for sustainability issues Air, water, or other environmental pollution Increasing employee’s interest in sustainability Water supply or access issues Population growth Food supply or safety issues Societal pressures—social license to operate your business Climate change Global political security Urbanization as populations migrate to cities Biodiversity reduction and habitat destruction Poverty and income differentials Global health inequalities Sustainability in the plastics industry: main used ways for improvement

Waste reduction Energy consumption minimization Designing with 3R in mind Banning toxicity or harmful chemicals Developing new sustainability-related opportunities Increase company and brand sustainability image Increase organization sustainability awareness Improving sustainability in packaging Increase supplier and customer sustainability… Including sustainability in strategic analysis Optimizing carbon or GHG emissions Reacting to sustainability policies and regulations Other Increase employee sustainability awareness Influencing policies on sustainability

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

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• waste reduction • energy consumption minimization • designing with 3R (repair, reuse, recycling) in mind

• developing

new

sustainability-related

opportunities

• banning toxicity or harmful chemicals • optimizing carbon or GHG emissions Second, they apply general recipes such as:

• Increase sustainability awareness all along the product life cycle: suppliers, various levels of the organization, company, brand, employees, and customers.

• Reacting

to

sustainability

policies

and

Of course there are counterbalancing features and negative points of view. For instance, plastics are perceived by about 75% of the consumers as the least environment-friendly type of packaging. On balance, sustainability should be beneficial. For example, the American Chemistry Council (ACC— https://www.americanchemistry.com/About/) estimates that a circular economy for plastics could add 5% new jobs and billions of dollars to the US economy by expanding the use of plastic recycling technologies. On the other hand, social networks reflect mass opinion of social structures including a set of social actors such as individuals, organizations, and business players. Choosing one social network and examining the flow of exchanges during a defined period of time may give a rough idea of the interest of the actors on a defined subject.

regulations. Third, they sustainability.

try

influencing

policies

on

1.3.2 General Public Opinions: Survey Example and Social Network Opinions According to a public opinion poll pertaining about 6000 consumers in 11 countries across North America, Europe, and Asia, Accenture (https:// newsroom.accenture.com/news/) found that consumers remain primarily focused on:

• quality (near 90%) • price (80% 1 ) • health and safety considerations (nearly 50%) If environmental impact is not so high, it is cited by 1 out of 3 respondents and is on an encouraging trend:

• Nearly 75% of respondents said they’re currently buying more environment-friendly products than they were five years ago.

• About 80% said they expect to buy more over the next 5 years. Moreover, 50% of consumers said they would pay more for sustainable products designed to be reused or recycled.

1.3.2.1 Plastics Concern Overview The general opinion of a social network oriented to individuals that will ultimately buy plastics or traditional materials is of a great interest. In this way, we analyze, during a defined period of time, the stream of posts of a social network oriented to individuals. Of course there are some opinions of companies having plastics activities. First and foremost, plastics are not the cup of tea of social networks with traffic below 0.0001%. In the following, without other indication, percentages are linked to identified posts pertaining to plastics only. Three topics take into account more than 95% of the post stream:

• Environment is the most important; • Use is second; • Technical concerns are third, coming often from companies. Economy and social or societal topics gather less than 5% of the post stream. This ranking (see Fig. 1.2A), more or less subjective, must be cautiously taken into account and, of course, other data could be found according to the social network, the period of time, the breakdown scheme, and so forth. The total percentage is higher than 100 because some posts are included in several categories.

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7

(C)

(A) 0

0

50

100

%

%

Packaging Environment

Engineering Automotive

Use

Medical Construction

Technical

E and E Industry

Economics

Composites Aeronautics+space

Social

Furniture Sports and leisure Appliance

(B)

0 Recycling

50

%

(D)

Pollution including ocean litter

0

50 %

Recycling

Environment

Technology

Sustainability

Waste

Waste Thermoforming Toxicity Design Health Reuse or repair Ecofriendly + green +clean Molding

Water

Extrusion

Reuse or repair

Water

Biobased, renewable

Blow molding

Climate change Circular economy Biodegradable Biodiversity

(E)

0

Renewable

Business

Ban

Economy

50 %

Compost, compostable Market Single use Ecodesign

Sales

Non renewable+fossil

Circular economy

Regulation

Consumption Prices

Figure 1.2 (A) Posts breakdown, categories, % linked to identified posts. (B) Environment: Posts breakdown, % linked to identified environment posts. (C) Use: Posts breakdown, % linked to identified application posts. (D) Technical features: Posts breakdown, categories, % linked to identified technical posts. (E) Economics: Posts breakdown, % linked to identified economics posts.

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1.3.2.2 Plastics Concern Details

• Processing methods—molding, extrusion, thermoforming—are topics of posts emitted only by plastics manufacturers.

Environment

“Environment” gathers multiple topics (see Fig. 1.2B) combining technical, economic, and health concerns. The main topics, in descending order, relate to:

• recycling • pollution, including a high share of “ocean pollution”

• • • • •

environment sustainability waste toxicity health

Most items appear rather general purpose, which is normal for a social network oriented to the general public. Some terms such as ecofriendly, green, and clean do not have a defined significance, but indicate a general concern. Other items are discreet. The expressed opinions are not systematically negative including solutions to obviate damages caused to the environment. Applications

The “use” category gathers 12 application fields (see Fig. 1.2C):

• Packaging supremely prevails over the categories engineering, automotive, medical, construction, electricity and electronics, industry, composites, aerospace.

• Furniture, sports and leisure, and appliance categories initiate a negligible stream of posts. We can note the ranking of post streams is not in accordance with consumption in the related sectors. Technical Features

These topics (see Fig. 1.2D) are not really concerns for individuals, but are of interest for plastics manufacturers.

• Recycling (already quoted) is the major concern followed by: • technology as general topic, and • waste (already quoted).

• Reuse and repair are ranked in 6th position, near to design.

• Water is the last significant concern. Economy

Economy gathers less than 5% of posts linked to plastics and mostly items appear rather general purpose, which is not abnormal for a social network oriented to the general public. Curiously, prices and societal topics are less quoted. Fig. 1.2E shows the ranking of various items. Once again, those data and ranking are more or less subjective and must be cautiously taken into account. Percentage of posts are only given for information and are not intrinsically significant. Of course, other data could be found according to the social network, the period of time, the breakdown scheme, and so forth.

1.4 Drivers of Change Promoters of change mainly include:

• standards and reporting; • policies and incentive measures; • voluntary drivers surfing on the green wave: marketing strategy based on sustainability;

• careful forecast of major changes in the environment: the best-known examples being crude-oil shortage and climate change.

1.4.1 Standards and Reporting Standards and reporting help to ask oneself on the sustainability of the product to be designed and on the targets. For example, Costello (2011). ISSN 1546-962X, describes key elements and targets linked to a roofing product. Key elements of the standard include:

• • • •

product design life cycle assessment considerations minimization of chemicals of concern product manufacturing

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energy consumption water consumption waste durability corporate governance (social responsibility) innovation

The target of information related to sustainability is to help manufacturers to point out major concerns, search options, and to take decisions about:

• choice of the raw material • supply chain modifications • product changes from derivatives up to totally new products

• research of step integration • manufacturing changes from adjustments up to alternative methods or completely new

• performance improvements • end-of-life options • corporate governance The goal is producing more sustainable products. Of course, standards, certification, and conformance are also applicable to the product to be designed, in this example, roofing membranes. More generally, the GRI (Global Reporting Initiative, https://www.globalreporting.org/information/) Sustainability Reporting Guidelines and the ISO 26000:2010 offer reporting principles, standard disclosures and an implementation manual for the preparation of sustainability reports by organizations, regardless of their size, sector, or location. Applications are voluntary. “GRI G4 Guidelines and ISO 26000:2010, How to use the GRI G4 Guidelines and ISO 26000 in conjunction” https:// www.iso.org/files/live/sites/isoorg/files/archive/pdf/ en/iso-gri-26000_2014-01-28.pdf compares the two main documents. In the context of this book, the following information is of interest, but many other topics are quoted including for example Environmental Grievance Mechanisms, Labor Practices and Decent Work, Employment, Labor/ Management Relations, Occupational Health and Safety, Training and Education, Diversity and Equal Opportunity, Equal Remuneration for Women and Men, among others. Readers must

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verify and update this information. The reader is solely responsible for the chosen solutions. Examples of quoted topics: Materials • materials used by weight or volume; • percentage of materials used that are recycled; • sustainable resource use. Energy • direct energy consumption within the organization; • energy consumption outside of the organization; • sustainable resource use; • energy intensity; • reduction of energy consumption; • reductions in energy requirements of products and services; • climate change mitigation and adaptation. Water • total water withdrawal by source; • water sources significantly affected by withdrawal of water; • percentage and total volume of water recycled and reused; • sustainable resource use. Emissions • climate change mitigation and adaptation; • direct GHG emissions (Scope 1); • energy indirect GHG emissions (Scope 2); • other indirect GHG emissions (Scope 3); • GHG emissions intensity; • reduction of GHG emissions; • emissions of ozone-depleting substances (ODS); • NOx, SOx, and other significant air emissions. Effluents and waste • total water discharge by quality and destination; • prevention of pollution; • sustainable resource use; • total weight of waste by type and disposal method; • total number and volume of significant spills; • Weight of transported, imported, exported, or treated waste deemed hazardous under

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the terms of the Basel Convention Annex I, II, III, and VIII, and percentage of transported waste shipped internationally; • Identity, size, protected status, and biodiversity value of water bodies and related habitats significantly affected by the organization’s discharges of water and runoff; • Protection of the environment, biodiversity, and restoration of natural habitats. Biodiversity • Operational sites owned, leased, managed in, or adjacent to, protected areas and areas of high biodiversity value outside protected areas; • Description of significant impacts of activities, products, and services on biodiversity in protected areas and areas of high biodiversity value outside protected areas; • habitats protected or restored; • Total number of IUCN (International Union for Conservation of Nature) Red List species and national conservation list species with habitats in areas affected by operations, by level of extinction risk; • Protection of the environment, biodiversity, and restoration of natural habitats. Products and services • extent of impact mitigation of environmental impacts of products and services; • prevention of pollution; • sustainable resource use; • climate change mitigation and adaptation; • percentage of products sold and their packaging materials that are reclaimed by category. Transport • Significant environmental impacts of transporting products and other goods and materials used for the organization’s operations, and transporting members of the workforce; • sustainable resource use; • promoting social responsibility in the value chain. Overall • total environmental protection expenditures and investments by type; Supplier environmental assessment • percentage of new suppliers that were screened using environmental criteria;

• avoidance of complicity; • promoting social responsibility in the value chain; • due diligence. Law compliance • Monetary value of significant fines and total number of nonmonetary sanctions for noncompliance with environmental laws and regulations; • Respect for the rule of law.

1.4.2 Policies, Directives and Regulations Regulated actions may be global, national, corporative, or private as well as voluntary or mandatory. Very few examples are quoted below. Of course, plastics activities must obey general and specific policies, directives, and regulations. The reader is solely responsible for his or her own problem and must study the requirements of the countries concerned by formulation, manufacture, commercialization, application, and waste disposal.

Likewise, sustainability reporting can be voluntary or mandatory according to countries and the importance of companies implicated. Mandatory regulations are efficient drivers with a defined framework and time limits. Example of mandatory European Directive: European Ecodesign legislation is based on Directive 2009/125/EC of the European Parliament and of the Council of 21 October 2009 establishing a framework for the setting of ecodesign requirements for energy-related products. This base is completed by numerous more recent directives dealing with many items such as for example:

• • • • • • • •

air conditioners and comfort fans air heating and cooling products circulators computers domestic cooking appliances electric motors external power supplies household dishwashers

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• • • •

household tumble driers

• • • • • • • •

local space heaters

• • • •

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household washing machines industrial fans lighting products in the domestic and tertiary sectors heaters and water heaters power transformers professional refrigerated storage cabinets refrigerators and freezers simple set-top boxes

Research commissioned by Unilever among 20,000 consumers in five countries found:

• 33% choose brands claiming social or environmental practices.

• 21% choose brands promoting sustainability. Big societies expand strategies based on all the facets of sustainability. For example, Ford Motor Cy identifies and studies a broad panel of key issues and impacts including:

standby and off mode electric power consumption of household and office equipment and network standby

• Financial health: the long-term viability of

televisions

• Product innovation is the key of sales, profit,

vacuum cleaners ventilation units water pumps

production and resourcing exchange and transfer accounting and regulation consumption and use labor and well-being technology and infrastructure wealth and distribution

The ecological domain may be divided into subdomains such as:

• • • • •

1.4.3 Examples of Marketing Strategy Based on Sustainability

solid fuel boilers

Sustainability reporting may include economics, ecology, politics, and culture domains. It is an important step that demands deep and long-term reflection. Only economics and environment are discussed in the framework of this book. The economic domain may include:

• • • • • • •

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materials and energy processing transport and distribution water and air pollution: emission and waste

companies is being judged on profitability and other financial metrics. and sustainability progress.

• Mobility Innovation: the goal is to make mobility affordable in every sense of the word—economically, environmentally, socially—and to provide seamless mobility for all.

• Brand perception. • Operations and logistics energy use and GHG emissions: Human activities are responsible for almost all of the increase in GHGs in the atmosphere over the past 150 years. The largest source of GHG emissions from human activities comes from burning fossil fuels for electricity, heat, and transportation.

• Product carbon footprint/fuel economy. Fuel economy: • reduces carbon dioxide (CO2) emission, • slowdowns climate change, • reduces oil dependence, • increases energy sustainability, • improves customer satisfaction responding to his(her) demand for fuel efficiency, • saves money.

• Materials and waste management: Sustainable materials management (SMM) is a systemic approach to using and reusing materials more productively over their entire life cycles.

• Water footprint: global manufacturing wateruse-per-vehicle reduction was of 30% for 6 recent years.

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• Environmental

management

and

process

innovation.

• • • • • • • • • • • • • •

greater efficiency and environmental performance in products, services, and facilities.

Human capital management. Diversity and inclusion. Employee wellness, health, and safety. Supply chain management, assessment, capacity building, and performance. Vehicle and traffic safety. Product quality. Customer satisfaction. Ethical business practices. Sustainability strategy and vision. Regulatory compliance. Voluntary standards and certifications. Fuel economy and GHG regulations. Other policy/regulations. Big data.

1.5 Sustainable Material and Waste Management 1.5.1 Sustainable Materials Management: A New Approach to Material Selection SMM (see https://www.epa.gov/smm/sustainable-materials-management-basics) is a systemic approach to using and reusing materials more productively over their entire life cycles. By examining how materials are used throughout their life cycle, an SMM approach seeks to:

• Use materials in the most productive way with an emphasis on using less.

• Reduce toxic chemicals and environmental impacts throughout the material life cycle.

1.4.4 Cautious Forecast of Major Changes in the Global Environment The best-known examples of major changes are crude oil shortage and climate warming. Among other concerns are, for example water stress, pollution, and so forth. For instance, as air travel expands around the world, Boeing is taking a leadership role to continue to reduce aviation environmental impact by reducing fuel use, GHG emissions and noise. Boeing’s environmental strategy includes:

• designing and building more fuel-efficient airplanes,

• improving gate-to-gate operational efficiency for customers,

• advocating for modernized air traffic management systems,

• developing sustainable aviation biofuel, • reducing environmental footprint. Today, airplanes are already 70% more fuel efficient and 90% quieter than the first jets. To make further progress, more than 75% of Boeing’s commercial research and development funding support

• Assure we have sufficient resources to meet today’s needs and those of the future. Global resources are finite, making that uses of materials are fundamental to global economy and environmental future. The growing world population and economies intensifies the competition for finite resources. More productive and less impactful use of materials are vital for the survival of our society, its competitiveness, and its prosperity. Without any change, many shortages of resources are forecast for the next few decades. At the global level, the consumption of natural resources and production of waste have exploded. The global raw material use rose during the 20th century at about twice the rate of population growth. For every 1% increase in gross domestic product (GDP), raw material use has risen by 0.4%. Furthermore, much of the raw materials return to the environment as waste sometimes within one year. We face a projected world population of more than 9 billion people by 2050 and rapid economic growth in newly industrializing countries. Unsustainable consumption of natural resources and concomitant environmental degradation translate into higher material costs, supply uncertainties, and disruptions. Resource efficiency and sustainable material management are essential for

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environmental and climate protection, employment, and social benefits. Improving resource efficiency requires the productive collaboration amongst policy-makers, business, academia, and consumers. The Annex to the G-7 Leaders’ Declaration, Schloss Elmau, Germany, June 8, 2015, describes some topics to be addressed in workshops under the G7 Alliance on Resource Efficiency:

• Business initiatives and best practices. • Policies to create favorable framework conditions.

• Lifecycle-based decision-making tools, data, concepts, and methodologies of resource efficiency.

• Industrial symbiosis, that is, the sharing of services, utilities, and by-product resources among industries, for example, through EcoIndustrial Towns.

• Support for small and medium-sized enterprises, including practical tools.

• Policy approaches and best practices in specific sectors.

• Sustainable products and purchasing, green public procurement, local supply chains and the integration of resource efficiency into decision-making in government agencies.

• Circular economies, eco-design, sharing economies, and remanufacturing.

• Fostering research and innovation for resource efficiency and integrating resource efficiency into education and training.

• Relevant activities in international forums and international organizations.

• Experience from bilateral cooperation with developing countries and possible ways for the G7 to collaborate with and in support of these countries.

• The potential of substituting nonrenewable resources resources.

with

sustainable

renewable

The G7 Alliance on Resource Efficiency will conduct workshops at least once a year under the leadership of the respective presidency. The use of virtual workshops and videoconferences is encouraged so as to maximize benefits while limiting travel requirements and resources.

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1.5.2 Sustainable Waste Management Sustainable waste management can be divided into:

• Waste reduction by using material resources efficiently, which reduces raw material consumption, save costs and optimizes the environmental pollution.

• Waste recycling of production wastes. If recycling of processing wastes is thought of at the start, this is the ideal and real case leading to the perfect closed loop recycling: sprues, runners, and defective moldings or profiles are not mixed and are safely stored before separate grinding for a reuse in the same part or profile. Most manufacturers use this scheme.

• Waste recycling, reuse, and remanufacture of postconsumer waste products.

1.5.2.1 Recycling of Production Wastes Of course, the best method of waste management is minimizing the waste level due to diligent planning and technical methods. The most common planning methods include, for example:

• no excess stock of raw materials, parts, finished products;

• no overprocessing: producing to a higher standard initiating extra wastes (and adding costs) that the customer does not want;

• no

over-production—producing the exact quantity required to meet customer demand;

• producing high quality without faulty or inadequate products that do not meet customer requirements. To be successful, the process must obey some basic rules, such as:

• Do not damage the material during processing with excessive temperatures, residence times, shear strains, etc.

• Sort materials at the exit of processing machines.

• Separate streams of different materials. • Keep clean avoiding dust and other pollutants.

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• Keep safe during storage avoiding moisture, high temperature, sunlight, UV and other aggressive environments.

• Dry the material before reprocessing if necessary. Generally, heat, moisture, and shear damage the processed polymers—often macromolecules are shortened, but sometimes there is also a crosslinking, materials are oxidized and eventually hydrolyzed leading to alteration of all the properties:

1.5.2.2 Treatment of Postconsumer Products Of course, management of postconsumer plastics is much difficult especially for mixed or comingled waste or single stream collection. Two basic issues concern the initial waste collection and the end step, the actual reuse. Fig. 1.3 shows some solutions by descending order of interest from a sustainability point of view.

• Rheology

is modified, often viscosity decreases but sometimes it increases.

Waste minimization

• Mechanical and thermal performances often

Repair and reuse

decrease with tensile strength and modulus decay. For fiber reinforced polymers, shortening of fiber length magnifies the phenomenon. Natural fibers, and to a less extent, synthetic and glass fibers can be chemically damaged by the service life.

Recycle and reuse Energy recovery Composting Landfilling

• Aging resistance, chemical behavior, flammability and electrical properties are altered by the loss of protective additives, the alteration of chemical structure, the uptake of chemicals during the service life.

• Color is often modified notably for white and light-colored compounds.

• Unwanted odors may be emitted. There are several ways to hide the property decreases if they are not upgraded by compounding:

• Use recycled material at tuned concentrations in place of the virgin material. Generally speaking, 20% or 25% is often chosen but according to the requirements concerning the new manufactured parts or goods, lower or higher rates can be used.

• Hide the recycled material with one or two layers of virgin material by coinjection or coextrusion. This technique is used for films, tubes, and injected parts.

• Use the recycled material as inert filler: this solution is often used for thermosets that cannot be de-crosslinked.

Figure 1.3 Examples of postconsumer waste treatments ranked by descending order of sustainability.

Waste minimization may be improved thanks to better and more efficient processing methods, and by lengthening of the actual lifetimes due to better design and use of more performing plastics. Repair is already applied, for example to liners, conveyor belts, composites, and so forth.

• Reuse may be in the initial domain or in a new one.

• Recycling may be more or less advanced leading to physical modifications for mechanical recycling up to renewed chemical structures for chemical recycling. Of course, the possibility to really use the recycled material is a key factor of success.

• Reprocessing in the production for the original purpose is the best recycling solution leading to a closed loop solution with relatively little loss of matter, low wastes but consuming energy. Really it is not an endless process but it is the most virtuous.

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Other solutions include, in a descending order of interest:

• energy recovery using used parts as fuel, • harmless incineration without energy recovery, • landfilling of wastes, the worst solution. The choice of the recycling method is not, free but depends on the nature of wastes:

• Polymers in rubbish cannot be sorted and reprocessed.

• Presorted polymers such as bottles can be reprocessed with optimized methods.

• Certain polymers, conventional or biodegradable, may be incompatible with others and a few percentages of one can disturb the quality of the recyclate and make it unsuitable for practical applications. This is an important parameter for biodegradable polymers.

• Some polymers are relatively easy to reprocess, others are not and lead to poor performances. Finally, there is not only one answer, but several, and there are multiple ways through the various steps of recycling strategies as we can see through a few examples. Sectorial routes lead to specific streams with general advantages such as, for example:

• A presorting resulting from the specificity of each stream, for example, bumpers of cars, bodies of fridges, etc.

• A limited number of probable polymers. For example, the most frequently used polymers for bottles are polyvinyl chloride (PVC), polyethylene terephthalate (PET), and PE.

• The opportunity to study the most accurately methods of dismantling and sorting. Carmakers provide procedures for each main part, bumpers, instrument panels, etc., of each car model.

• A better knowledge of the possible pollutants resulting in more efficient washing and cleaning processes.

• The possibility of a better industrialization and a more efficient marketing of the recyclates.

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Recycling achieves multiple goals: smartly dispose of wastes, add value to wastes, improve environment indicators, and save resources and money. Today, recycling is the first source of renewable plastics offering many advantages, but also some possible drawbacks. As for all other polymers, before selection, the designer must study the pros and cons related to economic, environmental, technical, regulatory, reliability, and performance consequences. Environment Advantages

Please remember that to make the comparisons easier between several materials or routes, CO2 emission has been chosen as a standard to quantify the greenhouse effect of the manufacture, use, and discarding of any good. The carbon footprint can be defined, in a simplified manner, as the sum of all emissions (and capture) of CO2 and other GHGs, expressed in equivalent CO2. (The capture of CO2 is negatively accounted) The balance includes all the steps of the product life: raw material synthesis, manufacture, transport, use, and endof-use treatments. Upstream and downstream steps are to be accounted for. It can be noted that the carbon footprint of any plastic part depends on:

• The feedstock and polymerization route. For example, the growing of plants leading to renewable raw materials absorbs CO2 and their footprint is negative for this step but positive for their transportation.

• The processing methods. • The actually used energy sources. For example, electricity from wind turbines has a negligible impact on the carbon footprint. Concerning recyclates, the carbon footprint depends on:

• The recycling route of the postconsumer wastes, mechanical or chemical recycling, burning, gasification etc.

• The level of reused recyclate. Consequently, such data can dramatically differ according to the sources.

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Most used recyclates are commodities, but engineering plastics are marketed or in-house recycled. For example:

• SoRPlas by Sony, made from recycled DVDs and optical sheets from TVs, could cut CO2 emissions by 77.3% over the manufacture of conventional plastic materials.

• by using 100% postconsumer recycled resin for bottles, the cradle-to-gate energy consumption of the resin compared to virgin is claimed reduced by 52% and the carbon footprint is claimed lowered by 57%.

• US-based Nestle´ Waters, manufacturer of the Arrowhead brand bottled water, has committed to using 50% recycled content in its water bottles.

• For recycling of PET, the carbon cost of producing recycled food grade rPET 78 pellet in 2010 was 254 kg/t, while the cost of producing virgin PET was 681 kg/t.

Cost Savings

Fig. 1.4A displays the material cost saving percentage when totally replacing the virgin polymer with recycled one but often in real life, just a fraction of the polymer is replaced by recyclate. Very different cost savings may be found according to prices of crude oil and virgin polymers. For the quoted example, we can remark that, according to the polymer, costs savings evolve between 10% and 40% in round figures. If there is a high demand for recyclates the prices rise and conversely. Prices of polymer and crude oil are highly volatile making that these data are not usable for economic forecasts. Regulations and Limitations

First of all, recycled plastics as all the virgin plastics must obey national, regional, global directives, rules, regulations, and other requirements related to the aimed parts, subsets, devices. Countries to be considered include those of production, transformation, use, and disposal.

(A)

Cost saving, %

50% 40% 30% 20% 10% 0% LDPE

PP

PS

HDPE

PET bottle

(B) LFRT TPE ETP ETP ETP ETP TPE ETP

%

TPE 0

10

20

30

40

50

60

Figure 1.4 (A) Recyclates save costs. (B) Examples of regrind levels for various thermoplastics.

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Let us remember two examples of limitation of regrind (the less risky form of recycled plastics) but many other rules or regulations exist. Once again, it is the responsibility of the reader to search the ins and outs concerning his or her own case. Underwriters Laboratories (UL’s) recommendations on the use of regrind: UL accepts:

• No regrind for thermosets, thermoplastic elastomers (TPEs) and recycled materials.

• Regrind up to a maximum of 25% by weight with the same grade of virgin thermoplastic at the same molder facility without further testing. For regrind levels exceeding 25% in the same virgin thermoplastic, UL requires a special evaluation of relevant performance tests such as mechanical, flammability and aging tests. Of course, these statements can evolve with time. Producer’s recommendation examples Fig. 1.4B displays some examples of maximum levels recommended by producers of long fiber reinforced thermoplastics (LFRT), engineering thermoplastics, and TPE. Maximum levels recommended for LFRT are very low because of the break of long glass fibers, which leads to a decrease of mechanical performances. For the other thermoplastics, levels depend on the sensitivity to hydrolysis and thermo-oxidation and the processing parameters. These indications relate to regrind of materials carefully processed and cannot be used without severe previous testing.

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1.6 Sustainability is Vital to Mitigate Environment Damages Caused by Booming Plastics Consumption To fight the unavoidable consumption rise leading to wrong consequences for resource depletion and pollution resulting in climate change, sustainable behaviors become essential to mitigate climate warming (see Fig. 1.5). Resource depletion and pollution, at a constant pace, evolve as global population and standard of living. Apart from energy, the Earth is an isolated system making that resources dry up, which needs cautious management. At the actual pace, some experts forecast shortages of common resources, crude oil, or some metals, for example. A universal sustainable behavior is the way to stretch the limits of resource availability.

1.6.1 Population Growth Evolution of global population is a key factor for geopolitics, technological development, economics, and environment. Between 1900 and 2000, the global population has been nearly multiplied by 4 from 1.7 billion up to 6 billion leading to deep adaptations for food and feed production, energy consumption, housing, material requirements, and pollution. More or less irrespective of that, scientific, technical, and industrial progress has modified our day life and our future.

Pollution Resources depletion

Climate warming

Consumption

Climate warming Population growth and GDP rising

Figure 1.5 Mitigation of climate warming thanks to sustainability.

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Most experts forecast an additional population growth for the next decades and, perhaps a stabilization at a level of 10 billion people in round figures.

1.6.2 Standard of Living GDP is a measure of the value of all final goods and services yearly produced. In other words, it determines the economic performance of a whole country or region. The combined gross national product of all the countries in the world is the gross world product. Because imports and exports balance exactly, the gross world product also equals the total global GDP. According to the calculation method and sources—CIA’s World Factbook, World Bank among others—the gross world product in round figures totals approximately US$ 80 trillion to US$ 110 trillion. The more familiar use of GDP estimates is to calculate the growth of the economy from year to year. The pattern of GDP growth is held to indicate the success or failure of economic policy and to determine whether an economy is “in recession.” GDP per capita is often used as an indicator of living standards. In fact, GDP may increase while real incomes for the majority of the population decline.

1.6.3 General Consequences of Population and Gross Domestic Product Growths Population growth and higher standard of living induce multiple consequences such as for example:

• Increase of basic needs: food and feed, energy, space, etc.

• Increase of land use, deforestation, (over) urbanization, desertification, etc.

• Resources: growth and decline may create imbalance even if, in the long run, population stabilizes. In all cases nonrenewable resources are a concern due to their depletion, the Earth being an isolated system from this point of view.

• Technological evolutions induced by adaptation to global population variations, economics, and space and time distribution of the population.

• Geopolitics: main nation rankings, risks of conflicts for space, food, economy.

• Economics: hypotheses based on population regression induce a risk of economic regression when, conversely, we can hope the persistence of the economic development.

• Health issues: people aging, risks of autopoisoning, degeneration.

• Pollution: CO2 and other GHG emission, ozone depletion, climate warming, sea level rise, biodiversity, etc.

• Day life: work time, mobility, sport, entertainment, culture, well-being.

• Education, language, etc. • Connected world.

1.6.4 Sustainability, the Expected Response to Climate Change Climate and climate change are very complex phenomena and it isn’t in our purpose to make a scientific exam of the problem, but we aim to help the reader to think about various parameters affecting the climate during the next years. The Earth is a semi-isolated system:

• Energy can be, to some extent, exchanged with space. Solar radiation brings heat by infrared radiations that are a part is reflected by the earth surface. Then those reflected IR radiations are partly reflected by the stratosphere or are lost in space according to the amount of GHGs. That leads to the global warming.

• In addition, it must be noted that UV radiations are also filtered by the ozone layer mitigating their harmfulness, the less so as ozone is depleted.

• Ore, fossil fuels, atmosphere and other physical resources have a defined potential without inlet stream. If we waste these resources their potential is lowered forever. This natural process is magnified by an overproduction of CO2 and other GHGs such as water vapor (H2O), methane (CH4), nitrous oxide Freon’s (chlorofluorocarbons—CFCs), (N2O), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and so on.

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The current overproduction of CO2 is partly offset by plants and trees consuming and sequestering CO2 via photosynthesis. In brief, the greenhouse effect allows solar radiations to pass through the Earth’s atmosphere, but prevent infrared radiations to pass from the Earth’s surface and lower atmosphere toward space. This natural process is magnified by an overproduction of CO2 and other GHGs. Atmospheric concentrations of CO2, mainly due to fossil fuel combustion (hydrocarbon-based fuels formed by the decomposition of prehistoric flora and fauna, e.g., oil, natural gas, coal, tar sands, and peat) are now about 30% above preindustrial levels. GHGs can be of natural origin such water (also produced by human activity) or coming from human activity such as CFCs, HFCs, or PFCs. Global warming potentials (GWP) are as diverse as their chemical formulae. GWP is the warming effect of 1 kg of the considered gas to the effect of 1 kg of CO2. Many figures can be found in the literature. For a medium period, a century in the framework of this book, GWP in round figures are about:

• • • •

• Agricultural activities. • Use of fertilizers leading to higher N2O concentrations.

• Use of CFCs in refrigeration systems. • Use of CFCs and halons in fire suppression systems and manufacturing processes.

• Transportation based on fossil fuels. Previous observed climate changes led nations to decide concrete measures, but response times to policy decisions (and effective actions) are very long, being often in the order of several decades. Unless energy policies are changing drastically, the world should continue to depend on fossil fuels until their scarcity and their costs become unbearable. In round figures, shares of various fuels could be:

• fossil fuels in the range of 60% 70%, • renewable origin about 20% • nuclear nearly 15%

1 for CO2 (baseline) 20 25 for methane 290 for nitrous oxide 1500 7500 for some CFC and HFC

The most important gases directly emitted by humans and human activities include:

• • • •

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water vapor carbon dioxide (CO2) methane (CH4) nitrogen oxide (NOx)

Among the main sources of GHGs due to human activity are:

1.6.4.1 Main Greenhouse Gases Overview Main GHGs include: Water Vapor

Water vapor comes from evaporation of ocean, sea, and river water on the one hand, and result in precipitations on the other hand. Water vapor is naturally produced as a by-product of respiration in plants and animals. Industrially water is produced by oxidation, specially burning, of hydrogenated species mainly fossil and renewable hydrocarbons. Environmentally speaking, water vapor probably accounts for about 60% of the warming effect. Carbon Dioxide

• Burning of fossil fuels rich in carbon and then producing high quantities of CO2.

• Land use change, mainly deforestation in the tropics leading to suppression of living absorbers of CO2.

• Livestock enteric fermentation and manure management, paddy rice farming, land use and wetland changes, pipeline and industrial leaks, landfill emissions, and septic systems, leading to higher methane atmospheric concentrations.

CO2 is naturally emitted by human and animal respiration, volcanic eruptions, and other natural phenomena. Industrial activities such as the combustion of wood, coal, municipal solid waste and fossil fuels producing heat and energy emit large amounts of CO2. Fermentation processes of organic materials leading to common products such as bread, beer and winemaking also emit CO2. Dissolved in water, seawater, groundwater, rivers, lakes, and oceans, CO2 modifies the aquatic life.

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• renewable energy of low carbon sources, for

CO2 is the main constituent of GHGs and has significantly risen from pre-industrial levels. Combustion of fossil fuels and deforestation have additive effects leading the atmospheric concentration of CO2 to increase by more than 40% since the beginning of the age of industrialization. CO2 is often claimed the main responsible of the climate warming. Moreover, it is chemically stable and has a long atmospheric lifetime, which worsens issues. Fig. 1.6 proposes an example among many others of forecasts of CO2 emitted by population without any change in our behavior. Without additional mitigation efforts beyond those in place today, warming by the end of the 21st century will lead to high to very high risk of severe, widespread, and irreversible impacts globally. Literature often displays temperature rises in the order of 0°C up to 5°C according to the scenario including or not adaptations (Climate Change 2014, Synthesis Report-Summary for Policymakers, https://www.ipcc.ch/pdf/assessment-report/ar5/syr/ AR5_SYR_FINAL_SPM.pdf). Reduction opportunities for CO2 include, for example:

example wind, photovoltaic, tide, geothermal, hydroelectric, etc.;

• Energy savings: • reducing personal energy use by turning off lights and electronics when not in use;

• reducing travels thanks to e-meetings; • reducing distance traveled in vehicles saving petroleum consumption thanks to optimized journeys; • redesign the tourism industry. If the previous measures are not efficient, CO2 can be captured and then:

• Used as feedstock for polymerization of plastics. For example, Bayer produces polyurethanes thanks to this process.

• Sequestration: A set of technologies could potentially reduce CO2 emissions from new and existing coal- and gas-fired power plants, industrial processes, and other stationary sources of CO2. Captured CO2 is compressed, transported, and injected into deep underground rock formations, which are overlaid with impermeable, nonporous layers of rock that trap the CO2 and prevent leaks.

• Better energy efficiency reducing energy consumption, and thus CO2 emissions: • improving the insulation of buildings; • traveling in more fuel-efficient vehicles; • using more efficient electrical appliances, etc.

Methane

Methane (CH4), the simplest alkane, is the main component of natural gas. From an environmental point of view, it is the second-most prevailing GHG naturally emitted or resulting from human activities. Naturally occurring methane is mainly produced by microorganisms through a form of anaerobic

• Fossil fuel and energy switching toward: • renewable fuel sources emitting less GHGs, for example, ethanol;

60,000

million tons

50,000 40,000 30,000 20,000 10,000 0 4

5

6

7 Population, Bn

Figure 1.6 CO2 annual emission versus population (Bn).

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9

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respiration used by organisms such as landfill microorganisms and cattle and other ruminants for the most known. Methane is increasingly abundant in Earth’s atmosphere notably since the industrial era due to human activities. CH4 concentrations are now more than 2, 5 times that of preindustrial levels. In recent decades, the rate of increase has slowed down somewhat. Human activities through petroleum and gas production, livestock farming (enteric fermentation), waste landfilling, coal mining produce large amounts of methane. According to the EPA (http:// www3.epa.gov/climatechange/ghgemissions/), shares of US methane emissions are in the order of:

• • • •

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Halogenated Gases

Halogenated gases include a broad variety of chloride, fluoride, bromide, iodide alkanes such as for example haloalkanes (Halons), methyl chloroform (CH3CCI3), carbon tetrachloride (CCI4), CFCs, hydrochlorofluorocarbons, HFCs, PFCs. They are often used in coolants, foaming agents, fire extinguishers, solvents, pesticides, and aerosol propellants. Generally they have a long atmospheric lifetime, and they can affect the climate for many decades or centuries. After a maximum in the 1990s the levels of major halogenated gases slowly decrease in the troposphere thanks to a significant decrease of the consumption in recent years.

36% livestock farming and enteric fermentation

Nitrous Oxide (N2O)

29% petroleum and gas production

Nitrous oxide, N2O is one of the oxides of nitrogen (nitric oxide, dinitrogen trioxide, nitrogen dioxide, dinitrogen tetroxide, dinitrogen pentoxide). It gives rise to nitric oxide (NO) on reaction with oxygen, and this NO in turn can react with ozone. As a result, it is the main naturally occurring regulator of stratospheric ozone. It is also a major GHG and air pollutant. Considered over a 100-year period, it is calculated to have between 265 and 310 times more impact per unit mass (GWP) than CO2. Nitrous oxide (N2O) generates roughly 5% of the human induced greenhouse effect. The human part comes from combustion, use of fertilizers in agriculture, and some chemical industries including nitric acid production.

18% waste landfilling 10% coal mining.

Combustion and more generally oxidation of methane emits CO2 in large amounts, nearly threefold in weight. In terms of global warming potential, methane is 20 30 times more detrimental to the atmosphere than CO2. Lifetime in atmosphere is in the order of 12 years. Reduction of methane emission can be obtained by:

• Capture of landfill gases. • Upgrading of industrial equipment reducing methane leaks.

• Development of new strategies at livestock operations or animal feeding practices.

• Fossil fuel and energy switching toward: • renewable fuel sources emitting less methane, for example ethanol;

• renewable energy of low carbon sources, for example wind, photovoltaic, tide, geothermal, hydroelectric, etc.;

• Energy savings: • reducing personal energy use by turning off lights and electronics when not in use;

• reducing travels thanks to e-meetings; • reducing distance traveled in vehicles saving petroleum consumption thanks to optimized journeys; • redesign the tourism industry.

Ozone

Ozone is an inorganic molecule made out of three oxygen atoms versus two for common dioxygen molecule. It is much less stable, breaking down in normal dioxygen. Consequently, ozone is far more oxidant than dioxygen. Ozone is formed from dioxygen by the action of ultraviolet light and electrical discharges naturally occurring during storms, or artificially generated by industrial activities such as corona or cold plasma discharge, and other electric discharges. Reactions from emissions of nitrogen oxides and volatile organic compounds from automobiles, power plants, and other industrial and commercial sources in the presence of sunlight commonly produce ozone pollution.

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In total, ozone makes up only 0.6 ppm of the atmosphere. Tropospheric ozone has a short atmospheric lifetime in the order of 1 up to several days according to conditions. Although ozone was present at ground level before the First Industrial Revolution, peak concentrations are now far higher than the pre-industrial levels, and even background concentrations well away from sources of pollution are substantially higher. We must point out that ozone in the ozone layer has a benefiting effect as it filters out sunlight wavelengths from about 200 nm UV rays to 315 nm. Sulfur Hexafluoride

According to the Intergovernmental Panel on Climate Change (IPCC—https://www.ipcc.ch/), sulfur hexafluoride is the most potent GHG. Its global warming potential is estimated to 23,900 times that of CO2 when compared over a 100-year period. Sulfur hexafluoride having an estimated atmospheric lifetime of 800 3200 years we should not expect a decrease in its atmospheric concentration, but rather a more or less steady growth. Estimations of concentrations vary in a broad range. Concluding Remarks

If we keep up the same lifestyle, the sum of estimations of climate warming taking into account all the estimations resulting from all the GHGs including water vapor is higher than 3°C for the period 1951 1980. Literature displays lower or higher figures, for example, 0°C 5°C according to the scenario. Climate warming and higher CO2 concentrations can affect ecosystems changing their composition, some species being benefiting when others will be unable to adapt and may disappear. Urgency of Decisions

Response times to policy decisions are in the order of several decades and it is necessary to take decisions now for effective results by 2050 and later. Decisions must be more ambitious than the targeted results because of the risks of laxity.

1.6.4.2 Climate Warming and Sea Level Rise: The Major Risks The following information, facts, and figures are only assumptions and must be cautiously considered.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Under the IPCC “Business as Usual” emissions scenario, an average rate of global sea level could rise of about some cm per decade over the 21st century mainly due to thermal expansion of the oceans and the melting of some land ice. The predicted average rise is about 20 cm in global sea level by 2030, and 65 cm by the end of the century but other hypotheses range from 0.4 up to 1.2 m by 2100. The most optimistic scenario takes into account very restrictive actions to reduce GHGs, which leads to expected sea level rise about 0.4 0.6 m by 2100. According to the most pessimistic scenario, the results should be as high as 0.7 1.2 m by 2100. Sea level rise is, perhaps, the most visible and the most damaging effect of climate warming. Heavily populated areas of coastal capitals will slip under the waves along with large swathes of megacities across the world even if a climate summit limits global warming to 2°C, A 2°C rise in Earth’s temperature would submerge land currently occupied by 280 million people, according to a study published by US-based research group Climate Central (http://www.climatecentral.org/) and an increase of 4°C would cover areas lived on by more than 600 million people. However, there is high uncertainty concerning the date of these dramatic previsions, from one to several centuries. Generally speaking, more threatened populations are displayed by Table 1.2 Population in LowElevation Coastal Zone (http://www.cgdev.org/ publication/quantifying-vulnerability-climate-changeimplications-adaptation-assistance-working). All continents are threatened by a 4°C increase:

• Some 145 million people living in Chinese cities and coastal areas would eventually become Table 1.2 Population in Low-Elevation Coastal Zones (million). Asia

465.8

Africa

58.5

Europe

50.2

Latin America and Caribbean

33.2

North America

24.2

Oceania Total Source: CIESIN (2010—http://www.ciesin.org/).

4.2 636.2

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flooded. Four of the 10 most devastated megacities would be Chinese: land occupied today by 44 million people in Shanghai, Tianjin, Hong Kong, and Taizhou would be underwater. Shanghai with a population of around 24 million at the edge of the East China Sea, has the most to lose from rising sea levels. Climate Central estimates that 76% of the Shanghai region current population lives in areas that would eventually be underwater if the Earth warms by 4°C by 2100.

• • • • • •

34 million people in Japan 25 million people in the United States 20 million people in the Philippines 19 million people in Egypt 16 million people in Brazil India, Vietnam, and Bangladesh are also threatened

Heavily populated areas of Australia’s coastal capitals could slip under the waves along with large swathes of megacities across the world even if an upcoming climate summit limits global warming to 2°C. Brisbane, Sydney could be among cities that will slip under the waves with 2°C global warming. Of course, the 2°C scenario should limit the sea level rise but that is a serious challenge. Costal megacities, for example Shanghai, Hong Kong, New York, and others, located in low-lying areas are inherently vulnerable to rising sea levels because of low-ground levels, pumping of high volumes of groundwater, high concentration of skyscrapers, and massive amount of reclaimed land. A 60 cm sea level rise could be a significant threat to Shanghai and its neighboring areas by exposing at least 18 million residents to the danger of flooding. The Hong Kong Observatory predicted that Hong Kong’s mean sea level would increase by 48 cm by 2100. The risk of typhoons increases the frequency and magnitude of floods. With the global mean sea level rise of 30 cm by 2030, massive flooding is foreseeable, which not only pose a threat to the livelihood of residents but also have the potential to damage above-ground railways and the subway system. New York (http://www.dec.ny.gov/energy/ 45202.html) has an estimated 1850 miles of tidal shoreline exposed to the action of tides, wind and

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waves, much of it being densely populated. By 2100, scientists project sea level rises of 0.45 1.2 m. Several projection tools such as ClimAID, CRRA (Community Risk and Resiliency Act) and New York State Sea Level Rise Task Force have been dedicated to ensure better projections of climate risks. In a report issued early in 2011, the New York State Sea Level Rise Task Force, assessed sea-level rise impacts and identified the greatest threats to coastal communities and natural resources:

• Increased frequency and intensity of severe flooding and storm surge damage, not only to communities and infrastructure, but also to critical ecosystems that buffer against floods, protect drinking water and provide habitat for important species.

• Increased erosion of beaches and bluffs. • Inundation of low-lying areas. • Saltwater infiltration of surface waters and aquifers.

• Possible compromise of low-lying sewage, wastewater, transportation, communication, and energy infrastructure and systems.

1.6.4.3 Biological Consequences The effect of climate warming on biological processes is poorly understood, but there are general risks for the biodiversity. Locally, benefiting or damaging effects can result from temperature increase, wet or dry period modification, CO2 concentration increase. There is a general consensus about desertification and an increase of mortality during extreme temperature periods. From a technical point of view, the increase of temperature, the lack of water and the modification of wind streams can lead to issues for industrial processes such as cooling of nuclear power units for example or the efficiency of photovoltaic or wind turbine farms.

1.6.5 Natural and Artificial Sinks Natural or artificial sinks (removal processes) can partly offset GHG concentration increase, but can have collateral benefiting or damaging effects. Among natural or artificial sinks, a number of technologies are proposed to remove CO2 from the atmosphere. The IPCC has pointed out that many

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long-term climate scenario models require large scale manmade negative emissions to avoid serious climate change:

• Chemical change, for example: • depletion of CO2 concentration by photosynthesis of plants; • methane oxidized by reaction with naturally occurring hydroxyl radical, OH
and degraded to CO2 and water vapor (also a GHG).

• Dissolving in the oceans and other water and then reacting to form carbonic acid, bicarbonate and carbonate ions. That removes CO2 from atmosphere, which contributes to climate warming limitation but leads to ocean and other water acidification with their damaging consequences.

• Physical change: condensation and precipitation remove water vapor from the atmosphere.

• Economic valorization of CO2 as feedstock for polymerization of plastics.

• Geological sequestration. Starting points for more in-depth reading: examples of related organizations and institutions:

• United Nations Framework Convention on Climate Change

• • • •

IPCC Convention on Biological Diversity National environment and energy authorities Nongovernmental organizations from the environmental conservation community

• UN Office for Disaster Risk Reduction • International, national and local civil society organizations

• National Civil Defense authorities • National Disaster Management Agency • National Disaster Risk Reduction or Disaster Management Council References

• NOAA Earth System Research Laboratory— http://www.esrl.noaa.gov/gmd/aggi/aggi.html

• United Nation Environment Programme— http://www.unep.org/

• EPA (US Environmental Protection Agency)— http://www3.epa.gov/climatechange/ ghgemissions/

• Wilson Center—https://www.wilsoncenter.org/ publication/climate-change-impacts-chinasenvironment-biophysical-impacts#sthash. KoPVdNIw.dpuf

• Wikipedia—https://www.wikipedia.org/

1.7 Overview of Specific Plastics Features Of course, plastics obey the same rules as all materials but they have their distinctive features leading to higher demand that traditional materials, but also they must endure some particular constraints.

1.7.1 Population and Gross Domestic Product Push the Plastics Demand Fig. 1.7 shows the effect of GDP per capita on consumption of plastics per capita. The fast growing of plastics consumption for low GDPs becomes temperate for high GDPs. A logarithmic model seems lead to fair values, but, of course, it is only a model among others and not the reality. Fig. 1.8 shows an example of the plastics demand per capita broken down by regions. Two classes of regions clearly appear: three regions with a demand far better than that of the Earth and three with a medium or low demand. The first group gathers mature industrial regions having a medium population and a high GDP per capita when the second group gathers medium to high population with medium to low or very low GDP per capita.

1.7.2 The Extent of the Problem: The Worldwide Plastics Demand at a Glance The plastics industry has grown continuously for over 50 years. Production increased from 1.5 million tonnes in 1950 to 335 million tonnes in 2017. The annual growth was hit hard by the global economic crisis during 2008 and 2009. In the long term, the plastics success story is expected to continue. Per capita consumption in Asia and central

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25

Kg

140 120 100 80 60

y = 61.209ln(x)–524.5 R² = 0.9388

40 20 0 0

10,000

20,000 30,000 40,000 GDP per capita, $

50,000

60,000

Figure 1.7 Example of plastics demand per capita versus gross domestic product per capita.

160

Kg

140 120

NAFTA

100

EU

80

Japan

60

World

40

Central Europe & Russia

20

Asia excluding Japan

0 1970

Middle East & Africa

1980

1990 2000 Year

2010

2020

Figure 1.8 Plastics demand per capita for various regions.

Europe is significantly below the levels of mature industrial regions and global per capita demand is growing at a long-term trend of 4%. Mature industrial regions are also expected to see growth rates slightly above GDP.

Table 1.3 Global Plastics Consumption Breakdown. % Commodity

76

Engineering

6

Composites

3

1.7.3 Plastics: A Generic Name for Very Diverse Materials

Specialty

,1

Thermoplastic elastomers

2

Plastics name gathers commodity resins up to composites, soft up to hard materials, environmentfriendly up to environmentally harmful compounds, and so forth. Therefore alternative materials should be very adaptive for their replacement. Table 1.3 and Fig. 1.9 indicate the orders of magnitude of global plastics consumption shares displaying the supremacy of the commodity class accounting for about 76%.

Environment-friendly

B1

Others

12

Total

100

Worldwide plastic growth is estimated between 2% and 3% per annum over the next few years, leading to a worldwide consumption estimated to 400 million tonnes by 2025 in round figures.

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200

Commodity

Engineering Composites

TPE

Others Specialty

Environmentfriendly

0

Figure 1.9 World plastic consumption (million tonnes).

Consumptions and growth rates broadly vary according to the area considered. China and other Asian countries excluding Japan are the leaders for commodity plastics consumption and growth rate, superseding North America and Western Europe, which, in return, are leaders for engineering and specialty plastics. Table 1.4 and Fig. 1.10 display consumption data for recent years and forecasts for 2025 according to a medium hypothesis of annual growth rate. Consumptions are uncertain and forecasts are more or less subjective. Consequently, other estimations can be found in other sources. FSU: Former Soviet Union; NAFTA: North American Free Trade Agreement covering Canada, the U.S. and Mexico.

1.8 Environmental Issues From a Plastics Point of View Plastics must obey to general and specific regulations dealing with health, environment and safety, but in addition some specific constraints are emitted by countries, organizations or even private companies concerning general or particular products. It is the responsibility of the reader to search the ins and outs concerning his own case for his own product, the countries of manufacture, use, and disposal.

1.8.1 Potential Pollutants The following refers to a few examples only and many other mandatory or voluntary regulations must be applied.

Potential pollutants may be included in the macromolecule, polymerization catalyzers, additives, compounding ingredients, and so forth. Table 1.5 reminds us of examples of macromolecule composition for synthetic and renewable plastics. Note some of them may be synthetic or renewable. PVC containing a high level of chlorine is the third-most consumed plastic. Be aware that some renewable polymers may contain as little as 30% of natural materials when others have a high content of natural origin. Apart from the used macromolecule, compounds may store pollutants as unreacted monomer or comonomer (e.g., bisphenol A or BPA), residues, plasticizers, fire retardants (FR), colorants, stabilizers, and so forth. For example:

• Heavy metals, including mercury, zinc, copper, cadmium, vanadium, and lead are harmful if spread in the environment. • Mercury (Hg) is used in catalysts and is released by the combustion of fossil fuels and wastes. Organic mercury compounds act as cumulative poisons that affect the nervous system. • Zinc (Zn) is used as curing activator for rubber and for PVC stabilization. • Copper (Cu) is used in pigments for plastics and rubbers. • Cadmium (Cd) is a cumulatively toxic element. • Lead (Pb) accumulates in biological systems and is linked to behavioral changes, paralysis and blindness. It was used as curing activator or stabilizer for certain polymers.

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Table 1.4 Consumptions and Growth Rates for All Plastics. Total Plastics (million tons)

Forecast (million tons)

Annual Growth Rate (%)

2015

2025

2025/2015

China

80

110

3

Rest of Asia excluding Japan

54

83

4

NAFTA

63

69

1

Western Europe

64

70

1

Japan

14

14

0

Latin America

15

16

1

Africa and Middle East

23

28

2

Eastern Europe/FSU

9

10

1

Total

322

400

2.2

Japan

Latin America

Western Europe

Africa and Middle East NAFTA Eastern Europe/FSU

Asia excluding Japan

China

Figure 1.10 Consumptions according to the regions.

• Various halogenated species from solvents and paints.

• Toluene, xylene, styrene, naphthalene, ethanol; trichloroethylene and other chlorinated solvents are harmful and contribute to the greenhouse effect.

• Phosphorus derivatives. An excess of phosphorus compounds in surface water leads to eutrophication and algal bloom.

• Some plasticizers, FRs, curing agents, etc., such as: • Chloroparaffins or chlorinated paraffins that are stable organic compounds resistant to degradation and oxidation. Used as softeners

and/or as flame-retardants in plastics and rubbers they are harmful primarily to aquatic life. • Polybrominated biphenyls and Polybrominated diphenyl ethers. These biologically persistent organic compounds containing bromine are used as FRs in plastics, for example in housings for electrical equipment. • Polychlorinated biphenyls are biologically persistent organic compounds containing chlorine, particularly toxic to marine life. Sometimes used in rubber seals for electrical transformers and capacitors they are now being phased out and disposed of.

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Table 1.5 Examples of Macromolecule Composition.

Macromolecules made of C, H, O

Synthetic

Renewable

Polyethylene or polyethene (PE)

PE

Polypropylene (PP)

PP

Polybutene-1 or polybutylene-1 Polymethylpentene Cyclic olefin copolymers Ethylene vinylacetate copolymers Polyvinyl alcohol Ethylene copolymers (EVOH, EMA, EBA, EGMA, EMAH, EEA, EAA, etc.) Polyvinyl butyrate Polyvinyl acetate Styrenics (PS, SB, SMA) Thermoplastic polyesters (PET, PBT, etc.)

Thermoplastic polyesters (PET, PBT, etc.)

Polylactate (PLA)

PLA

Aliphatic polyesters PBS

Aliphatic polyesters PHA, PHB Starch (TPS) Lignin Cellulose

Acrylics (PMMA)

PMMA

Acetals (POM) Polycarbonate (PC)

PC

Polyphenylene oxide (PPO, PPE) Cellulosics (CA, CAB, etc.) PolyEtherEther Ketone (PEEK), PolyEther Ketone (PEK) Liquid crystal polymers Unsaturated Polyesters (UP)

UP

Phenolic resins (PF)

PF

Common ThermoPlastic Olefin (TPO) Polymers containing Cl

Chlorinated polyethylene (CM) Polyvinyl chloride (PVC)

PVC

Chlorinated PVC Polyvinylidene chloride Polymers containing F

Fluorinated thermoplastics (Continued )

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Table 1.5 Examples of Macromolecule Composition.—Cont’d Synthetic Polymers containing N

Renewable

Acrylonitrile butadiene styrene, methylmethacrylate acrylonitrile butadiene styrene Styrene acrylonitrile, acrylate rubber modified styrene acrylonitrile, acrylonitrile EPDM styrene, acrylonitrile chlorinated polyethylene styrene

PA

Polyamides or nylons Polyetherimide Polyamide imide Polyimides Polybenzimidazole Polyacrylonitrile Polyurethanes, polyureas

Polyurethanes, polyureas

Epoxide resins

Epoxide resins

Polycyanates or cyanate esters

Polycyanates or cyanate esters

Melamine and urea formaldehyde resins (amino resins) Polymers containing S

Polysulfone PPS

Polymers containing Si

Silicones Thermoplastic elastomers

1.8.2 Specific Environmental Issues for Plastics: Visual Pollution, Marine Litter, Single-Use Items The bad image of plastics comes in part from several of their advantages: long lifetime, low density, and low cost being not incentive to cautious end-of-life treatment. Visual pollution is the most visible drawback but others are hidden and more harmful. Density of most plastics is in the order of one and bulky products such as bags and bottles fly easily with the wind, which produces a visual pollution prejudicial for the plastics image.

1.8.2.1 Marine Litter In 2010, the United Nations Environment Programme (UNEP—http://www.unep.org/newscentre/un-declares-war-ocean-plastic) estimated that between 5 and 13 million tonnes (1.5% 4% of global plastics production of plastics) leak to oceans. Other components of the debris include wood, metals, cardboard, glass, textile, and so forth. Many plastics float or remain suspended in water, making them more visible. Commingled with other solids, plastics form the marine litter with locally “islands” that are, at first glance, particularly impressive and hard-hitting.

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Marine litter can cause serious environmental, health and economic damages: losses for coastal communities, tourism, shipping, and fishing. Obviously, in addition, included plastics are lost for their regular use. UNEP estimates that damages to marine environment are at least USD 8 billion per year globally. The most common forms of debris are:

• • • •

cigarette filters plastic bags fishing equipment such as nets packaging

Most commonly identified plastics include:

• • • •

PE PET polypropylene PVC

Most of these polymers have an extremely long degradation time. As a result, the majority of plastics manufactured today will take decades or even centuries to disappear. Asia is suspected of being the leading source of mismanaged plastic waste. China alone could account for 25% 30% of plastics litter. Potential solutions to this important problem must include technical measures such as:

• • • •

reduction of plastics leakage reduction of waste recycling and effective reuse improved municipal waste management systems.

Following another way, mandatory laws and regulations are also efficient levers. Many governments and associations work on the marine litter problem, as we can see through two examples. In March 2011, leaders from 47 plastics associations across the globe signed a declaration to combat the causes of marine litter. The Declaration of the Global Plastics Associations for Solutions on Marine Litter (Global Declaration) represented a public commitment by a global industry to tackle a global problem—plastic litter in the coastal or marine environment.

The 4th Progress Report summarizes the status of commitments made under the Global Declaration. As of December 2017, approximately 355 projects have been planned, underway, or completed. The projects vary widely, from beach clean ups to expanding waste management capacities, and from global research to awareness and education campaigns. These projects have been undertaken by 74 plastics associations that have signed the Global Declaration in 40 countries, plus an additional 13 associations that have not signed the declaration. The Global Declaration and list of signatories can be found at: www.marinelittersolutions.com. In December 2018, the European Parliament and the Council of the European Union have reached a provisional political agreement on the ambitious new measures proposed by the commission to tackle marine litter at its source, targeting the 10 plastic products most often found on beaches as well as abandoned fishing gear. Products banned from the market should include:

• plastic cotton buds, cutlery, plates, straws, drink stirrers, sticks for balloons

• products made of oxo-degradable plastic • food and beverage containers made of expanded polystyrene

1.8.2.2 Microplastics, Microbeads, Microfibers The smallest plastics items, often referred to as microplastics (usually less than 5 mm), can be ingested by aquatic wildlife leading to potential risks, injuries, poisoning and other damages. Additives may be more easily dissolved by water that is polluted and releases pollution all along the food chain. Litter pollutes beaches and damages the environment. Microplastics result from:

• Leakage of plastic resin pellets during preprocessing operations such as polymerization, compounding, etc.

• Unwanted loss of plastics products in the water body. By erosion and wear the size is reduced to a micron level

• Intentionally use of microbeads in personal care products.

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• The 10,000 containers lost every year by container ships during storms. Plastic resin pellets (or nurdles) can enter freshwater and marine environments during ocean or land-based transport and handling, by leaking from trucks, factories or manufacturing sites. They can easily enter waterways via storm water run-off and then tend to fragment into smaller and smaller pieces. That may be an offence of illegal dumping of industrial waste or creating an environmental hazard. For example, discarded, rejected, unwanted, surplus or abandoned matter (such as plastic pellets) is defined as waste under the Australian Environment Protection Act 1970 and must be managed appropriately (https://www.epa.vic.gov. au/your-environment/waste/plastic-resin-pellets-nurdles). Pellets that are not properly managed and are discharged into the environment (e.g., waterways), can form the basis of such an offence. Any person that fails to contain their pellets faces a fine of more than $7500, or up to $777,300 if prosecuted. Businesses involved in the production, transport, storage, handling, use, or disposal of pellets may be liable to enforcement action if they fail to manage the risk of pellets escaping. Microfibers generally come from washing of textile products. Microbeads are intentionally manufactured plastic particles (often PE) used as exfoliant additives to health and beauty products, cleansers, toothpastes etc. Industrial water filtration systems are unable to stop these microscopic particles that end up in the water body, oceans, rivers, and so forth, posing a potential issue to marine life. According to the United Nations Environment Programme, plastic microbeads are used since about 50 years, but this issue is relatively little known, with a plethora of involved products and a weak consumer’s concerns. Coercive restraining measures have emerged in recent years, for example:

• On December 28, 2015, President Obama signed the Microbead-Free Waters Act of 2015, banning plastic microbeads in cosmetics and personal care products.

• EU Commission has therefore started the process to restrict the use of intentionally added microplastics, by requesting the European

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Chemicals Agency to review the scientific basis for taking regulatory action at EU level.

• The United Kingdom has banned microbeads in cosmetic and personal-care products.

1.8.2.3 Single-Use Products: What is the Problem? Single-use products are systematically expected of being unsatisfying from a sustainable point of view but every case must be considered before a decision. The useful life of an object is a basic parameter of the life cycle assessment (LCA). Thus the single-use feature must be taken into account at the design step and the raise of a general outcry against single-use plastics is not an objective behavior but a preconception. Some LCAs conclude that singleuse parts may be more environment-friendly than multiuse parts for example because the multiuse part may need thicker walls which leads to material overconsumption, higher part weights to be carried, higher energy, and so forth. That being said, the use of plastics may be forbidden by law. Worldwide there are many partial or total bans emitted by nations, states, territories, cities, or even organizations and companies concerning disposable single-use items made out of plastics. Some are already in force, but many others are scheduled later, often up to 2030. The ban may be limited to fossil plastics and noncompostable items. For example, thin plastics carrier bags made out from natural sourced polymers may be authorized, but that does not solve the problem of leakage into natural systems. Compostable polymers can be also disputed because they are compostable in dedicated facilities, but may be not compostable in natural conditions. There are several types of concerns: on the one hand the leakage of single-use products into natural systems due to the lack of user awareness and/or the lack of suitable collection and recycling streams. On the other hand the unsustainability may be due to other parameters of their life cycle. From an economic point of view that is also a problem with a market valued to more than $2 billion in the next years for cutlery industry alone (“Plastic Cutlery Industry: Global Market to Grow Over US$ 2920 Mn by 2025—QY Research, Inc.”—https://www.globenewswire.com/newsrelease/2019/03/07/1749694/0/en/Plastic-Cutlery-

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Industry-Global-Market-to-Grow-Over-US2920-Mn-by-2025-end-QY-Research-Inc.html). Biodegradable plastic cutlery based on wood, wheat bran, sorghum, rice, and corn may be an alternative way.

1.8.3 High Lifetimes are a Handicap for Waste Plastics lifetimes are often in the order of several decades and complete degradation may be in the order of a few centuries making abandoned wastes may be visible for a long time. Plastics micronized debris may be invisible at naked eye but are always polluting the oceans and other water bodies.

1.9 A Major Issue for Sustainability: Plastics Processing Needs (Polluting) Energy

energy. Fig. 1.11 shows energy consumption per capita versus GDP per capita for more than 100 very diverse nations. For a same GDP per capita, energy consumptions per capita broadly vary, for example in round figures at a given time, 3000 7000 for an average value of 5000 that is to say plus or minus 40%. Energy is expressed in toe. The tonne of oil equivalent (toe) is defined as the amount of energy released by burning one tonne of crude oil. It is approximately 11.63 megawatt-hours (MWh) or 42 gigajoules, although different crude oils have different calorific values. Same data lead to Fig. 1.12 GDP per capita ($) versus energy consumption (without unit) per capita showing that a same energy policy can be adopted by countries of very different GDP. For example, in round figures, a given energy per capita is consumed by countries having GDP per capita between $19,000 to $51,000, that is to say around 46%.

All activities need energy to initiate and monitor chemical reactions, physical modifications, and satisfy elementary survival. Energy demand increases with population, GDP, industry development, standard of living, and so forth. Traditional energy sources emit high quantities of CO2 and contribute to global climate warming. Essential for all economies, energy must become renewable with a recent trend to green electricity minimizing raw material depletion, pollution and other environmental issues.

1.9.2 Overview of Energy Demand Forecast

1.9.1 Energy Versus Gross Domestic Product

Renewable energy derives from natural processes (e.g., sunlight and wind) that are replenished at a faster rate than they are consumed. Solar, wind, geothermal, hydro, and some forms of biomass are common sources of renewable energy.

Rising of GDP per capita gives access to additional commodity and wellbeing means consuming

Some forecasters predict that humanity’s energy demand will be declining in a mid-future, perhaps about the mid-2030s or later. Energy resources can be split in two categories:

• Fossil and nonrenewable (oil, gas, nuclear), the most current today

• Renewable resources growing fast

0.001 tep

9000 8000 7000 6000 5000 4000 3000 2000 1000

$

0 0

20,000

40,000

60,000

80,000

100,000

120,000

Figure 1.11 Energy consumption (0.001 tep) per capita versus gross domestic product per capita.

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120,000 100,000 80,000 60,000 40,000 20,000 0

Figure 1.12 Range of gross domestic product ($) versus energy consumption per capita.

Most renewable sources are weather and time dependent such as wind, solar, wave, and tidal resources that fluctuate during the course of any given day or season. Variability obliges to constantly balance the supply and variable demand for electricity. Large shares of variable renewables supply may need increased flexibility of generating capacities (e.g., gas and hydro power plants), interconnections, storage (e.g., with batteries or pumped-hydro plants), and/or load-management empowered by smart grids. On the other hand, renewable resources generally contribute to energy diversification, in terms of the technology portfolio and also in terms of geographical sources. That leads to diversification of the energy mix and to a better security. Growth of use of renewable resources can also reduce fuel imports and alleviate the economy from fossil fuel price rises and swings. General trends include a higher energy efficiency, diversification of supply, growing share of renewable sources, and limitation of nuclear plants:

• High energy efficiency includes more stringent minimum requirements for appliances and new buildings, high renovation rates of existing buildings, and establishment of energy savings obligations on energy utilities. Therefore the EU expects a decrease in energy demand of 41% by 2050 as compared to the peaks in 2005 2006. Other estimates are more limited, for example 27%.

• Diversified supply technologies: All energy sources can compete on a market basis with no specific support measures. Decarbonization is driven by carbon pricing assuming public

acceptance of both nuclear and carbon capture and storage.

• Strong support measures for renewable energy sources (RES) aim a high share of RES in gross final energy consumption.

• Lower nuclear energy: No new project of nuclear sources (apart from reactors currently under construction) should be forecast. EPR projects under construction should be connected to the grid until 2026, apart from new delays. Taking into account population and GDP evolutions, wellbeing improvement, industry, and agriculture growths, but also energy savings, many scenarios of world energy consumption are proposed by forecasters (see Fig. 1.13) leading to about 700 900 Mtoe in 2050. Prospective and projections are mind games and as everyone knows, forecasts on long periods are more often wrong than true. The reader is solely responsible for the possible use of facts and features resulting from this brainstorming discussion. Very different data and opinions can be found elsewhere. They are also plausible and worthy of interest.

1.9.3 Potential Energy Sources for the Future Energy sources compete on the basis of price and availability, technologies being chosen in competitive markets, but the freedom can be limited by governments through grants, subsidizes, incentive actions and bans. Worldwide, the balance between renewable and fossil sources results from

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

1000 900 800 700 600 500 400 300 200 100 0

Frequency

Figure 1.13 Range of energy demand (Mtoe) forecast for the 2010 2050 period.

12 10 8 6 4 2 0 4

13.8

23.6

33.4

43.2

ou plus...

Classes, % of renewable energy

Figure 1.14 EU renewable energy share, %.

environmental commitments, availability of new resources, technical constraints coming from generation and storage issues, investments, potential risks, and end costs. Locally, some resources may be especially interesting or at the opposite unavailable. High shares of renewable energy can be viable in certain countries and unattainable today for others. Fig. 1.14 shows for EU countries, actual shares of renewable energy pointing out the wide range of data (4% up to 53%). A few countries reach levels higher than 2020 targets when other countries are late. Taking into account these considerations, Fig. 1.15 proposes a scenario of renewable and nonrenewable energy for the world up to 2100 without any warranty. That leads to about equal generations from renewable and nonrenewable resources in 2080. Renewable energy steadily grows when fossil energy smoothly decreases. Other forecasts lead to more or less different hypotheses from 2035 for the most optimistic forecasters up to beyond 2100. As for other forecasts the reader is solely responsible for the possible use of facts and features resulting from this

brainstorming. Very different data and opinions can be found elsewhere. They are also plausible and worthy of interest.

1.9.3.1 Fossil Energy For the nonrenewable energy Fig. 1.16 proposes a scenario without any warranty with peaks for oil, natural gas, and coal approximately about the middle of the century. Nuclear electricity could be approximately stable but a decrease is not excluded.

1.9.3.2 Renewable Energy Resources Renewable energy sources may generate continuously or intermittently energy. In this last case the source must be coupled with a smart grid or a storage device. Generally, wind, solar, and marine sources are intermittent when biofuels and hydropower such as dams are continuous sources. Hydropower

Hydropower has been used for a long time in water-mills built on rivers. Hydroelectric power is harnessed through the same principle, water driving

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Mtoe Grand total

25,000

Total renewable Total non renewable

20,000 15,000 10,000 5000 0 1980

2000

2020

2040

2060

2080

2100

2120

Figure 1.15 Renewable and nonrenewable energy forecast up to 2100 (Mtoe).

6000 5000

Total oil

4000

Natural gas

3000

Coal

2000

Nuclear

1000 0 1980

2000

2020

2040

2060

2080

2100

2120

Figure 1.16 Detailed nonrenewable energy (Mtoe).

electric generators but now, other sources are exploited such as tides and waves. Today, on a worldwide standpoint, it is the most used renewable energy. Hydroelectricity does not consume water or fuel, can be active 24/7 on demand, is clean without waste or emissions. Dams can shut their gates and conserve the water and its potential energy for use on demand. However, in case of longtime drought, electricity generation may be stopped which is not the case for tide and wave sources. Hydroelectric plants are very expensive to build. Often, building of dams disturbs the natural environment, creates flooding of land, destroys the natural habitat of animals and even people, and leads to water access problems including the loss of water flow control for downstream populations. Wind power turbine

Wind power has been used for a long time in windmills. Wind power turbines are based on the

same principle, wind driving electricity generators. The future for wind energy is excellent with a double-digit growth rate thanks to large-scale wind farms. It is a clean energy source on the basis of GHG emission, but noise emission disturbs their surrounding environment. Offshore farms solve that, but there are discussions linked to fish and bird disturbance. Generally, turbines tend to be very tall with a small plot of land at their base and are being connected to the electricity power grid but smaller models can produce electricity used on the spot. Obviously, wind turbines are wind dependent and farms must be located in countries where wind is strong and frequent. Connection to the electricity power grid or storage devices is needed to obviate fluctuation of the electricity generation. Some people have a negative feeling because of noise, sight and sometimes possible health hazards due to electric fields.

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Solar power

Geothermal Energy

Solar cells convert directly the energy from the sun to usable electricity. Photovoltaic cells utilize a semiconductor absorbing radiations from the sun and emitting electrons, which are harnessed as electricity. Solar panels require little maintenance. After installation and optimization, they are very reliable due to the absence of mechanical parts that can fail. Solar panels are also quiet producers of energy. Most governments have introduced tax credits for individuals and companies that invest in solar energy systems. The primary disadvantage of solar power is its inactivity during the night and the reduction of power generation during cloudy periods. Solar panel energy output is maximized when the panel is directly facing the sun. In a fixed location, such as the building roof, energy production is reduced when the sun is not at an optimal angle. Many largescale solar farms have adjustable panels that can track the sun to keep the optimal angle throughout the day. Most efficient solar cells only convert just over 20% of the sun rays to electricity. Conversion efficiencies of best research solar cells worldwide reach 46% but with increased advances in solar cell technology this number is likely to increase. Besides their low conversion efficiency, solar panels can be a substantial initial investment. Solar radiations are also used in relatively simple technology to heat water going through solar water heaters.

Geothermal energy can be used for heating or to produce electricity through turbines powering a generator. Geothermal electricity generation is currently underexploited according to the Geothermal Energy Association and the IPCC estimates. Geothermal power is considered to be a sustainable, renewable source of energy because the heat extraction is small compared with the Earth’s heat content. The GHG emissions of geothermal electric stations are less than 5% of that of conventional coal-fired plants. For the renewable energy forecasts, which are much rasher to assess, Fig. 1.17 proposes scenarios displaying high growths of biofuels and other renewable energies, combined with a slower increase of hydraulic energy. Of course, those human forecasts are without any warranty and expect that issues concerning the use of intermittent energy sources are solved. Biofuels and Other Biofeedstocks from Biomass

Biomass including products as diverse as cultivated or wild plants, vegetable oils, waste, animal fats, or recycled greases lead to bio products used in various ways for the production of biofuels, biooils, biohydrocarbons, and other biofeedstocks. For the most known example, cultivated sugarcane leads to ethanol, which is used as biofuel and as feedstock for PE production. Biofuels require a few changes in engines of cars and trucks or other devices. Properties of bio-PE are claimed similar to those of fossil PE.

16,000 14,000 12,000 Total renewable

10,000

Other renewables 8000

Biofuels

6000

Hydroelectricity

4000 2000 0 1980

2000

2020

2040

2060

2080

Figure 1.17 Detailed renewable energy production up to 2100 (Mtoe).

2100

2120

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From a carbon point of view, the carbon produced when harvesting the plant and burning fuel is offset by the carbon consumed by the plants they came from. Research suggests that biofuels help to reduce carbon emissions by 35% 60%. Ethanol or other chemicals coming from corn or sugarcane and other edible sources, compete food, lead to deforestation and pollution by fertilizers and insecticides. Of course, those arguments do not apply to waste, which in addition are usefully recycled. From an economy point of view, new imbalances have appeared concerning agricultural outlets because of the higher values of agricultural production of biofuels and other industrial bioproducts, which compete food crops. In addition, the deforestation increases to gain new arable soils. The large extent of the problem can be measured by some round figures:

• global consumption of polymer is around 330 million tonnes

• global consumption of crude oil for polymer production is around 330 million tonnes

• global production of vegetable oils is approximately 170 million tonnes

• global production of ethanol is approximately 50 million tonnes

• global production of natural rubber is about 12 million tonnes

• global production of cereals is about 2500 million tonnes

• global production of cotton is about 25 million tonnes

0

37

If renewable natural raw materials were to replace crude oil, it would be necessary to double (and more) the production of oils and ethanol (see Fig. 1.18) with the risk of intensify the economic imbalance of the agricultural markets satisfying the fundamental needs for the nourishment of humans and livestock. Biofuels requiring a few changes in engines of cars and trucks or other devices, the International Energy Agency predicts that they have the potential to meet a significant part of the world demand for transportation. Many ways are investigated for biofuels of second generation that does not compete with food. They include, among others, ethanol from cellulosics, hydrotreated vegetable oils, transesterified oils, furanics, biobutanol, dimethylether, methanol, biogas, biodiesel from microalgae (also called biofuels of third generation), and so forth. Sources are as diversified as lignocellulose from farm and forest residues, grasses and wood, woody and straw residues, algae, food and feed waste, harvesting residue, processing residues, nonfood crops grown on marginal, nonarable land, organic fraction of urban waste, short-rotation forestry, and so forth. It is quasi unanimously forecast a fast and steady growth of bioenergy production. Fig. 1.19 shows an example of forecast among many others. For example, estimates of global total energy demand lead to divergent results for 2050, ranging from 640 EJ/ year or 14,000 Mtoe up to 940 EJ/year or 21,600 Mtoe with an average 770 EJ/y or 17,700 Mtoe and a standard deviation 130 EJ/year or 30,000 Mtoe. On the other hand, estimates of the global potential of bioenergy production is even more divergent, from 27 to 1546 EJ/year that is to 500

1000

1500

2000

2500 MT

Today oil and ethanol consumption

Tomorrow oil and ethanol for polymers

Tomorrow oil and ethanol needs, total

Today cereals production

Figure 1.18 Approximate production and needs of oil and ethanol.

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12,000

Mtoe

10,000 8000 6000 4000 2000 0 2000

2020

2040

2060

2080

2100

2120

Figure 1.19 Example of bioenergy forecast (Mtoe).

say less than 10% of the total energy to approximately the double of the total energy demand per year.

1.9.3.3 Share Examples of Electricity Sources Electricity is a secondary source accounting for about 20% in round figure of the total energy. Table 1.6 displays four examples of electricity sources in round figures, Apart from Norway, fossil electricity is predominant. For the middle of this century, very diverse hypotheses are proposed between wished and reasonable forecasts. Fig. 1.20A C shows three hypotheses ranging from high to low shares of fossil sources. Please note that marginal sources are not taken into account and that fossil energy share is about 50% or more.

Among fossil sources:

• nuclear power is not negligible even for the most favorable case

• gas consumption is significant in all cases • coal use varies from high share to nearly zero Among renewable sources:

• hydro and wind powers are significant in all cases

• the share of solar energy varies from little up to significant. Intermittent source shares are significant in all cases needing use of storage and smart grid solutions.

Table 1.6 Examples of Grid Electricity Mix in Production Locations. Energy Type

Norway

Turkey

China

France

Oil and natural gas, %

46

4

2

Coal, %

23

78

1

2

80

Nuclear, % Fossil subtotal, %

1

69

84

83

Hydropower, %

99

31

16

10

Other renewables, %

6

Renewable subtotal, %

99

Miscellaneous, %

1

Total, %

100

31

16

16 1

100

100

100

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(A) Wind

Nuclear

Solar

Hydro Coal Gas (B) Wind

Nuclear

Solar

Coal Hydro Gas

(C) Wind Solar

Nuclear

Coal Hydro Gas

Figure 1.20 Different hypotheses for electricity production in midterm. (A) High fossil source shares. (B) Medium fossil source shares. (C) Low fossil source shares.

1.10 Water Footprint of the Plastics Industry and Water Stress As many human activities, resin production, processing, use and recycling of plastics consume water and pollutes it when tap water is not accessible to all the populations.

1.10.1 Overview The Earth is covered at 80% by water following a continuous cycle of evaporation, precipitation, runoff, and infiltration. This last step is the slowest, but the most interesting for water conservation. Salt water is the most abundant, but unsuitable for

39

human consumption and many industrial applications. Freshwater represents only 3% of the mass. During the past 50 years, the global population has doubled, and the water demand tripled. It becomes vital and urgent to save this precious resource to ensure our survival. The water stress is the consequence of the deterioration of the fresh water in terms of quantity (overexploitation of the underground reserves, drying of rivers, etc.) and in terms of quality (eutrophication, organic pollution, salt intrusion, etc.). Industrial uses account for about 20% of global freshwater withdrawals. Of this, 60% 70% is used for power generation and 30% 40% for other industrial processes. With the increase of the population and the economic development, there is a growing deterioration of the fresh water situation in terms of quantity and quality. The overexploitation of the reserves reduces the available water and the increase of pollution makes certain reserves unavailable. Tap water becomes a rare commodity and is not accessible to all the populations. A water footprint can be defined as the volume of water abstracted from local sources minus the volume released in the same place after treatment or directly made available for reuse. In a water stressed world, water footprint is a key concept to better assess and manage impacts on local environments and communities. Let us note that water consumption can have several senses corresponding to different states, for example:

• the total water needed for the plant operation • the destroyed water, which is the case for electrolysis

• the polluted water, which is the case for washing operations

• the net consumption resulting of the difference between the used water and the well treated water considered as fresh water

1.10.2 Water Consumption for Plastics Production Plastics as the other materials use water and affect it during the various steps of their life: resin production, processing, use and recycling (see Fig. 1.21).

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Resin production

Natural

Synthetic

Polymerization

Polymerization treatments

Farming

Cooling, heating, various treatments

Processing

treatments

Water recycling

Water savings

Use

Water pollution

Cooling heating various treatments

Plastics recycling

Water recycling

Water recycling

Figure 1.21 Water footprint of plastics.

Water consumption depends on many parameters taken into account or not by the data source, the incorporation or not of the energy source and its type. For example:

• For commodity plastics such as PE or polystyrene, the water consumption is two or threefold the polymer outlet, depending on the plant age, the country and the environmental concerns of the producer.

• According to Borealis findings the manufacturing of polyolefins has a limited direct Water Footprint—ranging from 1.2 to 6.5 m3 of fresh water per tonne of finished product. But the indirect Water Footprint originating from feedstock and the source of energy used is more critical and can triple the total Water Footprint of the product.

• According to Vinnolit, 3 4 m3 of fresh water are used for 1 tonne of PVC. Higher figures are quoted elsewhere, for example 12 m3.

• For unsaturated polyesters, water consumptions of 1 13 m3/t are quoted.

• For polyamides, water consumptions ranging from 2 up to 160 m3/t are quoted according to the polyamide type and the continuous or batch process.

• To make 1 tonne of PET bottles, 294 m3 of water are used in the process including the water used for cooling at the coal power plant, the water used in the cooling process at the PET manufacturing plant, the water used for cooling in the bottling plant.

• To make 1 tonne packaging, 3486 m3 of water are used in an undefined process.

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10

100

1000

10,000

41

100,000

Resin, PVC Resin, PO Resin, UP Resin, PA PET bottles Packaging Caps

Figure 1.22 Water consumption (tonne) by tonne of end product.

• To manufacture 1000 closures, 40 m3 of water

are used that is to say, perhaps 4000 m3 and more per tonne of plastic.

Fig. 1.22 shows these results expressed in tonne of water per tonne of end product. Beware the scale is logarithmic pointing out the high-water consumption for molded and extruded products. However net consumptions would be different, waste water being simply lightly heated, evaporated, polluted, treated, returned to the initial source, etc. Water consumption can have several consequences leading to:

• The destruction of the water by the processing method, which electrolysis.

is

the

case

of

water

• The physical or chemical pollution at more or less high intensity levels. To a certain extent this pollution can be reduced by waste water treatments (WWT) leading to water of an acceptable quality, sometimes better than that of the initial used raw water. Pollution can be rated by general analysis such as: • COD (chemical oxygen demand): the amount of potassium dichromate, expressed as oxygen, required to chemically oxidize substances contained in waste water. • BOD (biochemical oxygen demand): the quantity of dissolved oxygen required by microorganisms in order to decompose organic matter. The unit of measurement is mg O2/l. In Europe, BOD is usually measured after 3 (BOD3), 5 (BOD5) or 7 (BOD7) days. • Total suspended solids. • Hydrocarbons total.

1.10.3 Best Available Techniques in the Production of Polymers Water issues have been a worry from a long time and, for example, the European Commission Directorate-General published a Reference Document on “Best Available Techniques in the Production of Polymers” dated October 2006 dealing among other pollution problems with the water issues. Generally speaking, the chemistry of polymer production consists of three basic reaction types, polymerization, polycondensation, and polyaddition. In addition, the operations include the preparation and the separation of products. In many cases cooling, heating, or the application of vacuum or pressure is necessary. The unavoidable waste streams may be treated in recovery and/or reduction management systems or disposed of as waste. A key environmental issue of the polymer waste waters is the potential high loads of organic compounds. Generic and specific “best available techniques (BAT) concerning production of plastics involve the water use. Requirements can be of a good sense or more sophisticated and specific. Generic BAT related to water require, for example:

• To prevent water pollution by appropriate piping design and materials.

• To facilitate inspection and repair of effluent water collection systems at new plants and retrofitted systems must be made of: • pipes and pumps placed above ground; • pipes placed in ducts accessible for inspection and repair.

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• To use separate effluent collection systems for: • contaminated process effluent water; • potentially contaminated water from leaks and other sources, including cooling water and surface run-off from process plant areas, etc.; • uncontaminated water.

• To use a buffer for waste water upstream of the WWT plant to achieve a constant quality of the waste water. This applies to all processes producing waste water, such as PVC and others.

• To treat waste water efficiently. WWT can be carried out in a central plant or in a plant dedicated to a special activity. Depending on the waste water pollution, additional dedicated pre-treatment can be required. Specific BAT for PE recommends among others:

Specific BAT for PET recommends among others:

• To apply a waste water pretreatment such as one or more of the following techniques: • stripping • recycling • or equivalent before sending waste water from PET production processes to a general plant. Specific BAT for Viscose fibers recommends among others:

• To recover sulphate as Na2SO4 from the waste water, the by-product being economically valuable.

• To reduce Zn from the waste water by alkaline precipitation followed by sulfide precipitation.

• To use closed-loop cooling systems. Specific BAT for PVC recommends among others:

• Rinsing and cleaning the reactor with water. • Draining of this water to the stripping system. • To use stripping for the suspension or latex to

1.10.4 Polymers From Natural Sources: Not So Green From a Water Point of View Currently there is an interest for polymers from natural sources due to ecological trends, economic circumstances, and geopolitical reasons:

obtain a low VCM content in the product.

• To treat waste water with a combination of: • stripping • flocculation • biological WWT

2 Sustainability: apart wood, their origin is in fast growing plants. Even for wood, renewing duration is far shorter than that of the fossil energy and crude oil used for plastics production.

Specific BAT for unsaturated polyesters recommends among others:

2 Geopolitical motivations: many plants grow in developing countries and need agricultural means instead of industrial ones.

• To thermally treat waste water arising mainly from the reaction. Specific BAT among others:

for

ESBR

recommends

• To design and maintain the plant storage tanks to prevent leaks and resulting air, soil and water pollution.

• To recycle water. • To treat waste water using biological treatment or equivalent techniques.

2 The ecology wave is becoming a buoyant marketing argument. 2 Environmental motivations: the production of green polymers saves energy and decreases certain forms of pollution but, from a water point of view, there are some issues concerning phosphate and nitrate levels, as we can see in Table 1.7. Of course, an example does not make the rule and other data may be found elsewhere.

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Table 1.7 Examples of Water Concerns. Example of Polymer From Natural Source

Synthetic Commodity Plastics

Water consumption

1.5

1.2 4

COD to water (mg/kg)

2.27

20 168

Phosphates to water (mg/kg)

234

n.a.

Nitrates to water (mg/kg)

24,481

n.a.

COD, chemical oxygen demand.

Reference Costello, M., 2011. Single ply roofing: introduction to a new sustainability standard for the roofing industry. J. ASTM Int. 8 (9), 1 6. Available from: https://doi.org/10.1520/JAI103741.

Further Reading Biron, M., 2014. Thermosets and Composites. Elsevier Ltd.

Biron, M., 2015. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2017. Industrial Applications of Renewable Plastics. Elsevier Ltd. Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Plastics Additives & Compounding, Elsevier Ltd. Plastics News.com, Crain Communications. Reinforced Plastics, Elsevier Ltd.

2 Plastics Overview Of course plastics activities must obey general and specific policies, directives, and regulations. The reader is solely responsible for his or her own problem and must study the requirements of the countries concerned by formulation, manufacture, commercialization, application, and waste disposal.

2.1 Do Not Confuse Thermoplastics, Thermoplastic Elastomers, Thermosets, Composites, and Hybrids Plastics are versatile materials based on polymers that differ by their chemical structure, physical form, and combination with other materials leading to very diverse features. The following is just brief and fragmentary information.

Alloys of compatible thermoplastics allow applications to benefit from the attractive properties of each polymer while masking its defects. Some thermoplastics are cross-linkable and are used industrially in their two forms, thermoplastic and thermoset; for example, the polyethylenes (PEs) or the vinyl acetate ethylene (VAE) copolymers (the links created between the chains limit their mobility and possibilities of relative displacement).

2.1.1.1 Advantages • Softening or melting by heating allows welding and thermoforming.

• The processing cycles are very short because of the absence of the chemical reaction of cross-linking.

• Processing is easier to monitor because there is only a physical transformation.

• Thermoplastics do not release gases or water vapor if they are correctly dried before processing.

2.1.1 Thermoplastics Thermoplastics have the simplest molecular structure, with chemically independent macromolecules (Fig. 2.1). By heating, they are softened or melted, then shaped, formed, welded, and solidified when cooled. Multiple cycles of heating and cooling can be repeated without severe damage, allowing reprocessing and recycling. Often some additives or fillers are added to the thermoplastic to improve specific properties such as thermal or chemical stability, ultraviolet (UV) resistance, and so forth. Composites are obtained by using short, long, or continuous fibers. Thermoplastic consumption is roughly 80% or more of the total plastic consumption.

• The wastes are partially reusable as virgin matter because of the reversibility of the physical softening or melting.

2.1.1.2 Disadvantages • When the temperature rises, the modulus retention decreases due to the absence of chemical links between macromolecules.

• For the same reason, the creep and relaxation behaviors are not as good as for the thermosets.

• During a fire, fusibility favors dripping and annihilates final residual physical cohesion.

• There are only a few materials that are workable in the liquid state.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00002-1 © 2020 Elsevier Ltd. All rights reserved.

45

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Figure 2.1 Schematic structure of a thermoplastic.

• Liquid Crystal Polymer, Polytetrafluoroethylene

PBI

LCP,PTFE,PFA,FEP,PI ETFE,PEEK

(PTFE), Perfluoroalkoxy, Fluorinated Ethylene Propylene, polyimides (PIs): high-tech uses, more limited consumption.

• PolyBenzImidazole: highly targeted uses and

PSU, PEI,PPS…

very restricted consumption.

PA,PC,PMMA,POM,PPE,PET,PBT…

2.1.2 Thermoplastic Elastomers

ABS,SAN PE,PP,PVC,PS

Figure 2.2 Pyramid of excellence for some thermoplastic families.

Thermoplastic elastomers (TPEs) are copolymers or compounds of thermoplastics and rubber. The elasticity of TPEs (Fig. 2.3A and B) comes from:

• the structure of the macromolecules with alterThe “pyramid of excellence” (Fig. 2.2) arbitrarily classifies the main families of thermoplastics according to their performances, consumption level, and degree of specificity:

• PE, Polypropylene (PP), Polyvinyl Chloride (PVC), Polystyrene thermoplastics.

(PS):

commodity

• Acrylonitrile Butadiene Styrene

(ABS), Styrene AcryloNitrile (SAN): copolymers with more specific applications.

• Polyamide

(PA), Polycarbonate (PC), Polymethylmethacrylate (PMMA), Polyacetal (POM), Polyphenylene Ether (PPE), PE Terephthalate (PET), Polybutylene Terephthalate (PBT) . . .: engineering thermoplastics.

• Polysulfone

(PSU), PolyetherImide (PEI), Polyphenylene Sulfide (PPS) . . .: engineering thermoplastics with more specific performances.

• Ethylene-tetrafluoroethylene, Ketone (PEEK): consumption.

high-tech

Polyetherether uses, limited

nating soft and hard segments, the latter gathering together to constitute the nodes of a physical lattice or

• a dispersed phase of soft elastomer, vulcanized or not, forming microscopic droplets in a continuous phase of a hard thermoplastic. This structure allows processing in accordance with thermoplastic techniques. The rubber provides elasticity. TPEs account for roughly 1% of total plastic consumption. They lead to a combination of interesting properties, including:

• elasticity in a limited range of temperatures • ease of thermoplastic processing without curing and, often, without a mixing step

• ease of recycling (as for all thermoplastics). On the other hand, their mechanical properties decrease as the temperature rises because of their thermoplasticity.

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47

(A)

(B)

Figure 2.3 Schematic structure of TPEs. (A) Copolymer with hard segments arranged in domains. (B) Compound of rubber particles dispersed in thermoplastic matrix. TPE, Thermoplastic elastomer.

COPE,PEBA,TP/Si-V TPU PP/IIR-VD PP/NBR-VD PP/EPDM-VD SEBS SBS, TPE-PVC, TPO

Figure 2.4 Pyramid of excellence for some TPE families. TPE, Thermoplastic elastomer.

The “pyramid of excellence” (see Fig. 2.4) arbitrarily classifies the main families of TPEs according to their performances, consumption level, and degree of specificity:

• Styrene Butadiene Styrene

(SBS), PVCbased TPE (TPE-PVC), Thermoplastic Olefin (TPO): the less elastic TPEs, fair thermal resistance

• Styrene Ethylene/Butylene Styrene (SEBS): same elasticity but better thermal behavior

• Vulcanized terpolymer ethylene, propylene, diene (EPDM) dispersed in PP (PP/EPDM-V): better elasticity and good thermal resistance

• Vulcanized nitrile butadiene rubber (NBR) dispersed in PP (PP/NBR-V): same elasticity plus oil resistance

48

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

• Vulcanized IIR dispersed in PP (PP/IIR-V): same elasticity plus gas impermeability

• Thermoplastic

polyurethane mechanical properties

(PUR):

high

• Simplicity of the tools and processing for some materials worked or processed manually in the liquid state.

• COPE, Polyether Block Amide (PEBA), TPE/ Si-V: high performances but high prices.

2.1.3 Thermosets Thermosets before hardening, like thermoplastics, are independent macromolecules. But in their final state, after hardening, they have a threedimensional (3D) structure obtained by chemical cross-linking produced after (spray-up molding or filament winding) or during processing (e.g., compression or injection molding). Fig. 2.5 schematizes the molecular arrangements of these polymers. Some polymers are used industrially in their two forms, thermoplastic and thermoset; for example, the PEs or VAE. Thermoset consumption is roughly 12% 20% of the total plastic consumption. The links created between the chains of the thermosets limit their mobility and possibilities of relative displacement and have certain advantages and disadvantages.

2.1.3.1 Advantages • Infusibility: thermosets are degraded by heat without passing through the liquid state. This improves some aspects of fire behavior: except for particular cases, they do not drip during a fire and a certain residual physical cohesion provides a barrier effect.

• When the temperature increases, the modulus retention is better due to the 3D structure.

• Better general creep behavior due to the links between the chains restricting the relative displacements of the macromolecules, one against the other.

Figure 2.5 Thermoset after cross-linking.

2.1.3.2 Disadvantages • The chemical reaction of cross-linking takes a considerable time that lengthens the production cycles and, often, requires heating—an additional expenditure.

• The processing is often more difficult to monitor because it is necessary to take care to obtain a precise balance between the advance of the cross-linking reaction and the shaping.

• Certain polymers release gases, in particular water vapor, during hardening.

• The wastes are not reusable as virgin matter because of the irreversibility of the hardening reaction. At best, they can be used as fillers after grinding.

• The infusibility prevents assembly by welding. The “pyramid of excellence” (Fig. 2.6) arbitrarily classifies the main families of thermosets according to their performances, consumption level, and degree of specificity:

• urea-formaldehydes: old materials of modest properties

• phenolic resins (PF) and melamines (MF): good thermal behavior but declining

• unsaturated polyesters (UPs) and PURs: the most used for their general qualities

• epoxy (EP): broad range of properties; some are used for high-tech composites

• silicones (Si): flexibility and high heat resistance; physiologically harmless

2: PLASTICS OVERVIEW

49

The main advantages of these composites are: Cy PI SI EP UP et PUR PF et MF

• mechanical properties are higher than those of the matrix

• the possibility of laying out the reinforcements to obtain the best properties in the direction of the highest stresses.

UF

Figure 2.6 Pyramid of excellence for some thermoset families.

The development of polymer composites is held back by recycling difficulties, attenuated in the case of the thermoplastic matrices. The “pyramid of excellence” (Fig. 2.7) classifies, arbitrarily as for the previous polymers, the composites according to their performances, consumption level, and degree of specificity:

Cy/CF PI composites SI/GF EP/ArF or CF or honeycomb EP/GF PF/GF UP composites

Figure 2.7 Pyramid of excellence for some composite families.

• UPs reinforced with glass fibers (GFs): the most used for their performances and low cost

• PF reinforced with GFs: fire resistance, good performances, and low cost

• EP reinforced with GFs that perform better than the UP/GF

• EP reinforced with aramid fiber (ArF) or carbon fiber (CF) or with honeycombs: high-tech and high-cost composites performing better than the EP/GF

• silicone (Si) reinforced with GFs: flexibility, heat resistance, chemical resistance, and physiological harmlessness

• PI reinforced with ArF or CF or with honey• PIs: high-tech uses, limited distribution • polycyanates (Cy): highly targeted uses and very restricted distribution

2.1.4 Polymer Composites Polymer composites are made from:

• a polymer matrix, thermoset, thermoplastic, or TPE

• a nonmiscible reinforcement closely linked with the matrix: fibers of significant length compared to the diameter, yarns, mats, fabrics, foams, honeycombs, etc. The consumption of composites with organic matrices is a few percent of the total plastic consumption.

combs: very high-tech and high-cost composites performing better than the EP composites; the consumption is limited

• polycyanate matrices: very specific uses, hightech and high-cost composites; very restricted consumption

2.1.5 Hybrid Materials Hybrid materials are not a clearly defined material category but result from a design method that associates, by integrating them closely, one or more polymers on the one hand and, generally, one or more other materials, which provide one or more functionalities difficult or impossible to obtain with only one polymer. The dividing line between hybrid materials and associated materials is rather fuzzy. This definition does not regard as hybrids, for example, those

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

50

polymers joined after their manufacture onto structures of metal or concrete. On the other hand, overmolding on structural and functional inserts is regarded as hybrid. The hybrid techniques often associate polymers and metals and combine the benefits of the two material classes. Metal provides the rigidity and the overmolded reinforced plastic keeps the shape of the metal and adds numerous functionalities. There is also a growing interest in the association of elastic polymers, which assume sealing or damping functionalities, with rigid plastics or composites that have the structural role. One of the materials can be overmolded on the other, or the two materials can be comolded. By associating simple and inexpensive plastic processes (e.g., injection molding) with simple and inexpensive metal processes (stamping, embossing, bending), the polymer/metal hybrids allow the integration, thanks to the plastic elements, of the maximum number of functionalities: mountings, fastening points, fixings, cable holders, housings, embossings, eyelets, clips, and so forth. This leads to:

• the elimination of the assembling stages of the

sealing and is used as a mandrel to make the envelope by the filament winding technique. The ArF or CF ensures mechanical resistance. The weight saving is 30% 50% compared to all-metal tanks and the costs are optimized.

• The engines of the Polimotor and Ford projects are hybrid composites of PF/GFs and EP/ GFs with combustion chambers, cylinders, and pistons in metal. This permits the direct contact with hot combustion gases that the polymer could not withstand. The composite provides the rigidity of the engine.

• Certain incinerator chimneys are used in hybrid stainless steel with an inner lining in sandwich resin/GFs with a core in foamed PUR. The materials associated with the polymers can also be concrete or wood, for example:

• azurel structural panels for individual construction, developed by Dow, made of wood and expanded PS

• rigid elements for the modular design of dwellings made of hollow structures of GFreinforced UP filled with concrete

suppressed components

• the reduction of the dimensional defects of the assembled components

• the avoidance or reduction of welding operations that can cause metal deformations This principle, in more or less complex versions, is applied to:

• the front ends of cars such as the Audi A6, Ford Focus, and VW Polo

• footbrake pedals in metal/plastic hybrid • wheels of planes in hybrid metal/composite EP/carbon

• car doors • frame hull (MOSAIC project) in hybrid composite/aluminum. Inversely, the polymer can sometimes provide structural functions, while the metal ensures a role not easily assumed by the polymer:

• For high-pressure air tanks, a hybrid design gives the best results: a thin metal liner ensures

2.2 Compound Is Much More than Polymer: Build the Best Balance of Engineering, Cost, and Environmental Requirements Thanks to Formulation Virgin polymers are generally unsuitable for industrial applications and must be compounded with the one or the other additives such as, for example:

• • • • •

secondary polymer plasticizers reinforcements protective agents colorants, etc.

To give a rough idea, there are in order of magnitude:

• 100 polymer families

2: PLASTICS OVERVIEW

51

• 1000 subfamilies • 100,000 grades.

TS

Keep in mind some basic principles, such as:

• Two grades are generally not interchangeable. • An additive has generally collateral effects

CUT

EB

including, but not limited to, cost variations.

• Sustainability must be considered for the total life making that the most sustainable compounds do not systematically lead to the most sustainable solutions, setup, and use phases turning the original ranking upside down. Obviously, improving sustainability needs to optimize formulation in various ways, including among other benefits:

• • • • • • • • •

ABS ABS/PC PC HDT A

Impact

Figure 2.8 Property examples for ABS, PC, and ABS/PC alloy. ABS, Acrylonitrile butadiene styrene; PC, polycarbonate.

optimal use of raw materials minimal resource depletion long lifetimes weight reduction better insulation effective recycling and reuse lower energy consumption lower carbon footprint reducing global warming, etc.

Of course, the designer must comply with laws, regulations, directives, and so forth, prescribed by the various countries concerning manufacture, use, disposal, pollution, health hazards, and so forth, of the designed product.

2.2.1 Plastic Alloying Plastic families are diverse but their number is limited and often there are wide gaps between the properties of two basic polymer types. To bridge the gap, two polymer families can be mixed if they are compatible or if it is possible to compatibilize them with a third material. Examples are numerous: ABS (the most widespread), ABS/PC, ABS/PA, ASA/PC, ASA/PVC, TPO, TPV, PPE (marketed grades are actually alloys with PS or PA), PA/PP, and so forth. Fossil plastics can be also allied with bioplastics to decrease the environmental footprint of

fossil plastics or to enhance the performance of bioplastics. For example, Fujitsu and Toray have developed a fire retardant (FR) resin made of a blend of PC and PLA (50/50) designed for laptops. This composition has the processability, heat resistance, and flame resistance required in larger IT devices. For a suitable mixing of two components, the properties of an alloy, including the cost, are generally intermediate between those of each component, as we can see in Fig. 2.8 for an ABS/PC:

• mechanical properties: tensile strength, elongation at break, and notched impact strength

• thermomechanical

properties: deflection temperature) A

HDT

(heat

• thermal properties: CUT.

2.2.2 Compounding With Additives A multitude of additives are proposed for adjustment of processing, mechanical properties, carbon footprint, aging resistance, sensory properties, fire resistance, cost, and so forth. Of course, enhancement of properties leads to better sustainability. The following information is theoretical and cannot be used for design or financial studies. It is the responsibility of the reader to determine the appropriate use of each product, processing method,

52

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

machinery, and ideas, as well as compliance with processing rules, safety precautions, health hazards, and existing national laws and regulations prescribed by countries concerning processing, commercialization, use, and application. The safety data, facts, and figures herein are provided for information only and are no substitute for the content of Material, Safety Data Sheet and other information from producers, compounders, converters, and other suppliers.

• mineral fillers such as talc, calcium carbonate, etc.

• glass microspheres, etc. Highly promising nanofillers, nanoclays, and carbon nanotubes are also developing well. Depending on the reinforcement, the main difficulties are:

• achieving excellent adhesion between matrix and reinforcement

2.2.2.1 Mechanical Property Upgrading and Customization: Toughening, Reinforcement, Plasticization Reinforcement

The practical goals of reinforcement are:

• to increase the modulus and strength • to improve the HDT • to reduce the tendency to creep under continuous loading

• to save costs by decreasing the material cost used to obtain the same stiffening The most up-to-date reinforcements are:

• fibers and assemblies containing fibers: • natural fibers generally enhance sustainability • glass and carbon fibers are highly reinforcing but have high carbon footprints making that the sustainability of these compounds must be researched

• the risk of shortened fibers broken during processing

• anisotropy due to the filler or fiber orientation and settling. With some processes, this is an advantage: a correct placement of the fibers permits reinforcement at specific points in the right direction. Reinforcement With Fibers

The principle of reinforcement is to transfer a part of the structural role to fibers that have much higher modulus and strength than the matrix. Fig. 2.9 plots tensile strength versus modulus for some typical fibers and matrices, and clearly shows the gap between the performances of the matrix and glass or carbon fibers. Currently, GFs are the most widely used, accounting for about 95% of the reinforcement fibers consumed by plastics. Aramid and carbon fibers account for nearly all of the remaining 5%. Natural fibers such as jute and flax are being developed to conform to environmental trends.

Tensile strength, MPa

10000

Glass Fiber

Aramid Fiber

Carbon Fiber

1000 Textile Fiber 100 Matrix Modulus, GPa 10 1

10

Figure 2.9 Fibers: Examples of tensile strength versus modulus.

100

1000

2: PLASTICS OVERVIEW

53

• the form of the fiber reinforcement (filament,

Textile fibers like nylon and polyester are used to reinforce flexible materials such as soft PVC. The properties of polymers reinforced with chopped GFs dispersed in the polymer matrix depend on:

roving, etc.)

• orientation of the fibers • the adhesion of the fibers to the matrix anisotropy in the final part.

• the nature of the fiber • the fiber loading • the aspect ratio (length vs diameter of the

Table 2.1 shows some examples of the reinforcement of PP including tensile strength, impact strength, modulus, and reinforcement ratios for various unidentified reinforced thermoplastics and thermosets. For a given material, the reinforcement level is highly dependent of the considered property. The reinforcement ratio is the performance of the reinforced polymer divided by the performance of the neat polymer.

fibers)

• the sizing of the fibers to enhance adhesion to the matrix

• the real length of the fibers in the final part • the quality of the fiber dispersion • the anisotropy in the final part

Reinforcement and Filling With Mineral Fillers

The reinforcement effect with mineral fillers is not as evident as with fiber reinforcement. Often the cost is significantly decreased but only a few properties are improved and others can be altered. Table 2.2 shows some examples of the property effect ratios for mineral filler-reinforced PP. The effect ratio is the performance of the reinforced

The properties of polymers reinforced with continuous filaments, rovings, fabrics, and so on depend on:

• fiber type • fiber loading

Table 2.1 Mechanical Property Examples for Different Reinforcements of Polypropylene Average Tensile Strength Variation (%)a

Average Impact Strength Variation (%)a

Reinforcement

(MPa)

PP Ho

None

30

PP 10% 40% mineral

Spherical particles

21

30

74

185

PP 10% 20% GF

Fibers

45

150

97

1142

PP 30% 40% GF

Fibers

56

187

102

1155

PP 10% 40% talc

Platelets

24

20

115

1187

PP copolymer

Copolymer

32

17

280

1600

PP high impact

Dispersed polymer

30

0

554

11285

(J/m) 40

Examples of Reinforcement Ratios Based on Tensile Strength and Modulus Glass fiber

Strength

Modulus

None

1

1

Dispersed short GF

2.2

5

Dispersed long GF

3.3

6.7

Fabric reinforcement

5

5

Unidirectional reinforcement

20

20

a Variation (%) relative to the value measured for neat homopolymer polypropylene. GF, Glass fiber; PP, polypropylene.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.2 Examples of the Effect of Mineral Fillers on Polypropylene Properties Effect Ratio Talc

Mineral

Glass Fiber

Tensile strength

0.8

0.7

1.5

Tensile modulus

2.4

2.1

3.2

Notched impact strength

0.4

0.3

0.3

HDT A

1.2

1.1

2.0

Thermal conductivity

1.9

1.9

1.4

Coefficient of thermal expansion

0.5

0.4

0.5

Density

1.2

1.2

1.1

Shrinkage

0.5

0.4

0.3

HDT, Heat deflection temperature.

polymer divided by the performance of the neat polymer. Properties of low-level GF reinforced PP are given for comparison. Compared to neat polymer and GF reinforced polymer:

• tensile strength decreases compared to neat polymer

• elongation at break is intermediate between neat and GF reinforced polymer

• modulus increases and becomes intermediate between neat and GF reinforced polymer

• impact strength decreases • HDT increases and becomes intermediate between neat and GF reinforced polymers

• coefficient of thermal expansion and shrinkage are reduced while thermal conductivity increases

• price decreases but density increases Reinforcement With Glass Beads

Glass beads act as a mineral filler with an aspect ratio of 1. Table 2.3 displays results for glass bead reinforced PA. The effect ratio is the performance of the reinforced polymer divided by the performance of the neat polymer. These results are of the same order as those in Table 2.2 for mineral-filled PP versus neat polymer:

• tensile strength is unchanged • modulus increases and becomes intermediate between neat and GF reinforced polymer

• impact strength decreases

Table 2.3 Examples of the Effect of Glass Beads on Polyamide Properties. Effect Ratio Tensile strength

1

Tensile modulus

1.5

Notched impact strength

0.4

Hardness

1.2

HDT A

1.2

Thermal conductivity

1.7

Coefficient of thermal expansion

0.6

Density

1.2

Shrinkage

0.6

Water absorption

0.4

HDT, Heat deflection temperature.

• HDT slightly increases • coefficient of thermal expansion and shrinkage are reduced while thermal conductivity increases

• density increases • water absorption decreases due to the specific hygroscopic character of PA while glass beads are hydrophobic Nanofillers

Nanofillers are made up of:

• elementary particles in platelet form with thickness of the order of the nanometer and diameter of the order of 100 nm

2: PLASTICS OVERVIEW

55

Table 2.4 Property Examples for Polyamide Nanocomposites Processed by Various Methods PA Nanocomposites Neat PA

Property

Reinforcement Ratios

Tensile modulus (GPa)

2.7

3.3 4.3

1.2 1.6

Tensile stress at yield (MPa)

64

69 85

1.1 1.3

Elongation at break (%)

40

8 60

Izod notched impact (J/m)

37

36 50

1 1.3

PA, Polyamide.

• primary particles formed by stacking several elementary particles. The thickness is about 10 nm

• aggregates of numerous elementary particles To exceed the typical filler reinforcement and to obtain a real nanocomposite, it is necessary to destroy the primary particle structure during processing:

• either completely, by dispersing the elementary particles in the macromolecules—delaminated nanocomposite, or

• partially, by intercalating macromolecules between the elementary particles—intercalated nanocomposite. The most popular nanofiller is a natural-layered silicate, montmorillonite, that is subjected to specific treatments. The properties of the final nanocomposite depend on these treatments and the mixing efficiency. Table 2.4 displays property examples for PA nanocomposites processed by various methods. Practically, all polymers can be processed to make nanocomposites. This emerging technology is developing in PA and TPO nanocomposites with applications in the automotive industry, and there are experiments with saturated polyesters, acrylics, PSs, among others. The nanosilicates, because of their high-aspect ratio, high-surface area, and nanometric scale, are reinforcing at low-incorporation levels. The main nanocomposite properties are:

• mechanical performances between those of the neat polymer and short GF reinforced grades

• higher HDT than neat polymer but lower than short GF reinforced grades

• density much lower than reinforced grades

• lower gas permeability • better fire behavior Nanomaterials are emerging and their behaviors concerning humans and environment are not yet known. Regulations depend on the countries concerned and are rapidly evolving. Consequently designers, employers, users, and other players must continuously study regulations and the risks arising from the application of new technologies. Risks include, but are not limited to, inhalation of the material and emitted produces, absorption through the skin, contact with the skin or eyes, ingestion, fire and/or explosion (ultrafine dust), hazardous chemical reactions, damaging of installations by nanomaterials (corrosion etc.), and so forth. For an industrial example (see Table 2.5), the reinforcement ratios obtained with a loading of nanosilicate as low as 2% are attractive. The reinforcement ratio is the ratio of the nanocomposite performance versus that of the neat polymer. For a very similar density, the nanocomposite has significantly better thermomechanical properties than the neat PA. Impact Modifiers

Impact modifiers enhance impact strength at ambient temperature and reduce embrittlement at subzero temperatures. The principle is to distribute and dampen the energy of an impact by adding an elastomer or a rubbery polymer, which also reduces rigidity and some other properties. The impact modifier is finely dispersed in the thermoplastic and particles absorb the energy of the impact. Numerous polymers are used, for example, ABS, methyl methacrylate butadiene-styrene, chlorinated polyethylene, SBS, SEBS, polyacrylate, polybutadiene, EPDM, ethylene-acrylate, modified polyolefins, among others. The selected impact

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.5 Example Properties for a 2% Nanosilicate-Filled Polyamide Property Example

Reinforcement Ratio

Density (g/cm )

1.15

1

Tensile strength (MPa)

100

1.25

Flexural modulus (GPa)

3.9

1.3

HDT A (1.8 MPa) (°C)

140

1.9

3

HDT, Heat deflection temperature.

Table 2.6 Examples of Toughening Effects on Properties of Polyamide (PA) and Polyacetal (POM). Ratios: Performance of Impact Grades Divided by the Same Performance of Unmodified Grade PA66

POM

Impact strength

5

2

Hardness, Rockwell M

0.5

0.7

Tensile strength

0.6

0.8

Elongation at break

1

2.9

Tensile modulus

0.4

0.6

HDT B

0.9

0.9

HDT, Heat deflection temperature.

modifier must be compatible with the polymer to be enhanced and adhere strongly to it. It must have enough cohesive strength and a glass transition temperature low enough to maintain high-impact strength at low temperatures. Impact enhancers modify the balance of properties, notably stiffness, hardness, HDT (see Table 2.6), as well as, possibly, weatherability, and thermal stability. Some inorganic impact modifiers are also marketed, such as amorphous silicon dioxide. Plasticization

Plasticizers are mainly used to obtain better flexibility at ambient and low temperatures. However, they can also have other advantages, like the possibility to increase the amount of filler, which leads to cost savings, or, with specific grades, the possibility to bring other characteristics such as fire retardancy and antistatic effect. Processing is generally enhanced, as mixing and shaping are easier. Unfortunately, they can have some drawbacks, such as decreased tensile strength and modulus, pollution, toxicity, migration, or environmental risks, therefore the local and professional regulations, standards, and specifications must be studied.

For specific polymers, halogen- and phosphorusfree plasticizers can reduce the oxygen index. The transparency can be altered if the compatibility is low and/or the refractive index is inadequate. The plasticization benefits can be reduced or even suppressed if the plasticizers disappear during the service life by:

• volatilization, the more so as the temperature rises

• migration by contact with other solid materials, the more so as the temperature rises

• extraction by contact with fluids, etc. There are superabundant commercial products. The following is a list of some of them:

• the esters: • the phthalates: diethylhexyl (also called dioctyl), diethyl hexyl phthalate (DEHP) (or dioctylphthalate (DOP)), is the most widely used; dimethyl, diethyl, dipropyl, dibutyl, dipentyl, dihexyl, diisoheptyl, dinonyl, diisononyl, butylbenzyl, dibenzyl, etc.

2: PLASTICS OVERVIEW

57

Table 2.7 Examples of Polyvinyl Chloride Properties According to the Degree of Plasticization Negligible Plasticization

Low Plasticization

High Plasticization

Density (g/cm3)

1.35

1.35

1.15

Shrinkage (%)

0.3

0.8

5

Hardness, Shore D

75

70

15

Tensile strength (MPa)

45

25

10

Elongation at break (%)

40

200

500

Tensile modulus (GPa)

3

1

0.001

Notched impact strength (J/m)

20

NB

NB

HDT B (°C)

70

55

,30

Glass transition temperature (°C)

60

25

250

Minimum service temperature (°C)

25

210

240

Resistivity (Ω cm)

15

15

10

Oxygen index (%)

40

40

20

HDT, Heat deflection temperature.

• the phosphates • other esters are used to some degree, for

• aging resistance to heat, humidity, light, and

example, sebacates, adipates, azelates, glutarates, formates, hexoates, caprates, caprylates, tallates, trimellitates, and tricitrates

• volume cost • toxicity and environmental risks • stress cracking of other polymers by plasticizer

• petroleum oils, including the three main categories: paraffinics, aromatics, naphthenics

• low-molecular weight rubbers or plastics (PE, polyphenylene oxide), and liquid rubbers

• chlorinated hydrocarbons • epoxidized soya bean oil • fire-retardant additives such as tricresyl phosphates and chlorinated waxes The choice of plasticizer types and levels is a subtle compromise between the bestowed advantages and drawbacks:

• compatibility with the polymer to be plasticized • targeted processing and rheological properties • specified thermal, electrical, and mechanical properties of the end product

• optical properties: light transmission, haze, etc. • fire behavior: fire retardancy, smoke, toxicity, corrosivity, etc.

• chemical resistance

UV

migration, discoloration of rubber by contact

• suitability for contact with food and medical articles Table 2.7 displays three examples of PVC properties according to the degree of plasticization.

2.2.2.2 Aging Protection: Additives, Films Oxygen, heat, light and UV, shear, and dynamic stresses attack polymers, degrading performance and esthetic. Practical consequences of aging generally are:

• mechanical property degradation, weakening, embrittlement, etc.

• esthetics degradation, color change, blooming, cracking, crazing, staining, etc.

• weight loss, shrinkage • desorption and consumption of additives • pollution of environment, etc.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.8 Examples of Antioxidant Efficiencies in Polypropylene Films Air Aging at 130°C (Hours to Reach Brittleness)

Efficiency Ratio Linked to Control Performance

Without protective agent

5

1

Protective agent A

34

7

Protective agent B

89

18

Protective agent C

91

18

Protective agent D

264

53

Protective agent E

456

91

Protective agent E 1 D

456

91

Protective agent E 1 A

552

110

Protective agent E 1 B

576

115

Durable protection is needed to avoid damage during processing, to satisfy the customer’s specifications and requirements, and to give satisfaction during the complete service life of parts. Protective additives can be classified as follows:

Table 2.9 Examples of Interaction Between Antioxidant and Silica in Polypropylene Films Air Aging at 130°C (Hours to Reach Brittleness) Without protective agent

5

Silica

3

Protective agent E

456

thermooxidation during service life, avoiding molecular weight changes and loss of mechanical, physical, and esthetic properties

Protective agent E 1 silica

336

Protective agent B

34

• light stabilizers: decrease degradation initiated by

Protective agent B 1 silica

91

• processing stabilizers: antioxidants incorporated into the polymer to avoid heat degradation during processing

• antioxidants: added to the polymer to decrease

sunlight or UV exposure. Certain fillers absorb UV and act as filters protecting the polymer

• hydrolysis stabilizers: chemicals added to the polymer to avoid hydrolysis degradation during service life Of course other classifications may be found in the literature. Another route to protect polymers from oxygen, light, and UV is to encapsulate the part with a continuous film of another, more-resistant polymer to provide a barrier to oxygen. This technology is also used for decoration of plastic parts, such as in-mold decoration (IMD), painting, and multilayer sheets for thermoforming. These films offer no protection against heat. All these methods cannot totally inhibit polymer degradation. This is just a question of time, heat, and exposure to light, water, and other aggressive environments.

The efficiency of these additives depends on:

• • • •

the nature of the matrix the nature of the protective additive the actual level of additive in the part interaction with the other ingredients

Table 2.8 shows examples of the different efficiencies of eight antioxidants incorporated in the same polymer. The other additives in the compound can also influence aging as shown in Table 2.9, which displays the effect of silica in combination with two different protective agents. In one case, the silica degrades the aging resistance and in the other silica enhances aging behavior.

2: PLASTICS OVERVIEW

59

Days

500

250

mm 0 0

10

20

Figure 2.10 Days of aging leading to the same degradation level versus sample thickness. Table 2.10 Examples of Ultraviolet (UV) Degradation According to the Polymer and Exposure Location % Degradation Tensile Strength PC

Unstabilized

Elongation at Break

Arizona

93

UV stabilized PC white

Unstabilized

3 Florida

UV stabilized PE

Unstabilized

Impact

Florida

UV stabilized

4

78

9

7

22

15

44

41

48

24

22

5

PC, Polycarbonate; PE, polyethylene.

High thickness of parts decreases oxygen diffusion in the core of the polymer and reduces degradation, as shown in Fig. 2.10. Weathering is difficult to quantify because of the variation of the parameters according to the local conditions:

• • • • • • •

hours of sun per annum irradiation energy UV level average and extreme temperatures

Table 2.10 shows examples of the efficiencies of anti UV stabilization. Please note certain properties may be improved when a few others are damaged. The other additives in the compound can also influence weathering as shown in Table 2.11, which displays the effect of colorants in combination with UV stabilization. Aging behavior depends on the nature of the colorant and the UV filtering action of the filler. A black compound is by far the best choice.

hygrometry, rain ozone pollution, acid rain, etc.

The technical consequences of weathering are similar to heat aging with more pronounced surface degradation and notably:

• discoloration, yellowing, gloss loss, decreased transparency for transparent polymers

• chalking, crazing, hardening

2.2.2.3 Sensory Properties The market appeal of plastics is important for numerous applications such as packaging, automotive, and appliances. Color, transparency, gloss, and odor contribute to make a plastic part attractive, unappealing, or repulsive. Color can be obtained by adding colorants to compounds or encapsulating the part with a continuous film of another colored or printed polymer:

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.11 Examples of Ultraviolet Exposure Time to Reach the Same Level of Degradation of Polypropylene (PP) According to the Colorant Exposure Time of Colored PP Divided by Exposure Time of Pure PP Pure PP

1

Red A

1

Magenta

1

Blue C

1.8

Yellow

2

White

2.3

Red B

2.8

Brick red

3.3

Blue D

3.5

Green

3.5

Black

12

IMD, painting, multilayer sheets for thermoforming, and so forth. Colorants can be classified according to:

• their chemical structure: inorganic or organic • their form: powders, masterbatches, or concentrates in pellets, pastes, liquids, dustless powders, encapsulated, etc.

Scratch-Resistance Improvement

Soft polymers are more sensitive to scratch than some harder plastics. According to the used polymer, the addition of silicone, at a level of 2% to less than 10%, can help reduce the coefficient of friction and correspondingly improve the scratch resistance. For example, the scratch resistance of talcfilled TPOs modified with 2% 3% silicone from masterbatches is significantly improved and visible whitening is suppressed under conditions that damage the same TPO without silicone. Paintability must be verified but a low silicone level (e.g., 2.5%) does not affect paintability, and weathering resistance increases showing less change in aspect than the control without silicone. Surface treatments with hard resins are also used. Odors

Some virgin or recycled plastics can develop unpleasant odors during and after processing or after aging. To avoid or reduce this, it is possible to: • choose odorless grades and additives • add deodorants or specific fragrances marketed for polymers • add bactericides or preservatives to avoid growth of microorganisms, fungi, etc. during service life

• their function: colorants, brighteners, phosphorescent colorants, pearlescent colorants, metallic colorants, etc. Clarity and transparency can be enhanced by adding clarifiers. Matting can be obtained by adding special mineral fillers, another secondary polymer that is miscible to a greater or lesser degree with the main polymer, or proprietary additives. Glossy polymers can be obtained by polishing, postmolding into perfectly polished molds, lay out of films, IMD, film insert molding (FIM), in-mold coating (IMC), painting, and so forth. The choice of additives depends on numerous parameters concerning the nature of the polymer, the processing constraints (notably heat exposure, mixing technology), end-product esthetics, and the durability under service conditions of the end product.

2.2.2.4 Specific Properties: Specific Grades and Additives Fire Behavior

Polymers are rich in carbon and are potential fuels more or less easily flammable. Please note that fire retardancy does not mean nonflammable, noncombustible, unburnable, and so on. Fire behavior is very complex for several reasons:

• technically: it is necessary to converge on a difficult balance of fire retardancy and lowsmoke emission with constraints concerning the opacity, toxicity, and corrosivity of fumes

• legally: standards, regulations, and specifications are complex and evolving, and vary according to country and industrial sector

2: PLASTICS OVERVIEW

61

• FRs can modify mechanical properties and

Some FRs are:

esthetics

• Mineral fillers and additives: aluminum trihy-

FRs can be halogenated or not, or phosphorous derivatives. The first question is to decide between halogen-free and halogen-containing systems. The second question concerns the possible use of phosphorus additives. Fig. 2.11 schematizes some possible routes in each case.

Halogen free

Phosphorous free

drate (ATH), magnesium hydroxide, and boron derivatives are the best known but tin derivatives, ammonium salts, molybdenum derivatives, and magnesium sulfate heptahydrate are used to varying extents, and nanofillers are developing.

• Phosphorus additives: red phosphorus, phosphate esters, ammonium polyphosphate, melamine phosphates, and melamine pyrophosphate. Some of them are halogenated.

Halogen containing

Phosphorous containing

Mineral fillers

Phosphorous additives

Nanofillers

Mineral fillers

Expandable graphite

Nanofillers

• Halogenated derivatives: brominated organic compounds are the most used, often in combination with antimony trioxide to develop a synergistic effect. However, this generates a lot of smoke and toxic fumes, which is unacceptable under many countries’ regulations and standards.

Chlorinated additives

Brominated additives

• Brominated PS is marketed as a fire-retardant

Phosphorous additives

additive.

• Several halogenated FRs are banned or threat-

Synergists

Synergists

Expandable graphite

ened. It is the responsibility of the reader to study regulations relating their use in various countries.

Mineral additives

Expandable graphite

Figure 2.11 Examples of routes for fireproofing.

Table 2.12 shows some example of properties of fireproofed grades. These examples are not exhaustive and indicated limits concern only a few grades. Other data can be found in the literature relating to other grades.

Table 2.12 Examples of Flame-Retardant Grade Properties Rigid PVC Control

Limits of 10 FR Formulations

Oxygen index (%)

38

39

64

Smoke parameter (arbitrary unit)

164

57

230

Heat stability (arbitrary unit)

36

19

39

Impact strength (arbitrary unit)

14

7

20

EVA Control

Limits of 10 Halogen-Free FR Formulations

Oxygen index (%)

18

32

39

UL94 fire rating

Fail

V2

V0

Smoke, CO yield (arbitrary unit)

0.028

0.008

0.012

Tensile strength (MPa)

17

9

11

Elongation at break (%)

1470

65

160

EVA, Ethylene-vinylacetate; FR, fire retardant PVC, polyvinyl chloride; UL, Underwriters Laboratories.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.13 Conductive Polypropylene: Stainless Steel or Carbon Fibers Fibers

Stainless Steel

Carbon

3

103

Resistivity (Ω cm)

10

Tensile or flexural strength (MPa)

41

41

Flexural modulus (GPa)

1.4

4.3

Table 2.14 Properties of Electromagnetic Interference Grades Compared to Neat Polymers PA66 Aluminum level (%)

PPE

0

40

0

40

3

Specific gravity (g/cm )

1.1

1.5

1.1

1.5

Elastic modulus (GPa)

2.3

5

2.5

5.2

Tensile strength (MPa)

60

41

55

45

Elongation at break (%)

200

4

30

3

10

2.2

5

1.1

85

190

110

110

CTE (10

25

/°C)

HDT 1.82 MPa (°C)

CTE, Coefficient of thermal expansion; HDT, Heat deflection temperature; PA, polyamide; PPE, polyphenylene ether.

Conductive Polymers

Conductive polymer is a generic term covering a broad range of resistivities. Two routes are suitable for producing conductive polymers:

efficient at a relative humidity as low as 15%. Some are offered in masterbatches based on polyolefins, PSs, polyesters, acrylics, ABS, POMs, among others. Conductive Carbon Blacks

• Intrinsic conductive polymers obtained by polymerization of conductive macromolecules. This is a difficult route for industrial applications.

• Extrinsic conductive polymers obtained by adding specific additives to naturally insulating polymers. At present, this is the easiest industrial method. According to the conductivity level, the main additives used are:

• • • •

antistatic specialties conductive carbon blacks conductive fibers made out of carbon or steel

There are specific grades and masterbatches of carbon blacks especially marketed as additives for conductive plastics. It should be noted that the carbon blacks modify other properties of the polymer, especially its color. Conductive Fibers

Specific grades of carbon and steel fibers are especially marketed as additives for conductive plastics having resistivities of roughly 103 Ω/cm. The other properties of the final material, such as color, modulus, and impact strength, are modified. Carbon fibers have a large reinforcing effect. Table 2.13 compares some properties of conductive PPs obtained by adding stainless steel or carbon fibers.

metal powders or flakes Metal Powders or Flakes

Antistatic Specialties

Nonblack antistatics allow surface resistivities roughly in the range of 107 108 Ω/m2 to be obtained but their action generally depends on the relative humidity. However, new generations are being marketed without this drawback and are

Aluminum, copper, nickel, and silver powders or flakes are used to obtain electromagnetic interference (EMI) grades. The other properties—color, modulus, impact strength, and so forth—are modified. Table 2.14 shows some examples using aluminum powder for EMI shielding.

2: PLASTICS OVERVIEW

Additives for Antifriction Polymers

The most up-to-date additives for antifriction compounds are:

• specific fillers: MoS2, graphite • polymers: PTFE and silicone are efficient for providing antifriction properties but wear resistance falls. More rarely used are:

• carbon or ArFs to simultaneously enhance mechanical properties and coefficient of friction and decrease the wear

• ceramics such as boron nitride or silicon carbide To enhance mechanical properties and decrease wear, GFs are added to polymers but they are abrasive and attack the opposing surface. According to the circumstances, they can also increase the coefficient of friction. Carbon fibers are more satisfactory, simultaneously bringing a lower friction coefficient and lower wear. Table 2.15 shows the effects of several lubricating fillers on the friction properties of PAs 6 or 66 possibly reinforced with glass or carbon fibers. Silicon carbide is marketed as a surface enhancer (see Table 2.16). At levels of less than 10%, it significantly improves the coefficient of friction and the wear resistance. Polymers With High Thermal Conductivity

General-purpose polymers, being thermal insulators, cannot dissipate heat generated by mechanical work or by electronic devices and so on. If the temperature rises, the mechanical properties of the polymer decrease and aging speeds up. Eventually, the temperature can reach the melting point and/or the ignition temperature. To ease the dissipation of thermal flow, it is worthwhile to use dissipative additives such as ceramics, metal powders, or carbon fibers that have a high thermal conductivity. To provide some idea, thermal conductivities (W/m K) are roughly in the range of:

• 0.2 0.3 for neat polymers such as PP, PA, and PPS

• 25 300 for ceramics

63

• 60 400 for copper or aluminum • 10 170 for carbon fibers The possible limitations are:

• the cost, for example, boron nitride powder prices are in the range of USD 45 165/kg.

• the toxicity of, for example, beryllium oxide powders when inhaled The increase in the polymer thermal conductivity is far from the predicted values resulting from a mixing law and actual data are low, for example:

• 1 1.2 W/m K for structural plastics • 2 7 W/m K for carbon fiber reinforced thermoplastics according to the direction of testing

• 14 W/m K for nonstructural polymers Table 2.17 displays some example properties for polymers filled with ceramic, aluminum, or carbon fiber. Note that:

• ceramics also provide electrical insulation with generally some mechanical performance decay

• carbon fibers also provide high electrical conductivity with high mechanical performances

• aluminum provides medium electrical conductivity with some mechanical performance decay Magnetic Polymers

General-purpose plastics are not magnetic and cannot be used to produce magnets that generate permanent magnetic or electromagnetic fields for diverse applications, from domestic to highperformance devices: DC micromotors, telephones, coupling devices, toys, hardware, ore screening, and so forth. However, magnetic additives such as ferrites or rare earths can be added to plastics to produce polymer magnets. Health and safety hazards must be studied. The two main families of magnetic additives used for polymer magnets are ferrites and rare earths, which have very different characteristics. Anisotropic powders of ferrites have excellent cost-to-performance ratio, limited service temperatures, and low-electrical resistance.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.15 Effects of Several Lubricating Fillers on the Friction Properties of Polyamides Tribological Filler Type

Coefficient of Friction Level (%)

Polymer

Static

Dynamic

Wear (arbitrary unit)

Neat and glass fiber reinforced polyamides None, control

0

Neat PA

0.22

0.3

4

MoS2

5

PA6 30 GF

0.3

0.3

2.2

PA66 30 GF

0.3

0.3

2.8

PA6

0.18

0.11

120

PA66

0.17

0.11

100

PA66 30 GF

0.26

0.1

2

PA66

0.1

0.11

120

PA6 30 GF

0.19

0.13

2

PA66 30 GF

0.17

0.1

2.3

10

PA66 10 CF

0.22

20

PA6 20 CF

0.22

PA66 20 CF

0.2

PA6 30 CF

0.2

PA66 30 CF

0.19

PA66

0.11

0.08

1.5

0.12

0.08

0.8

PTFE

PTFE/silicone oil

15

13/2

Carbon fibers Carbon fibers

30 Carbon fibers and tribological fillers CF/PTFE

15/20

15CF/20PTFE CF/PTFE/silicone oil

15/13/2

PA66 15CF/13PTFE/ 2 Silicone oil

CF, Carbon fiber; GF, glass fiber; PA, polyamide; PTFE, polytetrafluoroethylene.

Rare earths have higher magnetic performances, service temperatures, electrical resistance, and costs. Table 2.18 shows property examples of plastic magnets based on ferrites or rare earths.

2.2.2.5 The Cost Cutters It is possible to cut costs by incorporating cheap fillers such as calcium carbonate, talc, kaolin, feldspar, wollastonite, silica, among others, or by using recyclates and, to a certain extent, by foaming, which leads to an increase of the volume for the same weight of resin and other expensive ingredients. Nonblack Fillers

The main nonblack fillers are, for example, calcium carbonates, broadly used in PVC; talcs,

broadly used in PP; titanium dioxide used as a white pigment; clays or kaolins; ATH used in flame-retardant compounds; precipitated silicates; micas, wollastonite, or calcium metasilicate; barium sulfate used for its opacity to X-rays and high density; and lithopone; quartz used in flour form. The cost savings are very different per weight and per volume. For two fillers with the same price, 10% of the polymer price, but of very different densities, 2 and 5 g/cm3, respectively, cost savings are:

• 30% per weight in both cases • 16% per volume for the light filler and only 5% for the heavy one.

2: PLASTICS OVERVIEW

65

Table 2.16 Examples of Some Polymer Characteristics Polymer

Thermal Conductivity (W/m K)

Tensile Strength (MPa)

Neat

0.2

34

Ceramic

1.2

17

Neat

0.2

93

Ceramic

1

93

Aluminum

1

41

Neat

0.3

79

Ceramic

1.2

52

Carbon fiber

2.2 7

139

Polypropylene

Polyamide

PPS

PPS, Polyphenylene sulfide.

Table 2.17 Examples of Some Polymer Characteristics. Polymer

Thermal Conductivity (W/m K)

Tensile Strength (MPa)

Neat

0.2

34

Ceramic

1.2

17

Neat

0.2

93

Ceramic

1

93

Aluminum

1

41

Neat

0.3

79

Ceramic

1.2

52

Carbon fiber

2.2 7

139

Polypropylene

Polyamide

PPS

PPS, Polyphenylene sulfide.

Table 2.18 Property Examples of Plastic Magnets Magnetic Additive

Ferrite

Rare Earth

Induction (kG)

1.5 2.7

4 8

Maximum energy product (MGOe)

0.5 1.7

3 12

Density (g/cm )

3.5 3.7

5 6

Tensile strength (MPa)

60 80

HDT (°C)

100 120

3

Service temperature (°C) HDT, Heat deflection temperature.

Up to 110

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.19 Performance Indices of Mineral-Filled Polyamide Linked to the Same Performances of Neat Polyamide (PA) Performances of 30% Mineral-Filled PA Divided by Neat PA Performances Density

1.2

Shrinkage

0.4

Water absorption after 24 h

0.6

Tensile stress at yield

0.8

Tensile strength

0.8

Elongation at break

0.3

Tensile modulus

2

Flexural modulus

2

HDT A

2

Coefficient of thermal expansion

0.5

HDT, Heat deflection temperature.

As already seen, the use of mineral fillers not only has economic advantages but also technical advantages (see Table 2.19 showing the performance indices of mineral-filled PA) such as:

• lower shrinkage • lower water absorption for hygroscopic polymers and nonhygroscopic fillers

• higher rigidity • higher HDT • lower coefficient of thermal expansion There are also some drawbacks such as:

• higher density • lower strength and elongation at break

As some properties are affected by recycling, the designer must be vigilant, notably concerning ultimate mechanical performances such as tensile and impact strengths. Some countries’ regulations can restrict the use of recyclates.

2.2.2.7 Structural Foams Use of limited blowing leads to structural foams with reduced weight and, therefore, reduction of raw material cost, but the designer must verify that the overall processing cost does not overrun that saved on material and that mechanical properties are good enough. Table 2.21 compares performance examples of structural foam and dense PEI. Drops in tensile strength and modulus are more important than the density change, but declines in flexural modulus and HDT are favorable and the coefficient of thermal expansion of the foam is significantly lower. These data are examples only and cannot be considered as representative.

2.3 Understand Particular and Surprising Behavior of Plastics Plastics are organic macromolecules generally made out of carbon, hydrogen, and some other chemical elements such as oxygen, azote, chlorine, sulfur, fluorine, silicon. All the properties depend on the composition, the chain architecture, the molecular weight, and so forth.

2.3.1 Elemental Composition Is Essential Although a limited panel of chemical elements is involved in plastic formulae, the composition is a determining factor for properties, as shown in Table 2.22 displaying the property spectrum of commodity and common engineering plastics.

2.2.2.6 Use of Recycled Plastics

2.3.2 Molecular Weight and Chain Architecture Are Also of High Importance

Suitably recycled plastics can have properties that are good enough for many applications, with a noticeable economic advantage. Table 2.20 compares properties of virgin and recycled PAs. These data are examples only and cannot be considered as representative.

Albeit having a simple chemical formula— (CH2 CH2)n—PE is a broad family with versatile properties (see Table 2.23) that depend on the molecular weight and the used polymerization process. In addition, please note some PE grades may be incompatible with others.

2: PLASTICS OVERVIEW

67

Table 2.20 Performance Examples of Virgin and Recycled Polyamide (PA) 6 Virgin Neat PA 6

Recycled Neat PA 6

Variation (%)

Density

1.13

1.13

5

Shrinkage

1.6

1.6

5

Water absorption saturation

9.4

9.5

5

Rockwell R hardness

119

119

5

Tensile stress at yield

85

80

26

Tensile strain at yield

5

3.5

230

Tensile modulus

3.3

3.2

5

Flexural modulus

3

2.8

27

Notched Izod, 230°C

5

4

220

Notched Izod, 23°C

5.5

4.5

218

HDT B

184

175

25

67

60

210

7.5

7.5

5

33% GF PA 6

33% GF PA 6

Variation (%)

Virgin

Recycled

Density

1.39

1.38

5

Shrinkage

0.2 0.9

0.2 1

5

Water absorption saturation

6.7

6.6

5

Rockwell R hardness

121

121

5

Tensile stress at break

200

165

217

Tensile strain at break

3

3

5

Tensile modulus

10.7

9.5

211

Flexural modulus

9.4

9.3

5

Notched Izod, 230°C

11

8

227

Notched Izod, 23°C

15

12

220

HDT B

218

215

5

HDT A

203

208

5

HDT A Coefficient of thermal expansion (10

25

/K)

GF, Glass fiber; HDT, heat deflection temperature.

2.3.3 Crystalline and Amorphous Thermoplastics, Glass Transition Temperature Polymers can be amorphous (randomly arranged chains), crystalline (well-ordered chains), or semicrystalline (see Fig. 2.12). Generally speaking, the crystallinity level induces common property trends.

2.3.3.1 Amorphous Polymers Amorphous chains of an amorphous polymer are randomly arranged. The degree of crystallinity (the weight fraction or the volume fraction of crystalline material) is zero. Amorphous polymers slowly soften when heated above their glass transition temperature (Tg). As examples we can quote among others, PMMA, PC, PVC, SAN, ABS, PS, PPE, PSU, special amorphous PAs, among others.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.21 Performance Examples of Structural Foam and Dense Polyetherimide Dense

Structural Foam

Variation (%)

Density

1.27

0.9

229

Tensile stress at break

90

40

256

Tensile strain at break

60

4

293

Tensile modulus

3

1.8

240

Flexural modulus

3.3

2.9

212

HDT B

210

195

27

200

175

212

5.6

4

229

HDT A Coefficient of thermal expansion (10

25

/K)

HDT, Heat deflection temperature.

Table 2.22 Commodity and Common Engineering Plastics: Examples of Property Ranges Density

0.917 1.32

Shrinkage, %

0.1 1.1

Shore hardness, D

40 up to more than 95

Tensile strength, MPa

10 100

Tensile modulus, GPa

0.130 3.9

Notched impact strength, J/m

20 up to nonbreak

HDT A (1.8 MPa), °C

30 200

Continuous use temperature, °C

80 250

Glass transition temperature, °C Coefficient of thermal expansion, 10 Dielectric loss factor, 10

2110 215 25

/°C

24

4 20 1 30

Oxygen index, %

17 47

UL94 fire rating

HB up to V0

UV behavior

Unsatisfying up to satisfying

Chemical behavior

Unsatisfying up to satisfying, according to chemicals

HDT, Heat deflection temperature; UL, Underwriters Laboratories; UV, ultraviolet.

When the temperature rises, mechanical properties decrease relatively slowly until the threshold of the glass transition temperature, which is the boundary of their ability to withstand low continuous efforts and also limits their dimensional stability under stress. In the absence of constraint, dimensional stability can be maintained up to 20 50°C above the glass transition temperature. Above Tg, these thermoplastics are extremely viscous liquids and it is necessary to reach significantly higher temperatures to sufficiently lower viscosities allowing

the extrusion or injection. Only amorphous thermoplastics can be transparent.

2.3.3.2 Crystalline and Semicrystalline Polymers For crystalline polymers, crystalline chains are ordered into compact domains. The degree of crystallinity is 1. Most often, polymers are semicrystallinecontaining regions of 3D ordering and amorphous

2: PLASTICS OVERVIEW

69

Table 2.23 Examples of Properties of Different Polyethylenes LDPE

Linear PE

HDPE

UHMWPE

Density, g/cm3

0.917 0.940

0.915 0.950

0.940 0.970

0.930 0.950

Shrinkage, %

2 4

2 2.5

1.5 4

4.0

Absorption of water, %

0.005 0.015

0.005 0.010

0.005 0.010

0.005 0.010

Shore hardness, D

40 50

55 56

60 70

60 70

Stress at yield, MPa

10 15

10 30

25 30

20 25

3 16

10 15

Miscellaneous properties

Mechanical properties

Strain at yield, % Tensile strength, MPa

10 20

25 45

30 40

39 49

Elongation at break, %

200 600

300 900

500 700

200 500

Tensile modulus, GPa

0.130 0.300

0.266 0.525

0.500 1.100

0.3 1

Flexural modulus, GPa

0.245 0.235

0.280 0.735

0.750 1.575

0.4 1

Notched impact strength ASTM D256, J/m

NB

54 to NB

20 220

NB

Thermal properties HDT B (0.46 MPa), °C

40 50

60 90

68 82

HDT A (1.8 MPa), °C

30 40

44 60

40 50

Continuous use temperature, °C

80 100

90 110

80 120

100 120

Glass transition temperature, °C

2110

2110

2110

2110

Melting temperature, °C

110 120

122 124

130

120 135

Minimum service temperature, °C

270

270

270 to 2100

2150 to 2200

Thermal conductivity, W/m K

0.32 0.35

0.35 0.45

0.40 0.50

0.4 0.5

Specific heat, cal/g/°C

0.55

0.55

0.55

0.55

Coefficient of thermal expansion, 1025/°C

10 20

6 15

13 20

Electrical properties Volume resistivity, Ω cm

1016 1018

1016 1018

1016 1018

1016 1018

Dielectric constant

2.3

2.3

2.3

2.1 3

24

Loss factor, 10

3 4

2 20

2 10

Dielectric strength, kV/mm

16 28

17 45

25 45

Fire behavior Oxygen index

,20

,20

,20

,20

UL94 fire rating

HB

HB

HB

HB

ASTM, American Society for Testing and Materials; HDPE, high density polyethylene; HDT, heat deflection temperature; LDPE, low density polyethylene; PE, polyethylene; UHMWPE, ultrahigh molecular weight polyethylene; UL, Underwriters Laboratories.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Figure 2.12 Micrographs of PP injected in a cold and a hot mold. PP, Polypropylene.

regions without any order. The degree of crystallinity (weight fraction or volume fraction of crystalline material) ranges from near 0 up to near 1. For a given polymer, the degree of crystallinity depends on the previous thermal history. Semicrystalline polymers are generally tougher than totally amorphous polymers but are opaque when some amorphous polymers are transparent. Semicrystalline thermoplastics are, for example, PA except some amorphous grades, PE, PP, POM, thermoplastic polyester (PET or PBT), and most fluorinated polymers. They differ from the amorphous polymers by the preservation of a notable percentage (35% 50%) of their mechanical properties, beyond the glass transition temperature. The dimensional stability is maintained approximately up to the threshold of the crystalline melting point. Unlike amorphous polymers the peak of melting temperature is sharp. The glass transition temperature of the amorphous domain leads to significant increases of the coefficient of thermal expansion, the permeability to oxygen (and others), and oxidation risks. Semicrystalline polymers cannot be transparent. For a given semicrystalline thermoplastic, the crystallinity depends on processing and subsequent thermal conditions. An annealing treatment followed by slow cooling leads to an increase in the degree of

crystallinity that can vary widely for a defined plastic, for example: • PA6 (%) • High density polyethylene (%)

40 70

• PP (%)

45 75

• PTFE (%)

50 90

30 40

Generally, increasing crystallinity leads to:

• specific gravity increase • stiffness increase • more slowly modulus decrease when temperature increases

• impact resistance decrease • impermeability and resistance to chemical product increase

• shrinkage increase. The following examples of variation of properties with crystallinity relate to low crystalline PPS injected into a cold mold and highly crystalline PPS injected into a hot mold (135°C)

2: PLASTICS OVERVIEW

71

Crystallinity

Low

High

Flex modulus, GPa

14

15

HDT 1,8 MPa, °C

,244

244

Notched impact

74

58

The Glass Transition Temperature

For amorphous polymers or amorphous domains of semicrystalline polymers, Tg is a reversible transition from a hard and brittle state into a molten or rubberlike state. There are sudden and significant changes in the physical properties including the coefficient of thermal expansion and specific heat. The Tg value depends on the testing conditions, notably the cooling or heating rate, and the frequency of the measured parameter. The Tg is always lower than the melting temperature of the crystalline domains. Fig. 2.13 schematizes modulus variations versus temperature for, on the one hand, an amorphous thermoplastic with the drop down when temperature reaches Tg and, on the other hand, for a semicrystalline thermoplastic with an additional platen. Crystallization is Time and Thermal Dependent and Isn’t Homogeneous

Fig. 2.12 shows different crystalline states for the bulk (left) and skin (right) of an injected PP part:

• in cold mold: skin (right) is clearly amorphous when bulk (left) is slightly crystalline

• in hot mold: the skin (right) is slightly crystalline but less than the bulk (left)

2.3.4 Viscoelasticity, Creep, Relaxation Rearrangement of macromolecules in plastics, notably thermoplastics, leads to significant viscoelastic properties that cannot be overlooked as far as temperature rises.

2.3.4.1 Time Dependency Table 2.24 displays examples of yield strength, yield strain, and modulus dependence of strain rate for several amorphous (sample A) or semicrystalline (samples B, C, D, E), neat (samples A, B, C, D), or filled (sample E) thermoplastics. Generally speaking, when the strain rate increases, stress and modulus increase, and strain decreases. Tensile properties are tested at defined strain rates, therefore data can be different at service strain rate. For longer load times, creep and relaxation must be taken into account. Creep is the time-dependent strain induced by constant mechanical loading. The strain evolves with the stress level, the time for which the stress is applied, and the temperature.

Modulus, GPa 5

Amorphous

Semicrystalline 0

300

–40

Temperature, °C

Tg Figure 2.13 Examples of modulus variations versus temperature for an amorphous and a semicrystalline thermoplastic.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 2.24 Tensile Properties at Room Temperature Versus Strain Rate Strain rate mm/min Amorphous A 5 Amorphous A 200 Amorphous A 1200 Amorphous A 60,000 SC B 5 SC B 50 SC C 5 SC C 50 SC D 30 SC D 300 SC D 3000 Filled SC E 30 Filled SC E 300 Filled SC E 3000 SC, Semicrystalline.

min–1

5 50 500 5 50 500

Yield Stress, MPa 49 52 70 90 70 75 63 68 35 38 40 27 28 30

Yield Strain, % Some % Some % Some % Some % 15 15 11 11 13 10 9 2.3 2.1 2

Stress at Break, MPa 51 49 50 82

The results can be presented graphically in various ways by combining these three parameters or in quantified forms—creep modulus and creep strength, for example. Creep can lead to breaking for levels of stress much lower than ultimate stresses measured by dynamometry. For example, to reach a breaking time superior to 8000 hours, a defined GF reinforced polyolefin cannot be loaded at more than 50% of the tensile strength measured by standardized dynamometry. Relaxation is the time-dependent stress resulting from a constant strain. The stress evolves with the strain level, the application time, and the temperature. The results of tests at a defined temperature can be presented as a load versus time curve or a stress retention versus time curve. The stress retention for a defined time and temperature is the actual measured stress divided by the original stress at time zero. For example, for a polyolefin, under 2% elongation at room temperature, the stress retention after 1000 hours (42 days) is about 67%.

2.3.4.2 Temperature Dependency Fig. 2.13 shows evolutions of moduli for temperatures evolving from 240°C to up to more than 200°C. Table 2.25 displays examples of yield strength, yield strain, and modulus dependence of temperature for several amorphous or semicrystalline, neat or filled thermoplastics. Generally speaking, when the temperature increases, stress and modulus

Strain at Break, % 175 120 30 5

Modulus GPa

1.6 1.8 1.9 7.7 7.7 9

decrease. Tensile properties being generally tested at room temperatures, data can be very different at service temperature. It must be pointed out significant property changes between 20°C and temperature as low as 50°C for certain polymers. When temperature decreases, generally tensile strength increases, elongation decreases and the material becomes brittle. For some materials, properties at 10°C and 30°C are significantly different from those tested at room temperature.

2.3.5 Isotropy, Anisotropy Polymer parts can be isotropic or, voluntarily or not, anisotropic. Isotropic polymers have equal properties in all directions (X, Y, and Z). Carefully molded glass bead filled thermoplastics are isotropic. A polymer or composite is anisotropic if its properties depend on the test direction. When measured along different axes (X, Y, and Z), physical and/or mechanical properties (modulus, aspect, refractive index, conductivity, etc.) are different. Unidirectional tapes are highly anisotropic. Long GF reinforced thermoplastics are more or less anisotropic. Oriented stretched films or fibers are voluntarily anisotropic aiming to improve properties in the stretched direction, however, this is not in the framework of this book. For usual molded parts, anisotropy is an unintended and adverse collateral effect of compound

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Table 2.25 Tensile Properties at Low-Strain Rate Versus Test Temperature

A A A F F F F G G G G H H H H H

Temperature, Yield

Yield Strain, Stress at

Strain at

Modulus

°C

Stress, MPa

%

GPa

20 50 100 20 50 75 100 20 50 75 100 20 100 150 200 250

70 63 35 35 26 18 15 27 20 15 12

15 11 8 13 16 17 15 2.3 2.6 3 10

Break, % 175

Break, MPa 51

1.6 0.8 0.4 0.2 7.7 5 3 0.5 85 51 25 8

formulation (fibers, for example) and/or processing conditions. Random sampling and use of the average of testing data can hide this phenomenon. Anisotropy coefficients are significant, depending on:

• • • •

the considered property the part geometry the location of sampling the formulation of the actual used grade

Anisotropy cannot be neglected in designing and the safety factor should include it, taking into account the location of the point of injection, the geometry of the parts, and the formulation. From a theoretical point of view, molecular orientation depends on the different flows of molten polymer. For a flat piece injected by its center, three types of flow come into play:

• shear flow near the walls • extensional flow of fountain type on the flow front

• extensional flow in the core of the piece Each flow type causes a different orientation of the molecules that can relax differently during cooling, which leads to a temperature gradient in the bulk of the part, with skins cooling faster than the core.

3.8 3.1 2.5 0.6 0.3

2.3.6 Potential Heterogeneity of Properties 2.3.6.1 Water Uptake Plasticizes Certain Polymers Fig. 2.14 shows the higher data and broader range of yield stress for samples of neat and GF reinforced PA exposed to equal temperature and humidity conditions. Table 2.26 displays for another GFPA, examples of water uptake effect on properties of GF-reinforced PA. Table 2.26 displays ranges (%) of mechanical properties for dry and conditioned (50% HR, 20°C) samples of GF reinforced PAs. Other properties may be affected. For example, Fig. 2.15 shows the effect of hygrometry on resistivity for a neat PA grade

2.3.6.2 Molecular and Filler Orientation Molecular orientation is due to alignment of macromolecules and their stretching in the direction of the flow during extrusion, injection molding, or calendering, the more so as the location is closer to the interface plastic/metal of the mold or die. Orientation is more pronounced in skins where the molecules are in contact with tools and are rapidly cooled. In contrast, the core of processed materials is less stretched and gently cools, which favors stress relaxation. The molecular orientation changes the properties in the flow and transverse directions. In the flow direction:

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Frequency

74

Neat

GF

0

50

100

150

200

250

300

350

MPa Figure 2.14 Yield stress of neat and glass fiber thermoplastics.

Table 2.26 Examples of Water Uptake on Properties of Glass Fiber Reinforced Polyamide (PA) PA 30GF Property Average Range, % Average Range, % Average Range, %

Average Range, % Average Range, %

Dry Tensile modulus 9684 32 Tensile strength 178 45 Elongation at break 3.2 56 Impact Unnotched charpy 78 64 Notched charpy 11.7 120

Conditioned Tensile modulus 6872 29 Tensile strength 125 48 Elongation at break 5.6 80 Unnotched charpy 91 44 Notched charpy 16.8 65

1.E+16

1.E+14

Ω cm

1.E+12 1.E+10 1.E+08 1.E+06 1.E+04 1.E+02

1.E+00 0

20

40

60

80

100

RH, % 120

Figure 2.15 Neat PA: examples of resistivity (Ω cm) versus relative hygrometry (%). PA, Polyamide.

2: PLASTICS OVERVIEW

• tensile yield strength and tensile impact strength are higher

• elongation at break is reduced • shrinkage increases • environmental stress cracking is better Consequences of orientation in the transverse direction are reversed.

2.3.6.3 Don’t Confuse Local and Bulk Properties: Take Into Account the Statistical Distribution of Properties Means are false friends: Fig. 2.14 shows two examples of property distribution: locally, the probability of a value lower than average is high and can initiate cracks.

2.3.7 Ambient Humidity Can Plasticize Polymers and Change Their Properties All the polymers absorb more or less humidity or water in quantities depending on:

• the form of the water: humid air, liquid water, pure, or polluted water

• the temperature • the recipe of the compound • the crystallinity of the polymer, etc. The extent of property changes including electrical properties depend on the polymer and uptake level. Table 2.26 displays some examples for PAs that are very sensitive to water absorption. The volume of absorbed water causes a dimensional increase. In reality, the absorption of water is very slow and, in the case of atmospheric changes, the equilibrium is not always reached, which dampens the effects of humidity variations. Anisotropic absorption of water can cause warpage, the more so as the material modulus is low. For example, a membrane covering a water container can curve because of the swelling of the inner face. Over the long term, absorbed water can promote hydrolytic aging.

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2.3.8 Often Properties Evolve Abruptly: Glass Transition, Yield, Knees, Frequency-Dependent Properties Kinetics of property changes may evolve during long-term tests under steady conditions. For example, aging kinetics can suddenly evolve with abrupt changes, thresholds, knees, or sudden failure, and so on. Dynamic mechanical properties and electrical properties, among others, are sensitive to the frequency of dynamic constraints. For example, tensile strength depends on the strain rate or loss factor depends on the courant frequency. More misleading, some testing methods may use several loading scenarios leading to differences in the resulting data. For example, glass transition temperature can be measured by static or dynamic methods resulting in more or less lower temperatures. Generally speaking, it must be noted that a mathematical model is an equation giving a result in all cases. In real life, results can be completely different and the studied part may fail when the model predicts a longer life. The user must be aware of these risks. Therefore certain predictions can be disastrous leading to completely false estimations. In optimistic cases, modeling can save time and money by reducing trials and property testing. The mathematical laws binding the effect on one property and a parameter such as time suppose that the property continuously evolves without abrupt changes. These laws cannot predict thresholds, knees, or sudden failure, and so on. These phenomena must be specifically modeled.

2.3.9 Dimensional Stability Several examples of volume variation have been mentioned above and anybody has already seen too little (or too big) a polymer part disturbing a device made by assembling several parts of various materials. Sometimes, the dimension is fair but a more or less strong warpage prevents a correct assembly. Generally, dimensional variations are the consequences of:

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• coefficient of thermal expansion • external or internal stresses, pressure, etc. • anisotropy of stresses or other polymer proper-

• The orientation of fibers or acicular fillers. • The crystallinity: A possible crystallization after molding leads to a volume increase that minimizes the total shrinkage.

ties or orientation can lead to warpage

• shrinkage after demolding • Moisture and water uptake particularly known

2.3.9.2 Warpage Warpage or distortion can be due to:

for PAs. Other chemicals can also swell polymers but they are rather relevant from chemical behavior.

• Anisotropy of internal stresses. • Shrinkage variations induced by local changes

• Desorption of humidity or additives such as plasticizers or other low-molecular weight organic additives. Plastics are often simultaneously used with conventional materials, notably metals whose coefficients of thermal expansion may be 10 100 times lower. This can promote high stresses and failure of the device including these materials. Dimension variations can be immediate (thermal expansion), time dependent (water uptake), or delayed after a given time of aging:

• Thermal expansion or retraction is reversible. • Water uptake and drying are almost reversible with a limited hysteresis.

• Releasing of additives is irreversible. • Bulk compression is time dependent: after a short time of compression and after a sufficient time of relaxation, the original geometry is recovered but for a sufficient time of compression there is a permanent set even after long times of relaxation.

2.3.9.1 Shrinkage Shrinkage after molding is a universal problem depending on:

• The coefficient of thermal expansion: for given conditions, the shrinkage increases with the coefficient of thermal expansion.

• The molding temperature: for given conditions, the shrinkage increases with the molding temperature.

• The additives. • The orientation of the macromolecules.

of formulation or processing parameters. Colorants, for example, can nucleate the polymer and locally favors shrinkage. Fibers and acicular fillers can accumulate in certain spots of the mold leading to local decreases of coefficient of thermal expansion, shrinkage, and increases of moduli, leading to warpage. Calcium carbonate (CaCO3) fine powder and other spheroid fillers such as microballoons or glass beads decrease shrinkage and easily flow in the mold, reducing warpage.

2.3.9.3 Release of Organic Additives Organic additives, particularly plasticizers, can degas the more so as the temperature and the airflow rise. Consequently dimensions decrease. High molecular weight or reactive additives minimize releasing.

2.3.10 Aging1 Organic macromolecules are sensitive to oxidation, hydrolysis, and some chemicals as far as the temperature rises are concerned. The technical consequences can affect skins and/or the core and are as varied as degradation of performances, discoloration, yellowing, gloss loss, decreased transparency for transparent polymers, chalking, crazing, and hardening. Heat and natural weathering are the most common causes. Heat affects the whole material but oxygen is less present in the core, which delays oxidation. For opaque materials, sunlight and UVs primarily affect the skins. Note that all properties degrade with their specific kinetics. 1

see also Section 2.2.2.2.

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Shelf aging and heat aging can be (imperfectly) simulated by accelerated aging in ovens. Test results must be carefully interpreted by specialists and are mainly comparative. Weathering is more difficult to quantify because of the variation of the parameters according to the local conditions, such as:

• • • • • • •

hours of sun per annum irradiation energy UV wavelength average and extreme temperatures hygrometry, rain ozone pollution, acid rain

The technical consequences of weathering are similar to heat aging with more pronounced surface degradation, notably:

• discoloration,

yellowing, gloss loss, and decreased transparency for transparent polymers

• chalking, crazing, and hardening Additives such as special fillers (e.g., carbon blacks), UV stabilizers, and so on, can enhance the basic resistance of the matrix to UV. Under quite precise conditions (angle of incidence, positioning, temperature, water vapor, surface water, etc.), tests can be done by exposure:

• to the natural light of the sun, or • to the radiation of xenon lamps (Xenotest, WeatherOmeter) or others. The interpretations of the results are difficult because of:

• climate diversity • the risks of industrial or domestic pollution in real life

• the lack of correlation between artificial and natural aging

• the different degradation kinetics of the various properties

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2.3.11 Chemical Resistance by Immersion or Contact 2.3.11.1 Exposure Without Constraint The action of a chemical on a plastic can induce three concomitant phenomena:

• absorption of the fluid (liquid or gas) by the plastic, which leads to swelling of the part

• extraction by the fluid of certain material components (plasticizers in particular, antidegradants, monomers and oligomers, colorants). This extraction can reduce the apparent swelling of the part or even lead to a retraction

• pollution of the fluid by the immersed polymer: desorption of particles and ingredients The tests themselves consist of immersing the sample in the fluid under consideration for a given time at a given temperature. The generated effects can be highlighted in several ways:

• evaluation of the volume, weight, or dimension swelling of the sample

• percentage of extracted materials • degradation of the mechanical characteristics, either immediately or after drying. For these tests, the service liquids (solvent, oil, hydraulic fluid, acid, base, etc.) can be used but to ease the establishment of specifications and comparative tests, reference solvents, oils, or fuels are often used. Note that the duration of chemical tests is generally short (e.g., days) making that good results are of uncertain—meaning if targeted lifetime is in the order of years.

2.3.11.2 Environmental Stress Cracking (ESC) Environmental stress cracking (ESC) is a specific aspect of chemical resistance. When a plastic exposed to air is subjected to a stress or a strain below its yield point, cracking can occur after a long duration. Besides this, when the same plastic

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is exposed to the chemical under consideration in a relaxed state, cracking can also occur after long duration. However, the simultaneous exposure to the same chemical environment under the same stress or strain can lead to a spectacular reduction of the failure time. The accelerated cracking in this way corresponds to an ESC.

2.4 Sensory Properties of Plastics: An Outstanding Advantage for Marketing The market appeal of plastics is important for numerous applications such as packaging, automobile, and appliances. Often, parts are used out of an injection press without surface treatment, painting, machining, and so on. Sensory properties depend on the general formulation and processing conditions. Specific additives can be needed to satisfy some of the sensory requirements. The choice of general additives depends on a subtle balance of numerous parameters concerning the nature of the polymer, the processing constraints (notably heat exposure, mixing technology), endproduct esthetics requirements, and the durability under service conditions of the end product. As mechanical or physical properties, sensory properties are also sensitive to aging. Color, transparency, gloss, touch, scratch resistance, acoustic properties, odor, taste, and fogging, among others, contribute to make a plastic part attractive, unappealing, or repulsive.

2.4.1 Optical Properties Color can be obtained by adding colorants to compounds, or encapsulating the part with a continuous film of another colored or printed polymer: IMD, painting, multilayer sheets for thermoforming, and so forth. Colorants can be classified according to:

• their chemical structure: inorganic or organic, etc.

• their form: powders, masterbatches or concentrates in pellets, pastes, liquids, dustless powders, encapsulated, etc.

• their function: colorants, brighteners, phosphorescent colorants, pearlescent colorants, metallic colorants, etc.

Clarity and transparency can be enhanced by adding clarifiers. Matting can be obtained by adding special mineral fillers, another secondary polymer that is miscible to a greater or lesser degree with the main polymer, or proprietary additives. Glossy polymers can be obtained by polishing, postmolding into perfectly polished molds, lay out of films, IMD, FIM, IMC, painting, and so forth.

2.4.2 Touch Touch can be as varied as rubber-like, metallic, or mimicking cloth, wood, and leather. Now a soft touch is particularly in fashion due to soft and ultrasoft TPEs. Touch can be tuned by modification of the used compound or by overmolding with a TPE or another soft compound. There are many soft-touch applications such as:

• soft-touch knobs, grips, handles for appliances, kitchenwares, housewares, etc.

• grips, feet, non-skid surfaces for hand and power tools, industry, lawn, and garden equipment, etc.

• feet, impact cladding, soft-touch handles for mobile phones, game consoles, computer mouses, MP3 players, other electronic/telecommunication equipment, etc.

• grips and soft touch buttons and panels, keypads, pencil grips for personal care applications, consumer goods, etc.

• soft-touch panels, cup holders, console and tray liners, instrument panel covers, arm rests and steering wheels, pillars for automotive interiors

• soft touch components for sports and leisure, etc.

2.4.3 Scratch-Resistance Improvement Soft polymers are more sensitive to scratch than some harder plastics. The use of silicone helps reduce the coefficient of friction and correspondingly improves the scratch resistance. Surface treatments with hard resins are also used.

2: PLASTICS OVERVIEW

2.4.4 Acoustic Comfort Generally speaking, conventional plastics have sound and vibration dampening properties that conventional metals do not. For example, PEEK, UHMW-PE, and other engineering thermoplastics (ETPs) are used to build silent gears. But plastic parts can also initiate unwanted noises by vibration. For example, certain automotive parts can vibrate at frequencies of engine rotation. Plastics rubbing on other plastics or various materials can also emit annoying noises.

2.4.5 Odors Some plastics can develop unpleasant odors during and after processing or after aging. To avoid or reduce that, it is possible to:

• choose odorless grades and additives • add deodorants or specific fragrances marketed

79

problem for optical applications, packaging, horticulture, and so on. For a given difference of temperatures between the air and the plastic part, the duration of the fogging depends on the thermal conductivity of the polymer. Other materials such as glass are subject to the same problem.

• Desorption of additives, oligomers, or lowmolecular weight polymer from the plastic parts and their condensation on other cold parts: glazing of cars and particularly windscreens, optical lenses, or electronic devices where the deposit of additives can also make electrical insulation. To avoid these troubles, two main ways are used: Choice of lowoutgassing additives and polymers without monomers or oligomers, spreading of a permanent barrier coating onto the surface of the plastic part.

for polymers

• add bactericides or preservatives to avoid growth of microorganisms, fungi, etc., during service life. Certain recycled plastics can smell bad. Plastics can adsorb surrounding odors and then release unpleasant odors.

2.5 Outline of the Technical and Economic Possibilities of Processing A satisfactory combination of part, polymer, and process, is essential:

• each process does not allow the fabrication of

2.4.6 Taste Some plastics can develop unpleasant taste during and after processing, use, or aging. The selection of special polymers and tasteless additives must be carefully studied under actual conditions of processing and use. High temperatures and interactions between ingredients can provoke the development of undesired taste. Plastics may also adsorb surrounding substances and take on a bad taste.

2.4.7 Fogging The word “fogging” relates to two different phenomena:

• One is the condensation of the air moisture on the cold plastic, formation of tiny droplets of water on the surface, light scattering, and obscuring of the polymer. This is an important

all types of parts

• polymers are not all suitable for processing by all methods It is pointless to select a polymer of high performance if it is not technically and economically suitable for manufacturing the part under consideration. For the choice of the process according to the part, some points to be taken into account are listed here but other issues could be considered depending on specific contexts:

• The shape: parts of all shapes and limited sizes are, generally, manufactured by molding by compression, injection, transfer, thermoforming, and the derived methods such as rotomolding, reaction injection molding (RIM), reinforced RIM (RRIM), resin transfer molding (RTM), etc. Parts of constant sections are,

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80

generally, manufactured by extrusion, pultrusion, and derived methods.

• The size: parts of enormous size are manufactured by boiler making, hand layup, spray layup, centrifugal molding, filament winding, etc.

• The aspect: a good aspect on the totality of the part surface is only obtained by molding. The other processes leave either rough-cut sections or a more or less rough face.

• The quantity to be produced: the rate of output depends on the process. Injection molding, RTM, and SMC allow mass production whereas boiler making, hand layup, or spray layup molding hardly exceed 1000 parts. The processes used for thermoplastics are diversified because of the thermoplasticity, which allows:

• • • •

easy molding, extrusion, calendering thermoforming welding assembly and boiler making

Just to give an idea of the importance of the various processing methods, the shares of the major processes used for the most used thermoplastic (PE) are roughly:

• • • • •

extrusion: 35%

2.5.1 Molding Solid Thermoplastics Injection is by far the most used molding process but compression and compression transfer are used for specific cases. Rotomolding is specifically used for PE and a few other powdered resins. Slush molding is broadly used for automotive dashboards. Generally, but there are significant exceptions:

• the part sizes are limited by the mold size and the machinery performances

• the parts are isotropic if the compound is isotropic and if the drawing is regular

• the whole surface of the part has a good finish Each process presents some particularities:

• Injection molding: • permits the total automation of the process • is suited for mass production • shot capacities cover a large range, for example, a few grams up to more than 100 kg

• overmolding and comolding are usable • optimization of the molding parameters can • • •

injection molding: 25% blow molding: 35% rotomolding: .1% others: 4%.

Note that the processes used for thermoplastics must be modified for the thermosets because:

• after obtaining the part shape, it is necessary to heat for a sufficient time to cross-link the thermoset that solidifies and gains its cohesion and final properties.

• due to the irreversible formation of a 3D network during hardening, the thermosets cannot be processed by thermoforming or welding, and boiler making is very limited.

•

be difficult and part warpage is sometimes difficult to predict normally, finishing is unnecessary apart from the particular cases of resins filled with fibers and other acicular or lamellar fillers, the parts are isotropic the output rates, the mold, and press prices are high, and the labor costs are reduced to the minimum for standard, mass-distributed parts, it is the cheapest process

• Injection blow molding: • is suited for the production in large quantities of bottles, similar containers, and other hollow objects • the aspect and dimensional quality are excellent compared to extrusion blow molding • the outputs are high

• Rotomolding: • is suited for the fabrication of hollow parts such as containers, dolls, tanks, and kayaks

• is convenient for the production of small parts and giant ones such as tanks of more than 75,000 L capacity

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• is used for small and medium output • products are essentially stress free and there

• the aspect is correct for the outer surface but

are no weld lines • finishing is often essential • the output rates are low • the mold and machinery are relatively inexpensive, and the labor costs are high.

• several extruders can be arranged to fabricate

• Compression molding (not much used for thermoplastics): • is suited for small and medium output of unusual shapes • finishing is often essential • the output rates are low, the mold and press are relatively inexpensive, and the labor costs are high

• Compression transfer molding (not much used for thermoplastics): • is suited for medium output • finishing is often simple • the output rates, mold and press prices, and labor costs are halfway between compression and injection molding

• Slush molding used with thermoplastics in powder form for the fabrication of automotive dashboards: • is suited for medium and high output, for example, the dashboards of BMW series 7 up to the Polo by VW. • the machinery is rather sophisticated

2.5.2 Extrusion and Connected Processes Extrusion and derived processing methods are the most used in terms of weight, allowing the fabrication of profiles, cast and blown films, wire sheathing and coating, blow-molded hollow parts, and expanded materials such as expanded PS (EPS). Generally:

• the output is medium or high, varying from kg/h to tons/h

• the section sizes are limited by the die size and/or the machinery size (the length is unlimited)

• arrangements of reinforcements are limited • the parts are often anisotropic. Properties are different in the machine and the transverse directions.

cuts are rough multi-material profiles

• The cost of the tools and machinery depends on its sophistication. Each tool is appropriate for a single section. Universal screws are not always convenient and some profiles or materials need special screws or special extruders.

2.5.3 Calendering • Calenders are very expensive and specific machines that are used only for high-output production.

• The section sizes are limited by the roller sizes. The length is practically unlimited.

• It is possible to calender thermoplastics onto fabrics to obtain a reinforcing effect.

• The parts are often anisotropic. Properties are different in the machine and the transverse directions.

• The aspect is correct.

2.5.4 Blow Molding This combination of extrusion and molding:

• is used for large series of bottles, similar containers and other hollow objects

• the aspect and dimensional quality are not as good as injection blow molding

• the outputs are high

2.5.5 Molding Liquid Thermoplastics The most commonly used liquid thermoplastics are plastisols (pastes of PVC with a high content of plasticizers). There is also a PA of very low consumption. Some of the processes can be applied to powders in suspension. The plastisols can be molded by:

• Dipping: • suited for small and medium output • the part sizes are limited by the size of the former

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82

• reinforcements can be arranged onto the for-

• Machining: practically all the thermoplastics

mer before dipping the parts are isotropic with neat resins or with isotropic fillers the aspect is correct for the outer surface and a finishing step is often essential the molds are inexpensive and the cost of the machinery depends on its sophistication the output rates are low.

can be machined to some degree by almost all the metal or wood machining methods after adaptation of the tools and processes to a greater or lesser extent: • sawing, drilling, turning, milling, tapping, threading, boring, grinding, sanding, polishing, engraving, planing, etc. The lowthermal conductivity and the decrease of the mechanical characteristics at elevated temperature limit the machining temperature and it is necessary to cool and reduce the tool feed motion. • machining is suited for prototypes and low output of complex parts made from blanks whose mold could be simplified; it is also suited to making thick or tight tolerance parts.

• • • •

• Low-pressure injection molding, RIM, RRIM for liquid PA: • suited for medium output • the part sizes are limited by the mold size • reinforcements can be arranged in the mold before injection • the parts are isotropic with neat resin or with isotropic reinforcements • the aspect is well finished for the whole part surface • The low-pressure resistant molds are more expensive than for the casting but cheaper than injection molds. A press and a mixing/ injection unit are necessary but the labor costs are moderate. Provides medium output rates.

2.5.6 Secondary Processing • Thermoforming: • is convenient from prototype to mass production • allows the production of large parts • machinery can be simple or sophisticated, and, consequently, the shapes and tolerances can be rough or precise. Under the best conditions, fine tolerances and sharp details are obtained, and with excellent finishing techniques, the thermoformed parts can match injected parts.

• Welding: • can be very simple or sophisticated • allows small or continuous joining • can avoid the design and tooling constraints of complex parts by assembling several pieces of standard production (sheets, tubes, films, etc.) or more simple parts produced with economical tools • needs skilled workers • machinery is generally relatively inexpensive but there is a lot of labor.

• Boiler making is commonly used for the fabrication of large vessels, piping, etc., thanks to the use of techniques such as welding, forming, machining, bonding of sheets, slabs, pipes, blanks, etc. This processing method allows the building of very large size tanks, cisterns, tubing, geomembranes, and so forth, from prototypes up to medium output. The workers must be skilled and the labor costs are high.

• Fabrication is also commonly used to build inflatable boats, protective clothing, and inflatable structures, particularly those made of soft PVC. The workers must be skilled and the labor costs are high.

2.5.7 Three-Dimensional Printing and Other Additive Manufacturing Methods AM techniques build up objects from 3D data generated from 3D computer-aided design (CAD) or 3D scanning systems. The various techniques include stereolithography, fused deposition modeling, laminated object modeling, selective laser sintering, 3D-printing, and PolyJet process. General objectives of 3D printing include:

• Affordability: financially accessible to smalland medium-sized businesses

• Ease of use for everyone

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83

• Office friendly without polluting emissions • Fast operating: short development time and

• Higher costs of special materials, often in tens of dollars.

• End cost: material cost is often the main

low end-costs producing parts in hours instead of days.

parameter but printing time also determines the end cost. Complexity and number of parts are not determining (no economy of scale)

As all other processes, 3D printing has advantages and drawbacks and must be intelligently chosen, which needs:

• • • •

• Printing speed is low: Items regularly take hours to print, even days. Thicker layers speed up manufacture but finish quality is poorer. Currently production speed is expected in the range 10 20 cm3/h and forecasts reach 80 cm3/h in 2023.

Access to the right 3D printable file Use of the right machine Operation by highly trained professionals Building parts with the adapted technology/ special material solutions

The main direct advantage is the suppression of molds and other tools. Possible drawbacks may be:

• Weaker parts, not as strong as injected parts because of the lack of pressure and the layer-bylayer technique of manufacturing. In 3D printing new layers must bond onto previous layers, which could lead to lower strength compared to intrinsic strength of bulk material in injected parts.

• Rough surface finish depending on layer thickness creating apparent lines.

Additive manufacturing (AM) may use special or common families of materials but the grades must be devoted to AM. According to the broad choice of processes, all the thermoplastics may be selected from the most common such as ABS up to renewable thermoplastics such as PLA through engineering plastics, for example, PC or PEI. But again, all processes aren’t suitable for all plastics. AM uses also specific thermosets.

2.5.8 Brief Economic Comparison of Some Processing Costs Table 2.27 illustrates schematically some general economic possibilities of various processes without

Table 2.27 Linked Processing Costs of Some Thermoplastic Processesa Process

Standard Output

Linked Processing Cost

Injection

1,000,000

1

1000

14

1,000,000

1.5

1000

12

1,000,000

2.5

100

16

10,000

5

10

16

1000

6

10

15

1000

12

1

14

Blow molding Rotomolding, sophisticated machinery Thermoforming Rotomolding, basic machinery Fabrication by machining, cutting, welding, gluing, etc. a

Relative to the processing cost of a standard part injected at 1 million units.

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claiming to be exhaustive. Other values may be recorded for the concerned parameters and not all the processes are examined. These figures are only orders of magnitude used simply to give some idea of the costs. They cannot be retained for final choices of solutions or estimated calculations of cost price. All parts are not necessarily producible by all the processes. The costs are all relative to the processing cost of a standard part injected at 1 million units, which is defined as 1.

2.5.9 Repair Possibilities: A Significant Thermoplastic Advantage for Large Parts Large parts made from thermoplastics have the significant economic advantage of being rather easy to repair. A good professional can correctly repair the most-common thermoplastic parts, such as piping, geomembranes, inflatable boats, and structures by

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welding or gluing patches after removal of the soiled and damaged part. Generally speaking, thermoset parts are more difficult to repair.

Further Reading Biron, M., 2014. Thermosets and Composites. Elsevier Ltd. Biron, M., 2015. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2017. Industrial Applications of Renewable Plastics. Elsevier Ltd. Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Plastics Additives & Compounding, ISSN: 1464-391X Elsevier B.V. https://www.journals.elsevier.com/ plastics-additives-and-compounding. Plastics News.com, Crain Communications. https:// www.crain.com/brands/plastics-news Reinforced Plastics, ISSN: 0034-3617, https://www. journals.elsevier.com/reinforced-plastics/. Elsevier Ltd.

3 Metrics of Sustainability in Plastics: Indicators, Standards, Software Plastics synthesis, processing, use, and disposal—do as all human activities—consume resources and energy, pollute and compromise the future of the planet by global warming, atmospheric ozone depletion, and accumulation of pollutants often under organic forms, which is particularly harmful for human, animal, vegetal, and aquatic life. To preserve the essential needs of future generations for a maximum time, it is essential to rethink all our actions and to design products and goods for better sustainability. There are no perfect answers to this grave problem, but it is essential to compare different solutions with efficient and unbiased methods, preferably standardized. Those methods allow the study of the whole life from resource use up to waste disposal, as well as specific steps. Methods are very diverse and may be globally or regionally applied, from general purpose to detailed level, and voluntary or mandatory application. Laws, regulations and trends are rapidly evolving. The provided information is only a quick glance needing a more deeply study before application to the problem of the reader. Practitioners of those technics must be competent, trained, and skilled. This chapter does not take into account social and societal aspects, or regulatory requirements.

3.1 Environment Management Systems Environmental management systems (EMS) cover extended complex features including, but not limited to:

• Definition of the environmental policy of the organization.

• Inventory of relevant environmental features of products, activities, and services that could have significant impacts on the environment.

• Identification of suitable legal and other mandatory or voluntary requirements, access to relevant laws, regulations, and others.

• Clear definition of environmental objectives, targets, and goals of the organization.

• Definition of concerned stakeholders and distribution of roles.

• Building the environmental management program of the organization.

• Definition of roles and responsibilities for environmental management.

• Access to essential, necessary, and sufficient resources including skilled staff, continuous training, and competence in environmental responsibilities.

• Delegation of responsibilities to personnel having adequate and actual power.

• Building of an EMS control system including, but not limited to: • Procedures and other documents. • Operational control in accordance with the policy, objectives, and targets. • Monitor key activities and track performance. • Periodically, verification of compliance with environmental requirements. Identification, corrective, and preventive actions of nonconformance and problems. • Maintain, manage, store, and treat records of EMS performance. • Organize periodical EMS audits that verify the conformity to the environmental policy. Obviously this complexity and the diversity of subjects lead to the possible involvement of countless standards. We quote only some of them and the reader must search the standards suitable for his/her own problem.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00003-3 © 2020 Elsevier Ltd. All rights reserved.

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3.2 Life Cycle Accounts: LCI, LCA, LCIA

from grid is a mix of various energy types and may include nuclear energy, which leads to nuclear pollution.

Life cycle study (see Fig. 3.1) is a multistep procedure including goal and scope definitions, inventory analysis, impact assessment, interpretation, and iterations for improvement. Standards and other tools may be of general purpose or may deal with specific subjects. All the steps of the studied product, all the stakeholders of the supply chain, and all the relevant users should be taken into account.

• Water use, taking into account the inlet and

3.2.1 Life Cycle Overview Life cycles are generally complex taking into account several subparts, many individual processes in the supply chain (e.g., the extraction of raw resources, various primary and secondary production processes, transportation, etc.) as well as many tracked substances. LCI must take into account all the steps of the life of the considered device including, but not limited to:

• Raw resources: ore, sand and other minerals, renewable materials—including extraction, transformations, transportation, etc.

• Energy by type, that is, renewable and nonrenewable, primary and secondary. As far as possible, used data must be representative of actual used energy. For example, electricity

Concept and design Raw material extraction

End of life

Polymerization and preparation

Use

Distribution

Manufacture

Figure 3.1 Life cycle example.

output conditions.

• Emissions to air, water, and land of specific substances.

• Packaging, inserts, and other auxiliary items must be taken into account.

• Distribution. • Use. • End-of-life. These complex concepts (see Fig. 3.2) relate to the whole life cycle of the product and depend on the methods of production of raw materials, processing methods, type of energy used, applied logistics and transportation, disposal method, and so forth. Therefore when examining results, it is necessary to clearly understand what the used methods are, and what is being measured or assumed. For example, take into account the renewable nature of the electricity is not relevant if clearly actual users cannot have access to it. End-of-life may also lead to misleading data; for example, a device may be theoretically recyclable but may be landfilled in real life. Most often, results are briefly expressed as data concerning the energy consumption and the greenhouse effect or CO2 emission. Additionally, results can relate to more detailed pollution such as:

• • • • • • • • • •

sulfur oxides (SOx) carbon dioxide carbon monoxide methane nitrogen oxide (NOx) emissions acidification carcinogenicity indicators water emissions (phosphates, nitrates) terrestrial ecotoxicity human toxicity, etc.

Of course, results highly depend on the end of the studied cycle: resin, pellet, new part or product,

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Raw material supply (fossil or renewable resources) Polymer production (synthesis, treatments, etc.)

Resources energy, etc.

Part processing (molding, extrusion, thermoforming, etc.) Commercialization (packaging, transport, etc.)

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Emissions

Pollution: Air : CO2, NOx, SOx Water : BOD, COD Soil: solid waste, etc.

Use Disposal (recycling, energy recovery, landfilling, etc.)

Figure 3.2 General chart of plastics life cycle.

used part or product, use of recycled polymer, or end-of-life scenario. Lastly, as with all measurements be careful of the units of the results.

3.2.2 Life Cycle Inventory Life cycle inventory (LCI) is the inventory of the total energy consumption, raw material use, air and water emissions and the total solid waste produced from the cradle to grave (grave being the ultimate disposal). The LCI gives the basic data for the LCA. It is equivalent to the eco-profile covering the complete life cycle. In the strict sense of the term, the LCI of resins, pellets, new films, or tubes, and so forth does not exist because the pellets and new parts or products are not usually thrown away, but are usefully used. LCI is generally complex involving many individual unit processes in the supply chain (e.g., the extraction of raw resources, various primary and secondary production processes, transportation, etc.), as well as many tracked substances. LCI includes, but is not limited to:

• Raw resources: ore, sand and other minerals, renewable materials—including transportation, etc.

extraction,

• Energy by type, renewable and nonrenewable, primary and secondary.

• Water use. • Emissions to air, water, and land of specific substances.

• Packaging, inserts, and other auxiliary items must be taken into account.

• • • •

Distribution. Maintenance and repair. Resources used for the service life. Disposal.

3.2.3 Life Cycle Assessment Life cycle assessment or life cycle analysis (LCA) evaluates environmental impacts resulting from all the stages of a product or part life, including raw material extraction, material processing, manufacture, distribution, use, repair and maintenance, and disposal or recycling. Of course, packaging, inserts, screws, and other auxiliary items must be taken into account. ISO 14040, ISO 14044, and ISO/TS 14072:2014 deal with LCA requirements and guidelines. These standards detail:

• The application of LCA principles and methodology to organizations.

• The benefits that LCA can bring to organizations by using LCA methodology at organizational level.

• The system boundary which is of a prime importance for the resulting data.

• Specific considerations when dealing with LCI, LCIA, and interpretation.

• The limitations regarding reporting, environmental declarations, and comparative assertions.

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3.2.4 Life Cycle Impact Assessment

3.2.6 Beware, Life Cycle Costing is Not an Environmental Feature

The life cycle impact assessment (LCIA) analyzes the environmental impact of the life cycle inventory. For example, for a defined product, LCI can determine the consumption of a defined weight of crude oil, while LCIA determines the induced global warming impact. The life cycle impact analysis depends on:

Life cycle costing (LCC) is another approach considering the monetary costs involved with the concerned product without any particular environmental consideration. However economic considerations are important from a sustainable point of view. LCC involves evaluation of all costs related to the life cycle of the studied system, contributing to enhance sustainable design and helping to the final decisions.

• The system boundaries (e.g., allocations between main product, secondary products, by-products, etc.).

• The precise nature of the studied parameter (e.g., energy may be renewable, fossil, total, etc.).

• Used units for the manufacturing of the concerned product [e.g., pipe units may be kilograms, tons, length (diameter must be known), etc.].

• Used units for the consumed or emitted entities [e.g., energy may be expressed in Joules, BTU (about 1055 J), kWh, GJ, toe (about 42 GJ)].

3.2.5 Incorporation of Eco-Design or Sustainable Design in the Life Cycle Through ISO 14006 ECD or sustainable design targets the reduction of adverse environmental impacts of a product throughout its entire life cycle. Often several ways may be investigated with diverse environmental benefits or drawbacks. All the steps of the life cycle must be considered; one way may benefit a given step but may be detrimental for another step. For example, a renewable polymer can avoid consumption of crude oil as feedstock, but may require agricultural means thereby initiating pollution of soil and water; used natural resources can compete with food crops and lead to deforestation. This can involve balancing the environmental aspects of the product with its intended use, performance, cost, marketability and quality, and choosing methods to meet legal and regulatory requirements in the most environment-friendly way.

3.3 General Purpose and Specific Standards Linked to the Environment The following lists of ISO standards are not exhaustive, and ISO standards evolve every day. Some of the quoted standards may be withdrawn and some active standards may be omitted. Consequently, the reader must consult https://www. iso.org/home.html, Global Green Standards ISO 14000 and Sustainable Development (https://www. iisd.org/pdf/globlgrn.pdf), and other websites dedicated to standards to update the information. Other origins of standards must be tested according to the concerned countries of manufacture, use and disposal. For example:

• ASTM standards (https://www.astm.org/). • The European Commission’s Eco-Management and Audit Scheme.

• The United States Environmental Protection Agency (EPA) (https://www.epa.gov/ems).

• The

China Steering Committee of Environmental Management Systems Accreditation is responsible for administration and EMS certification and the implementation of ISO 14000 standards in China.

• And many others. Some standards deal with EMS and others deal with more detailed subjects such as GHG, and so forth. Of course, the following does not preclude, override, or in any way change legally required

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environmental information, claims or labeling, or any other applicable legal requirements.

ISO 14006 helps organizations in integrating ECD in other management systems.

3.3.1 Overview

3.3.2 Environmental Management: ISO 14000 Family and a Few Related Standards

At the base of sustainable products, four ISO standards (see Fig. 3.3) must be primarily considered:

• ISO 14000 family including: • ISO 14001 and its supporting standards. • ISO 14006 EMS guidelines for incorporating

List of ISO 14000 series standards includes, but is not limited to:

• ISO 14001 Environmental management systems—Requirements with guidance for use.

ECD. • ISO/TR 14062 environmental aspects into the design and development process.

• ISO 14004 Environmental management sys-

• ISO 9000, including ISO 9001, the criteria for

• ISO 14006 Environmental management sys-

a quality management system. ISO 14001 links management of an organization’s processes with environmental impacts, but does not include design management processes. ISO 9001 covers the design management process, but does not explicitly cover environmental impacts. ISO/TR 14062 and IEC 62430 assist incorporation of the evaluation of environmental aspects and impacts into the design and development process, but they do not fully explain the activities involved within an environmental and business management framework, such as those described in ISO 14001.

tems—General guidelines on implementation. tems—Guidelines for incorporating Ecodesign.

• ISO 14015 Environmental assessment of sites and organizations.

• ISO

14020 series (14020 to 14025) Environmental labels and declarations.

• ISO 14030 discusses post-production environmental assessment.

• ISO 14031 Environmental performance evaluation—Guidelines.

• ISO 14040 series (14040 to 14049), Life Cycle Assessment, LCA, discusses pre-production planning and environment goal setting.

• ISO 14046 sets guidelines and requirements for water footprint assessments of products, processes, and organizations. Includes only air and soil emissions that impact water quality in the assessment.

ISO 14001 Environmental impacts of processes

ISO 14006

• ISO 14050 defines terms of fundamental concepts related to environmental management, published in the ISO 14000 series of International Standards.

Ecodesign ISO/TR 14062 Environmental impact of design

ISO 9001 Design management

Figure 3.3 ISO 14006: convergence of ISO 14001, 14062, 9001 and specifics of eco-design.

The ISO 14000 family of standards deals with environmental management for companies and organizations of all kinds looking to manage their environmental responsibilities. The ISO 14001:2015 and its supporting standards such as ISO 14006:2011 focus on environmental systems. The other standards in the family focus on specific approaches such as audits, communications, labeling, and life cycle analysis, as

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well as environmental challenges such as climate change. ISO 14001 links management of an organization’s processes with environmental impacts. ISO 14001 is the world’s most recognized framework for EMS, helping organizations both to manage better the impact of their activities on the environment and to demonstrate sound environmental management. ISO 14001 is intended for use by an organization seeking to manage its environmental responsibilities in a systematic manner that contributes to the environmental pillar of sustainability. ISO 14001 provides value for the environment, the organization itself, and interested parties. Consistent with the organization’s environmental policy, the intended outcomes of an EMS include:

• enhancement of environmental performance; • fulfilment of compliance obligations; • achievement of environmental objectives. ISO 14001 is applicable to any organization, regardless size, type, and nature, and applies to the environmental aspects of its activities, products, and services that the organization determines it can either control or influence considering a life cycle perspective. ISO 14001 does not state specific environmental performance criteria. ISO 14001:2015 can be used in whole or in part to systematically improve environmental management. Claims of conformity to ISO 14001:2015, however, are not acceptable unless all its requirements are incorporated into an organization’s EMS and fulfilled without exclusion. ISO 14004:2016—Environmental management systems—General guidelines on implementation. ISO 14004:2016 provides guidance for an organization on the establishment, implementation, maintenance, and improvement of a robust, credible, and reliable EMS. The guidance provided is intended for an organization seeking to manage its environmental responsibilities in a systematic manner that contributes to the environmental pillar of sustainability. This International Standard helps an organization achieve the intended outcomes of its EMS, which provides value for the environment, the

organization itself and interested parties. Consistent with the organization’s environmental policy, the intended outcomes of an EMS include:

• enhancement of environmental performance; • fulfilment of compliance obligations; • achievement of environmental objectives. The guidance in this International Standard can help an organization to enhance its environmental performance, and enables the elements of the EMS to be integrated into its core business process. Note: While the EMS is not intended to manage occupational health and safety issues, these can be included when an organization seeks to implement an integrated environmental and occupational health and safety management system. ISO 14004:2016 is applicable to any organization, regardless size, type, and nature, and applies to the environmental aspects of its activities, products, and services that the organization determines. The guidance in this International Standard can be used in whole or in part to systematically improve environmental management. It serves to provide additional explanation of the concepts and requirements. While the guidance in this International Standard is consistent with the ISO 14001 EMS model, it is not intended to provide interpretations of the requirements of ISO 14001. ISO 14005:2010 provides guidance for all organizations, but particularly small- and medium-sized enterprises, on the phased development, implementation, maintenance, and improvement of an EMS. It also includes advice on the integration and use of environmental performance evaluation (EPE) techniques. ISO 14005:2010 is applicable to any organization, regardless of its level of development, the nature of the activities undertaken, or the location at which they occur. The auditing standard, ISO 19011:2018 provides guidance on principles of auditing, managing audit programs, the conduct of audits, and on the competence of auditors. ISO 19011:2018 provides guidance on auditing management systems, including the principles of auditing, managing an audit program, and

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conducting management system audits, as well as guidance on the evaluation of competence of individuals involved in the audit process, including the person managing the audit program, auditors, and audit teams. ISO 19011:2018 is applicable to all organizations that need to conduct internal or external audits of management systems or manage an audit program. The application of ISO 19011:2018 to other types of audits is possible, provided that special consideration is given to the specific competence needed. ISO 14031:2013 Environmental management— Environmental performance evaluation— Guidelines. ISO 14031:2013 gives guidance on the design and use of EPE within an organization. It is applicable to all organizations, regardless type, size, location, and complexity. ISO 14031:2013 does not establish environmental performance levels. The guidance in ISO 14031:2013 can be used to support an organization’s own approach to EPE, including its commitments to compliance with legal and other requirements, the prevention of pollution, and continual improvement. ISO/TR 14062:2002 describes concepts and current practices relating to the integration of environmental aspects into product design and development.

3.3.3 Incorporation of Eco-Design or Sustainable Design in the Life Cycle Through ISO 14006 ECD or sustainable design targets the reduction of adverse environmental impacts of a product throughout its entire life cycle. This can involve balancing the environmental aspects of the product with its intended use, performance, cost, marketability and quality, and choosing methods to meet legal and regulatory requirements in the most environment-friendly way. ISO 14006:2011 provides guidelines to assist organizations in establishing, documenting, implementing, maintaining, and continually improving their management of ECD as part of an EMS. ISO 14006:2011 is intended to be used by those organizations that have implemented an EMS in

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accordance with ISO 14001, but can also help in integrating ECD in other management systems. The guidelines are applicable to any organization regardless of its size or activity. ISO 14006:2011 applies to those product-related environmental aspects that the organization can control and those it can influence. ISO 14006:2011 does not establish by itself specific environmental performance criteria, and is not intended for certification purposes. IEC/DIS 62959, under development will deal with principles, requirements and guidance of ECD. Topics include:

• integration of ECD into the management strategy of an organization;

• incorporating

ECD

into

design

and

development;

• analysis of stakeholder requirements; • identification and evaluation of environmental aspects;

• ECD review; • examples on implementing ECD; • ECD methods and tools selection.

3.3.4 Environmental Assessment of Sites and Organizations ISO 14015:2001 deals with environmental management—environmental assessment of sites and organizations (EASO). Organizations are increasingly interested in understanding the environmental issues associated with their sites and activities or those of potential acquisitions. These issues and their associated business consequences can be appraised by means of an EASO. Such an assessment may be carried out during operations or at the time of acquisition or divestiture of assets, and may be conducted as part of a broader business assessment process often referred to as “due diligence.” This International Standard gives guidance on how to conduct an EASO. It provides the basis for harmonization of the terminology used and for a structured, consistent, transparent, and objective approach to conducting environmental assessments. It can be used by all organizations, including smalland medium-sized enterprises, operating anywhere in the world.

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3.3.5 Environmental Labels and Declarations: The ISO 14020 Series of Standards The ISO 14020 series of standards addresses a range of different approaches to environmental labels and declarations, including eco-labels (seals of approval), self-declared environmental claims, and quantified environmental information about products and services. This International Standard is not intended for use as a specification for certification and registration purposes. Note: Other International Standards in the series are intended to be consistent with the principles set forth in this International Standard. Other standards currently in the ISO 14020 series are ISO 14021, ISO 14024, and ISO/TR 14025. ISO 14021:2016 specifies requirements for selfdeclared environmental claims, including statements, symbols, and graphics regarding products. It further describes selected terms commonly used in environmental claims and gives qualifications for their use. This International Standard also describes a general evaluation and verification methodology for self-declared environmental claims and specific evaluation and verification methods for the selected claims in this International Standard. ISO 14021:2016 does not preclude, override, or in any way change, legally required environmental information, claims, labeling, or any other applicable legal requirements. ISO 14024:2018 environmental labels and declarations: environmental labeling Type I, guiding principles and procedures. ISO 14025:2006 establishes the principles and specifies the procedures for developing Type III environmental declaration programs and Type III environmental declarations. It specifically establishes the use of the ISO 14040 series of standards in the development of Type III environmental declaration programs and Type III environmental declarations. ISO 14025:2006 establishes principles for the use of environmental information, in addition to those given in ISO 14020:2000. Type III environmental declarations as described in ISO 14025:2006 are primarily intended for use in business-to-business communication, but their use in business-to-consumer communication under certain conditions is not precluded.

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Type III environmental declaration provides quantified environmental data using predetermined parameters and, where relevant, additional environmental information.

3.3.6 Environmental Performance Evaluation: ISO 14030 and ISO 14031 Environmental performance evaluation: ISI 14030 and ISO 14031 give guidance on the design and use of EPE within an organization. ISO/CD 14030 ISO/NP 14030 will deal with environmental performance of nominated projects and assets. ISO 14031:2013 gives guidance on the design and use of environmental performance evaluation (EPE) within an organization. It is applicable to all organizations, regardless type, size, location, and complexity. ISO 14031:2013 does not establish environmental performance levels. The guidance in ISO 14031:2013 can be used to support an organization’s own approach to EPE, including its commitments to compliance with legal and other requirements, the prevention of pollution, and continual improvement.

3.3.7 Detailed Accounts of LCA, LCI, LCIA: The ISO 14040 Series ISO 14040:2006 ISO Environmental management—Life cycle assessment—Principles and framework. ISO 14040 describes the principles and framework for life cycle assessment (LCA) including: definition of the goal and scope of the LCA, the life cycle inventory analysis (LCI) phase, the life cycle impact assessment (LCIA) phase, the life cycle interpretation phase, reporting and critical review of the LCA, limitations of the LCA, the relationship between the LCA phases and conditions for use of value choices and optional elements. The intended application of LCA or LCI results is considered during definition of the goal and scope, but the application itself is outside the scope of this International Standard. ISO 14042:2000 environmental management— Life cycle assessment—Life cycle impact assessment

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ISO 14043:2000 environmental management— Life cycle assessment—Life cycle interpretation. ISO/TR 14047:2012, environmental management—Life cycle impact assessment—Examples of application of ISO 14044. The purpose of ISO/TR 14047:2012 is to provide examples to illustrate current practice of life cycle impact assessment according to ISO 14044:2006. These examples are only a sample of all possible examples that could satisfy the provisions of ISO 14044:2017. They offer “a way” or “ways” rather than the “unique way” of applying ISO 14044. They reflect the key elements of the LCIA phase of the LCA. The examples presented in ISO/TR 14047:2012 are not exclusive and other examples exist to illustrate the methodological issues described. ISO/TS 14048, Environmental management— Life cycle assessment—Data documentation format. This technical specification provides the requirements and a structure for a data documentation format, to be used for transparent and unambiguous documentation and exchange of LCA and LCI data, thus permitting consistent documentation of data, reporting of data collection, data calculation, and data quality by specifying and structuring relevant information. The data documentation format facilitates the reporting of LCI data and compliance with the requirements from ISO 14040 and ISO 14041 on data collection, data documentation, and data quality. It also facilitates interpretation of LCI data as described in ISO 14043. In addition, the data documentation format allows the documentation and use of important information for LCIA, ISO 14042, including environmental information, environment condition, and location. ISO/TR 14049, Environmental management—Life cycle assessment—Examples of application of ISO 14044 to goal and scope definition and inventory analysis. ISO/TR 14049:2012 provides examples about practices in carrying out an LCI analysis as a means of satisfying certain provisions of ISO 14044:2006. These examples are only a sample of the possible cases satisfying the provisions of ISO 14044. They offer “a way” or “ways” rather than the “unique way” for the application of ISO 14044. These examples reflect only portions of a complete LCI study.

3.3.8 Risk Management Risks affecting organizations can have consequences in terms of economic performance and

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professional reputation, as well as environmental, safety, and societal outcomes. Therefore managing risk effectively helps organizations to perform well in an environment full of uncertainty. ISO 31000:2018, Risk management—Principles and guidelines, provides principles, a framework, and a process for managing risk. It can be used by any organization regardless of its size, activity, or sector. Using ISO 31000 can help organizations increase the likelihood of achieving objectives, improve the identification of opportunities and threats, and effectively allocate and use resources for risk treatment. However, ISO 31000 cannot be used for certification purposes, but does provide guidance for internal or external audit programs. Organizations using it can compare their risk management practices with an internationally recognized benchmark, providing sound principles for effective management and corporate governance. When implemented and maintained in accordance with this International Standard, ISO claims the management of risk enables an organization to, for example:

• increase the likelihood of achieving objectives; • encourage proactive management; • be aware of the need to identify and treat risk throughout the organization;

• improve the identification of opportunities and threats;

• comply with relevant legal and regulatory requirements and international norms;

• • • •

improve mandatory and voluntary reporting; improve governance; improve stakeholder confidence and trust; establish a reliable basis for decision making and planning;

• improve controls; • effectively allocate and use resources for risk treatment;

• improve

operational

effectiveness

and

efficiency;

• enhance health and safety performance, as well as environmental protection;

• improve

loss management;

prevention

and

incident

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• minimize losses; • improve organizational learning; • improve organizational resilience.

3.3.9 Quality Management Systems: ISO 9000 Family Addresses Various Aspects of Quality Management ISO 9000:2015—The ISO 9000 family addresses various aspects of quality management and contains some of ISO’s best-known standards. The standards provide guidance and tools for companies and organizations who want to ensure that their products and services consistently meet customers’ requirements, and that quality is consistently improved. It describes the fundamental concepts and principles of quality management that are universally applicable to the following:

• Organizations

seeking sustained success through the implementation of a quality management system.

• Customers seeking confidence in an organization’s ability to consistently provide products and services conforming to their requirements.

• Organizations seeking confidence in their supply chain that their product and service requirements will be met.

• Organizations and interested parties seeking to improve communication through a common understanding of the vocabulary used in quality management.

• Organizations performing conformity assess-

focus, the motivation and implication of top management, the process approach, and continual improvement. These principles are explained in more detail in the pdf Quality Management Principles. Using ISO 9001:2015 helps ensure that customers get consistent, good quality products and services, which, in turn, brings many business benefits. ISO/TS 9002:2016 provides guidance on the intent of the requirements in ISO 9001:2015, with examples of possible steps an organization can take to meet the requirements. It does not add to, subtract from, or in any way modify those requirements. ISO/TS 9002:2016 does not prescribe mandatory approaches to implementation, or provide any preferred method of interpretation. ISO 9004:2018 provides guidance to organizations to support the achievement of sustained success by a quality management approach. It is applicable to any organization, regardless size, type, and activity. Many other standards are also of interest for this feature, for example: ISO 10005:2018 Quality management systems—Guidelines for quality plans ISO 10006:2017 Quality management systems—Guidelines for quality management in projects ISO 10007:2017 Quality management—Guidelines for configuration management Other standards deal with specific products or services.

ments against the requirements of ISO 9001.

• Providers of training, assessment or advice in quality management.

• Developers of related standards. ISO 9001:2015 sets out the criteria for a quality management system and is the only standard in the family that can be certified to (although this is not a requirement). It can be used by any organization, large or small, regardless of its field of activity. In fact, there are over one million companies and organizations in over 170 countries certified to ISO 9001. This standard is based on a number of quality management principles including a strong customer

3.3.10 Environmental Product Declaration Environmental product declarations (EPDs) provide quantifiable environmental data to compare products that fulfill the same function. In order to create comparable EPD, they must follow the same rules and guidelines called product category rules (PCR). ISO 14025 (see Section 3.3.5) deals with PCR. For example, EPDs from ASTM show:

• material content • recycled content

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service life global warming potential (GWP) water consumption emissions to air and water waste generation ozone depletion potential (ODP) respiratory effects

The EPD development process, described by ASTM (https://www.astm.org/CERTIFICATION/ filtrexx40.cgi?-P 1 PROG 1 7 1 cert_detail.frm), includes four steps:

• Step 1: Development of PCR—PCRs are developed through the consultation of interested parties. In order to promote harmonization, the existing PCR should be used and adapted prior to the development of a new PCR.

• Step 2: Conduct an LCA—An LCA must be conducted to gather the necessary data in order to compile the environmental impact of the product across its life span from cradle to grave.

• Step 3: Development of the EPD—The manufacturer uses the PCR to compile the LCA data and other relevant environmental information to create the declaration.

• Step 4: Verification of the EPD—The EPD must be verified by the program operator (ASTM in this case), to ensure that the contents of the declaration conform to the requirements of the PCR, including the LCA.

3.4 Environmental Indicators Environment issues are very complex, needing more simple and transparent measures that are more easily usable. Environmental indicators provide a more practical and economical way to track and characterize the state of the environment and serve as a basis for sound and informed environmental characterization.

3.4.1 Overview There are many environmental indicators, and only some examples are provided here. Some

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definitions may overlap. Without claiming to be exhaustive, let us quote:

• • • • • • • • •

Energy consumption CO2 and other GHG, and GWP Water footprint Human toxicity Particulate emission Ozone depletion Smog Acidification Eutrophication

Generation of wastes is broken down by type, for example:

• Municipal waste in kilogram per product unit (weight, length of pipes, number of bottles, etc.).

• Hazardous waste in kilogram per product unit (weight, length of pipes, number of bottles, etc.).

3.4.2 Energy Consumption Primary and secondary energy: Primary energy (crude oil, coal, natural gas, uranium, solar, wind energy, etc.) is often transformed to more convenient forms of energy called “secondary energy” that can directly be used by society, such as electrical energy, refined fuels, or synthetic fuels, heat, and so forth. Tonne of oil equivalent (toe) is defined as the amount of energy released by burning one tonne of crude oil, which is approximately 42 GJ. Fossil energy demand represents a depletion of these finite reserves. For example, concerning polyethylene, for petrochemical PE, fossil energy demand includes fossil feedstock (ethylene) that is converted into the PE polymer itself as well as fossil process energy usage for this conversion. It can be expressed in toe or MJ per product unit (weight, length of pipes, number of bottles, etc.). For bioPE, fossil feedstock is replaced by ethylene issued from sugar cane but process energy may be from fossil or renewable energy. Mean energy consumed for fossil PE is approximately 80 MJ when mean energy consumed for bio-PE is approximately 34 MJ per kilogram of polymer.

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3.4.3 CO2 and other Greenhouse Gases, Gas Warming Potential GWP is an appraisal of greenhouse gas (GHG) (e.g., CO2, methane, nitrous oxide, etc.) contribution to global warming. Global warming comes from an increase in the atmospheric concentration of GHG that changes the absorption of infrared radiation in the atmosphere leading to changes in climatic patterns and higher global average temperatures. GWP is measured in terms of CO2 equivalents and can be expressed in gram (or derived unit) equiv. CO2 per product unit (weight, length of pipes, number of bottles, etc.). Many gases are more detrimental than CO2. The following examples of activity relate to unknown conditions and are provided to get a rough idea:

• • • • •

Carbon dioxide Methane

1 21 28

Nitrous oxide

265 310

Hydrofluorocarbon gases 680 15,000 Sulfur hexafluoride

22,800

Those figures are not rules, and depend on context. They cannot be used for designing, computing, forecasting, and so forth. GHG are often expressed in terms of the amount of CO2, or its equivalent of other GHG, emitted through transport, land clearance, and the production and consumption of food, fuels, manufactured goods, materials, wood, roads, buildings, and services. Example of related standard: ISO 14064-2006: specifies principles and requirements and provides guidance at the project level for quantification, monitoring and reporting of activities intended to cause GHG emission reductions or removal enhancements. It includes requirements for planning a GHG project, identifying and selecting GHG sources, sinks, and reservoirs relevant to the project and baseline scenario, monitoring, quantifying, documenting, and reporting GHG project performance and managing data quality. ISO 14065:2013 complements ISO 14064 by specifying requirements to accredit or recognize organizational bodies that undertake GHG validation or verification using ISO 14064 or other relevant standards or specifications.

3.4.4 Water Footprint The water footprint measures the amount of water used to produce each of the goods and services we use. It can be measured for a single process, such as growing rice, or for a product, such as a pair of jeans. ISO 14046:2014 specifies principles, requirements, and guidelines related to water footprint assessment of products, processes, and organizations based on a LCA. A water footprint assessment can assist in:

• Assessing the magnitude of potential environmental impacts related to water.

• Identifying opportunities to reduce water related potential environmental impacts associated with products at various stages in their life cycle as well as processes and organizations.

• Strategic risk management related to water. • Facilitating water efficiency and optimization of water management at product, process, and organizational levels.

• Informing decision-makers in industry, government or nongovernmental organizations of their potential environmental impacts related to water (e.g., for the purpose of strategic planning, priority setting, product or process design or redesign, decisions about investment of resources).

• Providing consistent and reliable information, based on scientific evidence for reporting water footprint results. A water footprint assessment alone is insufficient to be used to describe the overall potential environmental impacts of products, processes, or organizations. The water footprint assessment according to this International Standard can be conducted and reported as a standalone assessment where only impacts related to water are assessed, or as part of a LCA where consideration is given to a comprehensive set of environmental impacts and not only impacts related to water. In this International Standard, the term “water footprint” is only used when it is the result of an impact assessment. The specific scope of the water footprint assessment is defined by the users of this International Standard in accordance with its requirements.

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Polluted water can be expressed in m3 per product unit (weight, length of pipe, number of bottles, etc.)

3.4.5 Toxicity, Unwanted Emissions Toxicity is the degree to which something is able to produce illness or damage to an exposed organism. Toxicity is often divided into:

• • • •

human toxicity terrestrial ecotoxicity marine aquatic ecotoxicity

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• Fog is the general term applied to a suspension of droplets in a gas. Photochemical smog results from reactions in the atmosphere between NOx, VOCs, and oxidants under the influence of sunlight, that leads to the formation of oxidizing compounds. Smog can cause poor visibility, eye irritation, and damage to material and vegetation if sufficiently concentrated. Photochemical oxidation is measured using photo-oxidant creation potential (POCP) which is normally expressed in gram of ethylene equivalents per product unit (weight, length of pipes, number of bottles, etc.).

fresh water aquatic ecotoxicity

Toxicity is often measured in terms of dichlorobenzene equivalents. Volatile organic compounds (VOCs), formaldehyde for example, form a broad category of volatile chemical compounds, some of which pose a health hazard. The presence of VOCs in the atmosphere can also lead to greenhouse effect, ozone-layer depletion, and acidification. This succinct information is only provided to alert the reader and these topics should be more deeply studied according to the actual problems.

3.4.6 Other Common Indicators 3.4.6.1 Ozone Depletion, Photochemical Oxidation At ground level, ozone is a pollutant, but it forms a stratospheric layer that filters out harmful UV radiation from the sun and protects life. Depletion of this layer increases UV radiation at ground level and can cause skin cancer and other disorders. International convention and national laws prohibit the production, use, and release of ozone-depleting substances.

3.4.6.2 Photochemical Smog Smog, derived from the terms smoke and fog, is extensive atmospheric pollution by aerosols, arising partly through natural processes and partly from human activities.

• Smoke is visible aerosol usually resulting from combustion. This does not include steam.

3.4.6.3 Acidification Acidification results from the deposition of acids, which leads to a decrease in the pH and increase of potentially toxic elements. The major acidifying pollutants are SO2, NOx, HCl, CO2, and NH3. Acidification, measured in terms of SO2 equivalents, can be expressed in gram equiv. SO2 (or derived units) per unit of product (weight, length of pipes, number of bottles, etc.).

3.4.6.4 Eutrophication Eutrophication is caused by the addition of nutrients to a soil or water system that leads to an increase in biomass, damaging other life forms. Water acquires a high concentration of nutrients, especially phosphates and nitrates promoting excessive growth of algae. Eutrophication is measured in terms of phosphate (PO43 ) equivalents and can be expressed in gram (or derived unit) equiv. (PO43 ) per product unit (weight, length of pipes, number of bottles, etc.).

3.4.7 Other Diverse Indicators Abiotic depletion refers to the depletion of nonliving (abiotic) resources such as fossil fuels, minerals, clay, and peat. Abiotic depletion is measured in kilograms (or derived units) of antimony (Sb) equivalents. Biochemical oxygen demand (BOD) measures the amount of dissolved oxygen needed by aerobic biological organisms present in the water to break down organic material. The BOD value is most commonly expressed in milligrams of oxygen consumed per liter of sample during 5 days of incubation at 20°C.

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Example of related standard: ISO 17556:2012— Plastics—Determination of the ultimate aerobic biodegradability of plastic materials in soil by measuring the oxygen demand in a respirometer or the amount of carbon dioxide evolved. Chemical oxygen demand (COD) measures the amount of organic compounds in water. COD measures everything that can be chemically oxidized. Other features can be investigated for special cases, for example:

• Nature conservation, biodiversity, etc. • Land use, deforestation, etc. • Risk of nuclear accidents, etc.

3.4.8 Examples of Indicators Table 3.1 displays environmental indicators for two simple parts (A and B), a tile and a pipe, made out of two commodity plastics, PVC and PE: the results relating to entire life cycle are expressed in usual units for A and B and in relative values (maximum/minimum) to give a rough idea of spreading. Ratios are in broad ranges from 1.3 to 6. Table 3.2 displays the share of various steps of the life cycle of parts A and B: generally speaking, extraction and production subtotal accounts for the main share of the environmental indicators.

system. Synthetization of indexes is very difficult due to the aggregation of dissimilar environmental effects. Synthetization can be more or less partial.

3.5.1 Overview This index can be an assessment according to a scale such as Good Fair Bad, “1 10,” or a figure resulting from a calculation. The goal is to easily manage the various parameters generated by LCIs and to provide some idea of the overall environmental implications of the system for a nonprofessional stakeholder. The root is figures provided by the LCA, but the biggest problem is to “compare oranges and apples” thanks to a subjective equation weighting the various parameters to obtain the eco-index. That implies an equivalence relation between parameters as diverse as consumed energy, feedstock, eutrophication, and so forth. Fig. 3.4A and B shows environmental properties of a PA66 indexed on values of a PE chosen as Base 1 highlighting huge behavior differences:

• PA66 consumes more fuel energy, has higher GWP, AP (acidification potential), POCP, eutrophication potential.

• PA66 consumes less feedstock and has lower ODP, total particulate and dust.

3.5 Synthetic Indices Resulting From Environmental Indicator Integration The goal of indexes is to provide a single figure summarizing the environmental quality of a

An aggregating index cannot be scientifically built because there is no scientific equivalence between the various data. The weighting factors are totally subjective and depend on the general context, local requirements, general trends, the targeted use, and the feeling of the decision-maker.

Table 3.1 Examples of environmental indicators for undefined tile and a pipe. A

B

Maximum/ Minimum

Primary energy

MJ

154

94

1.6

Global warming potential

kg CO2 equiv.

7

4.2

1.7

Acidification potential

kg SO2 equiv.

0.0274

0.0548

2

0.0025

0.0018693

1.3

3

Eutrophication potential

kg PO4 equiv.

Ozone depletion

kg R11 equiv.

8.57E 09

5.45E 08

6

Photochemical ozone creation potential

kg ethene equiv.

0.0026

0.00064743

4

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Table 3.2 Examples of share of various steps of the lifecycle of undefined tile and a pipe. Part A Extraction

Production

Subtotal

Installation and Use

End of life

Primary energy

%

51

22

73

26

1

Global warming potential

%

46

31

77

22

2

Acidification potential

%

55

19

74

23

3

Eutrophication potential

%

50

12

62

33

4

Ozone depletion

%

91

6

97

3

0

Photochem ozone creation potential

%

62

15

77

23

0

Part B Production

Transport, Installation

End of life

GWP

%

73

27

Ignored

ODP

%

45

57

Ignored

AP

%

75

25

Ignored

EP

%

54

46

Ignored

POCP

%

72

28

Ignored

ADPE

%

32

68

Ignored

ADPF

%

84

16

Ignored

ADPE, abiotic resource depletion potential—elements; ADPF, abiotic resource depletion potential—fossil fuel; AP, acidification potential; EP, eutrophication potential; GWP, global warming potential; ODP, ozone depletion potential; POCP, photochemical oxidant formation potential.

(A)

(B)

Nonrenewable energy

GWP

Particulates Abiotic depletion fossil fuels

ODP

Fuel energy Dust

Abiotic depletion elements PA66/PE

AP

Feedstock energy EP PE=base 1

PA66/PE

POCP PE=base 1

Figure 3.4 (A) PA66: indexed environmental data. (B) Indexed environmental indicators.

As a consequence, generally speaking, the ecoindex can be useful but is inevitably subjective leading to subjective decisions. ISO (https://www.iisd.org/pdf/globlgrn.pdf) displays two private examples issued by:

• Volvo • CML (Institute of Environmental Sciences— https://www.universiteitleiden.nl/en/science/ environmental-sciences)

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• Normalization data for all interventions and

3.5.2 Eco-Profiling System— Volvo/Swedish Industry (https:// www.iisd.org/pdf/globlgrn.pdf)

impact categories at different spatial and temporal levels.

The eco-profiling system (EPS) uses four different environmental indices as a primary tool in its approach to environmental impact analysis. These indices are:

• • • •

Natural resource index Substance effect index Material index

• Connection with CMLCA. The process encompasses four components:

• • • •

Goal definition Inventory Impact analysis Valuation

Process index

The natural resource and substance effect indices are developed through the application of six ecological scores which are multiplied together to yield a single numerical index number. The determining criteria are:

• Type and extent of environmental impact or problem;

• Intensity and frequency of occurrence of impact;

• Real distribution of impact; • Durability of problem; • Contribution to problem by emission of 1 kg of the substance;

• Possibility and associated costs of remedying problem.

CML-IA was created by CML (https://www.universiteitleiden.nl/en/research/research-output/science/cml-ia-characterisation-factors#features). CML-IA is a database that contains characterization factors for LCIA and is read by the CMLCA software program. Included are:

• The characterization factors for all baseline characterization methods mentioned in the handbook on LCA, such as GWP100, POCP, HTPinf, and AP.

• Additional characterization factors for nonbasuch

as

• Additional characterization methods, such as eco-indicator 99 and EPS.

The following is a brief overview (not an in-depth study) and focuses on technical aspects. The quoted company names, trademarks, and websites are only examples provided “as they are” and do not constitute any legal or professional advice. Many other software solutions are proposed and may be suitable. It is the responsibility of the reader to determine the appropriate use of each database and software. Providers of sustainability reporting guidance include, among others:

• Global Reporting Initiative (https://www.globalreporting.org/information/about-gri/Pages/ default.aspx) GRI (GRI’s Sustainability Reporting Standards).

3.5.3 CML-IA by CML

seline characterization methods, GWP20, HTP100, and MSETP.

3.6 Databases and Software Help in Environmental Management, but Can Lead to Some Discrepancy

• The Organisation for Economic Co-operation and Development (OECD Guidelines for Multinational Enterprises) (http://www.oecd. org/investment/mne/1922428.pdf).

• The United Nations Global Compact (the Communication on Progress, CoP) (https:// www.unglobalcompact.org/participation/report/ cop).

• The

International Organization for Standardization (ISO 26000, International Standard for social responsibility).

The website http://www.plasticseurope.org/plastics-sustainability-14017/eco-profiles.aspx provides access to PlasticsEurope’s Eco-profiles. Ecoprofiles are LCI datasets and EPDs for plastics.

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EPA (https://www.epa.gov/research/methods-models-tools-and-databases): EPA’s ecosystems research is working to protect ecosystems and the air and water resources that provide numerous benefits for humans and other living things. EPA edits several databases. IPCC (Integrated Pollution Prevention and Control): The Data Distribution Centre (DDC) (http://www.ipcc-data.org/) of the IPCC provides climate, socio-economic and environmental data, both from the past and also in scenarios projected into the future. For example, the website http:// provides www.ghgprotocol.org/calculation-tools coefficients relative to GHG.

3.6.1 Examples of Software Solutions Among other software providers, let us quote about 20 examples without claiming to be exhaustive. Targets are diversified with more or less complete examination of more or less numerous parameters and more or less ease of use. Accucio (https://www.accuvio.com/) proposes a suite dealing with:

• • • • • •

Sustainability reporting Energy and carbon Compliance and regulation Corporate responsibility Supply chain emissions reporting

• • • •

• Sustainable design • Automatic sustainability report generation • GaBi environmental database

Environmental impact dashboard Material optimization Assembly visualization Screening-level LCA

EcoImpact (http://trayak.com/ecoimpact/) offers a platform including Compass-Package, CompassProduct, and Score, to operationalize product and corporate sustainability goals. EcoImpact can generate environmental profiles and compare up to four packaging/product alternatives simultaneously. LCA takes into account consumption metrics, emission metrics (GHG, toxicity, eutrophication), use of recycled materials, solid waste generation, and the various phases of the life cycle. Score can generate customizable eco-scoring for decision making that meet business goals. Sustainability needing optimization of all the involved parameters, areas of interest are very diverse, including, for example, without claiming to be exhaustive:

• • • • • • •

Audit and compliance assurance

• • • • • • • • • • • • • •

Contractor management

Waste management

CMLCA (https://www.universiteitleiden.nl/en/ research/research-output/science/cml-cmlca) (http:// www.cmlca.eu/) is a software tool that supports the technical steps of the LCA. The focus of the program is the computational aspects of LCI calculations (LCA; IOA: input output analysis, EIOA: environmental input output analysis, etc.). Cority (https://ehsq.cority.com/environmental/whatis-strategic-ehsq-why-does-it-matter) proposes environment, health, safety, and quality (EHSQ) suites. Dassault Syste`mes SolidWorks Corporation distributes SOLIDWORKS Sustainability solution (http://www.solidworks.com/sw/products/simulation/solidworks-sustainability.htm) providing:

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Audits and inspections Business risk management Chemical inventory Chemical management Compliance assign Compliance with GHS (globally harmonized system of classification and labeling of chemicals) Dashboard analysis and trending Data warehouse Document management Emission inventory Employee engagement Energy management Engage with stakeholders Ensure compliance Environmental compliance Environmental remediation Environmental reporting Equipment maintenance Hazardous materials control

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• • • • • • • • • • • • • • • • • • • • • •

Health and safety audits

• SDS authoring software deals with GHS compliance SDSs, ensuring that all regulations and chemical classifications are up to date.

Health and safety: incidents, injuries Incident management Management systems Mobile apps

• Compliance management and risk minimization software

• Health and safety software allows to track,

Near-miss reporting

prevent and respond to any incident, keeping the facility in full OSHA compliance.

Operational risks Performance improvement Product compliance Quality management system Regulatory compliance Responsible sourcing Risk management Safety data sheets (SDSs) management Security program management Sustainability management Systems integrations Tasks and corrective actions Track and manage any task or project Training compliance Training management Training: health and safety features

EHS SmartStart (http://www.ehssmartstart.com/) is an environmental, health and safety solution including:

• Compliance with standards such as ISO, occupational safety and health administration (OSHA), RIDDOR, and COSHH for local and international regulatory requirements.

• Incident managements at any time with imme-

eVerdEE (http://genesi-fp7.eu/everdee/) (https:// www.sustainabilityprofessionals.org/everdee). eVerdEE is a web-based streamlined LCA tool for small- and medium-sized enterprises. Its main feature is the adaptation of ISO 14040 requirements to offer easy-to-handle functions with sound scientific bases. It supports the assessment of the environmental performance throughout the whole product life cycle. Impacts are quantified on the basis of 12 impact categories:

• • • • • • • • • • • •

consumption of mineral resources consumption of biomass consumption of fresh water consumption of nonrenewable energy consumption of renewable energy climate change acidification eutrophication photochemical oxidation ozone-layer depletion amount of hazardous waste amount of total waste

diate root cause analysis and assessment.

• Audit

management: Establish continually updated legal compliance, using legislative checklists and country legal registers.

• Risk management: Monitor, measure, and mitigate risk with real-time status reports for any site, region, or globally. ERA (Environmental Management Solutions) (http://www.era-environmental.com/) offers:

• Environmental management software deals with air, water, and waste reporting and compliance management.

The toxicity category is not assessed. The global emissions model for integrated systems (GEMIS) (http://iinas.org/about-gemis.html) consists of an analysis model to determine energy and material flows, and a database. The analysis model calculates for processes and scenarios so-called life cycles, that is, it takes into account all processes from resource extraction (primary energy, raw materials) to final energy or material use, and includes auxiliary energy and material uses as well as materials for constructing energy, material, and transport systems.

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For all processes, GEMIS stores:

• data on efficiency, power, operating time, and lifetime;

• direct air emissions (SO2, NOx, halogens, particulates, CO, NMVOC, H2S, NH3);

• GHG emissions (CO2, CH4, N2O, as well as SF6 and CFCs);

• solid wastes (ash, FGD residues, sewage treatment sludge, production wastes, overburden);

• liquid effluents (adsorbable organic halides, AOX, BOD5, COD, N, P, inorganic salts);

• land use. GEMIS can also analyze costs—the respective data of fuels, energy, and transport processes (investment, O&M) are part of its database—and employment. Results of GEMIS are the environmental flows given above, but also aggregated values:

• Resources as cumulated energy demand • GHG as CO2 equivalents • Air emissions as SO2 equivalents (AP) and ozone precursor equivalents (summer smog)

• External environmental costs Gensuite (https://www.gensuite.com/productsand-services/) proposes solutions including:

• • • • • • • • • • •

Audit and compliance assurance Change management Chemical management Contractor management Employee engagement Environmental compliance Environmental remediation Equipment maintenance Gensuite insight and analytics Incident management Management systems

• • • • • • •

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Product stewardship Quality management systems Responsible sourcing Safety programs and procedures Security program management Sustainability/energy management Training compliance

Granta (https://www.grantadesign.com/products/ data/ecoselectorprops.htm) proposes diverse software including MaterialUniverse Eco Data dealing with:

• • • • • • • • • • • • •

Embodied energy, primary production (MJ/kg)

• • • • • • • • • • • •

RoHS (EU) compliant grades? (yes/no)

CO2 footprint, primary production (kg/kg) NOx creation (g/kg) SOx creation (g/kg) Recycle fraction in current supply (%) Water usage (l/kg) Polymer molding CO2 and energy Polymer extrusion CO2 and energy Polymer machining CO2 and energy Nonstandard machining CO2 and energy Simple composite molding CO2 and energy Advanced composite molding CO2 and energy Toxicity rating (nontoxic, slightly toxic, toxic, very toxic) Approved for skin and food contact? (yes/no) WEEE prohibited? (yes/no) Recycle? (yes/no) Embodied energy, recycling (MJ/kg) CO2 footprint, recycling (kg/kg) Recycle fraction in current supply (%) Down cycle? (yes/no) Biodegrade? (yes/no) Landfill? (yes/no) Heat of combustion (net) Combustion CO2, nonrecyclable-use fraction

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This data is provided as standard with the MaterialUniverse data module. Integrum (http://www.integrumsystems.com/integrum) proposes QHSE risk and compliance software, a fully integrated management platform including:

• • • • • • • • • • •

Incident and investigation management Audit and inspection management Training management/eLearning Controlled document management Compliance management

• Continuous improvement and implementation of new features. Perillon (http://www.perillon.com/environmental-management-system) offers EHS software solutions dealing with:

• • • •

Risk and control management Business intelligence (BI) reporting BI system

Geographic information system and spatial reporting

Intertek (http://www.intertek.com/consumer/sustainability/instant-life-cycle-assessment-software) Instant LCA Packaging proposes an ECD and ecolabeling tool, enabling nonexperts to immediately evaluate the environmental impacts of their packaging. This tool uses preintegrated LCA models based on ISO standards and recognized LCA databases. openLCA (http://www.openlca.org/) is an open source and free software for sustainability and LCA, with the following claimed features:

• Calculation of sustainability assessment and/or LCA.

• Detailed insights into calculation and analysis results; identify main drivers.

• Throughout the life cycle, by process, flow or impact category, visualize results and locate them on a map.

• Import and export capabilities; easy to share the models.

• LCC and social assessment integrated in the life cycle model.

• Repository and collaboration feature (currently developed).

Corporate sustainability. Risk management. Environmental data: Centralize air, water, and waste data into a system with a configurable calculation engine and generate regulatory reports in seconds.

• Audits and inspections: Streamline environmental audits and inspections, and generate reports immediately.

“Drag and drop” reports and dashboards Predictive analytics

Environmental health and safety management.

• Incidents: Centralize and standardize environmental compliance responsibilities with automated alerts and notifications.

• Nonconformance events: Drive investigations, notifications, and actions to reduce future occurrence.

• Carbon management: Manage and track GHG and other carbon data, and create reports immediately.

• Energy management: Define energy usage metrics and efficiently analyze results. SimaPro (https://simapro.com/about/) is a professional tool to collect, analyze, and monitor the sustainability performance data of products and services. The software can be used for a variety of applications, such as:

• • • • •

Sustainability reporting Carbon and water footprinting Product design EPDs Key performance indicators.

ThinkStep (formerly PE INTERNATIONAL AG) proposes the Supplier Engagement Software Suite (https://www.thinkstep.com/software/supplychain-transparency/supplier-engagement-suite) that

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Table 3.3 Discrepancies Between One Property and Ranking According to 4 Software Solutions. PET

PLA

Traditional Materials

31

31

17 30

Rank

Min

Mean

Max

PET

2

2.25

3

PLA

3

3.5

4

Glass

1

1

1

Al can

2

3.25

4

Aseptic carton

5

5

5

Coefficient of variation of raw data, % Ranking

PET, Polyethylene terephthalate; PLA, polylactic acid

targets collecting, verifying, and analyzing supplier sustainability data and integrates:

• GaBi Database, an LCA database providing

notifications submitted by WTO members as well as environmental measures and policies mentioned in the trade policy reviews of WTO members. The database is updated on an annual basis.

more than 10,000 environmental profiles of materials and processes.

• SoFi software targets all sustainability reporting solution.

• BOMcheck THINKSTEP, a centralized web solution keeping up-to-date with new substance regulations around the world allowing to manage data securely in the database and download declarations. Umberto (https://www.ifu.com/en/umberto/lcasoftware/) is a software for material flow management and material flow analyses. It can help:

• • • •

improve material and energy efficiency; reach resource efficient processes; reduce the climate impact of production systems; increase the sustainability performance of products.

The World Trade Organization’s (WTO) environmental database (https://www.wto.org/english/tratop_e/ envir_e/envdb_e.htm) contains all environment-related

3.6.2 Software May Lead to Some Discrepancies Software are designed to obtain compromises between various levels of sustainability complexity and ease of use that can lead to some discrepancies between property data and even ranking of a same part manufactured with various raw materials. For example, Ricky Speck and All. “Choice of Life Cycle Assessment Software Can Impact Packaging System Decisions” (https://doi.org/10.1002/pts.2123) compare one usual indicator measured on bottles or other containers made out of polyethylene terephthalate (PET), polylactic acid (PLA), glass, aluminum, or aseptic carton. Table 3.3 displays:

• Coefficient of variation of raw data. • Ranking: • Two materials have the same rank. • One material has consecutive ranks. • One material is ranked on a range of three classes.

Abiotic depletion refers to the depletion of nonliving (abiotic) resources such as fossil fuels, minerals, clay, and peat. Abiotic depletion is often measured in terms of antimony (Sb) equivalents. Acidification results from the deposition of acids which leads to a decrease in the pH and increase of potentially toxic elements. The major acidifying pollutants are SO2, NOx, HCl, CO2, and NH3. Acidification is measured in terms of SO2 equivalents. BOD measures the amount of dissolved oxygen needed by aerobic biological organisms present in the water to break down organic material. The BOD value is most commonly expressed in milligrams of oxygen consumed per liter of sample during 5 days of incubation at 20°C. Example of related standard: ISO 17556:2012—Plastics—Determination of the ultimate aerobic biodegradability of plastic materials in soil by measuring the oxygen demand in a respirometer or the amount of carbon dioxide evolved. Certification: Procedure by which a third party gives written assurance that a product, process or service conforms to specified requirements. COD measures the amount of organic compounds in water. COD measures everything that can be chemically oxidized. CML methodology is developed by the Institute of environmental sciences at the University of Leide. There are CML 1996 and CML 2001 methods. The results are presented in the form of a spreadsheet that presents characterization for more than 1700 flow factors (2001). Cradle to factory gate: Cycle beginning with raw material extraction from the earth and ending with the product leaving the factory. Cradle to grave: Complete cycle beginning with raw material extraction and ending with the final disposal of the product or part (recycling, composting, landfilling, etc.). Design: Conscious design, eco-design, environmental design, green design, sustainable design, and so on are new ways of designing aiming to comply with the principles of social, economic, and ecological sustainability. They are based on principles concerning the native resource preservation, renewable source uses avoiding competition with food crops, energy saving, ban of toxic elements and molecules, carbon footprint reduction, effectiveness of recycling, and end-cost optimization. Eco-Indicator 95, Eco-Indicator99 are methods having attempted to overcome the complexity of LCA by: a. Providing a weighing method that allows summing up of individual impacts. b. Developing a library of eco-indicator values for the most common material and processes used in industrial activities. Eco-profile: Assessment of the total energy use, raw material use, air, and water emissions and the total solid waste produced from the cradle to the factory gate. An eco-profile always ends with the production of the considered part or product. Ecotoxicity assessment: Effect of a compound or mixed contamination on an organism can be assessed with a biotest. The goal of ecotoxicity assessment is to understand the link between the concentrations of chemicals and effects on organisms in the environment. Examples of related ISO standard: ISO 11269 Soil Quality—Determination of the effects of pollutants on soil flora. ISO 11267 Soil Quality—Effects of pollutants on collembolan (Folsomia candida). ISO 11268 Soil Quality—Effects of pollutants on earthworms. ISO 14238 Soil Quality—Determination of nitrogen mineralisation in soils and influence of chemicals on the process. ISO 14240 Soil Quality—Determination of soil microbial biomass. ISO 15685, Soil Quality—Ammonium oxidation, a rapid method to test potential nitrification in soil. ISO 15799 Soil Quality—Guidance on the ecotoxicological characterisation of soils and soil materials.

Eutrophication is caused by the addition of nutrients to a soil or water system which leads to an increase in biomass, damaging other life forms. Water acquires a high concentration of nutrients, especially phosphates and nitrates promoting excessive growth of algae. Eutrophication is measured in terms of phosphate (PO43 ) equivalents and can be expressed in g (or derived unit) equiv. (PO43 ) per product unit (weight, length of pipes, number of bottles, etc.). Feedstock energy: Heat of combustion of a raw material input that is not used as an energy source to a product system, expressed in terms of higher heating value or lower heating value. Care is necessary to ensure that the energy content of raw materials is not counted twice. Fossil energy demand represents a depletion of these finite reserves. For example, concerning polyethylene, petrochemical PE’s fossil energy demand includes fossil feedstock (ethylene) that is converted into the PE polymer itself as well as fossil process energy usage for this conversion. It can be expressed in toe or MJ (or derived unit) per product unit (weight, length of pipes, number of bottles, etc.) GWP is an appraisal of GHG (e.g., CO2, methane, nitrous oxide, etc.) contribution to global warming. Global warming comes from an increase in the atmospheric concentration of GHG which changes the absorption of infrared radiation in the atmosphere leading to changes in climatic patterns and higher global average temperatures. GWP is measured in terms of CO2 equivalents and can be expressed in gram (or derived unit) equiv. CO2 per product unit (weight, length of pipes, number of bottles, etc.). GHG: GHG are often expressed in terms of the amount of carbon dioxide, or its equivalent of other GHGs, emitted through transport, land clearance, and the production and consumption of food, fuels, manufactured goods, materials, wood, roads, buildings, and services. IPCC edits equivalent CO2 values such as:

• 21 28 for methane • 265 310 for nitrous oxide • About 10,000 for the perfluoropolyethers

Example of related standard: ISO 14064-2006 specifies principles and requirements and provides guidance at the project level for quantification, monitoring and reporting of activities intended to cause GHG emission reductions or removal enhancements. It includes requirements for planning a GHG project, identifying and selecting GHG sources, sinks, and reservoirs relevant to the project and baseline scenario, monitoring, quantifying, documenting, and reporting GHG project performance and managing data quality. Indicator unit examples: be careful: • Many derived units are used, for example, MJ and GJ for J.

• Units of the products must be reported. They may be as diverse as weight, length of pipes, number of bottles, area of windows, etc. (Continued )

—Cont’d

• A few examples are quoted below:

Topic

Impact Category

Examples of Unit for the Indicator

Consumption of resources

Total energy

MJ

Air pollution

Global warming potential

g equiv. CO2

Acidification potential

g equiv. SO2

Photochemical oxidation

g equiv. ethylene

Eutrophication potential

g equiv. PO4

Water pollution (critical volume)

m3

Municipal waste

kg

Hazardous waste

kg

Water pollution

Waste

Life cycle assessment or life cycle analysis (LCA) assesses environmental impacts resulting from all the stages of a product or part life including raw material extraction, material processing, manufacture, distribution, use, repair and maintenance, and disposal or recycling ISO 14040, ISO 14044, and ISO/TS 14072:2014 deal with LCA, requirements, and guidelines These specifications detail: • the application of LCA principles and methodology to organizations,

• • • •

the benefits that LCA can bring to organizations by using LCA methodology at organizational level, the system boundary, specific considerations when dealing with LCI, LCIA, and interpretation, the limitations regarding reporting, environmental declarations, and comparative assertions.

Life cycle inventory (LCI) is the inventory of the total energy use, raw material use, air, and water emissions and the total solid waste produced from the cradle to grave (grave being the ultimate disposal). The LCI gives the basic data for the LCA. It is equivalent to the eco-profile covering the complete life cycle. In the strict sense of the term, the LCI of resins, pellets, new films or tubes, and so forth, does not exist because the pellets and new parts or products aren’t usually thrown away. Material flow cost accounting: A management tool to promote effective resource utilization, mainly in manufacturing and distribution processes, in order to reduce the relative consumption of resources and material costs. ODP

At ground level ozone is a pollutant but it forms a stratospheric layer that filters out harmful UV radiations from the sun and protects life. Depletion of this layer increases UV radiations at ground level and incidence of skin cancer and other disorders. International convention and national laws prohibit the production, use, and release of ozone-depleting substances. ODP is measured in terms of CFC-11 equivalents and can be expressed in g (or derived unit) equiv. CFC-11 per product unit (weight, length of pipes, number of bottles etc.). Photochemical oxidation: The formation of photochemical oxidant smog is the result of complex reactions between NOx and VOCs under the action of sunlight (UV radiation) which leads to the formation of ozone in the troposphere. The smog phenomenon is very dependent on meteorological conditions and the background concentrations of pollutants. Photochemical oxidation is measured using POCP which is normally expressed in ethylene equivalents per product unit (weight, length of pipes, number of bottles, etc.). Price elasticity: The percentage change in quantity of supply or demand in response to a percentage change in price. Primary and secondary energy: Primary energy (crude oil, coal, natural gas, uranium, solar or wind energy, etc.) is transformed to more convenient forms of energy called “secondary energy” that can directly be used by society, such as electrical energy, refined fuels, or synthetic fuels heat, and so forth. Primary product: Basic raw material that has not been processed and is therefore in its natural state, specifically products of agriculture, forestry, and mining. Product: Activity output with a positive either market or nonmarket value, subdivided into goods (tangible products) and services (intangible products). Raw material: Primary or secondary material that is used to produce a product. Secondary material includes recycled material. Recycling Primary recycling: Secondhand use of a product without changing or altering the product that is simply reused. Secondary recycling: Mechanically processed product to allow its reuse. Regrind is an example. In some cases, regrind can be upgraded by addition of additives. Tertiary recycling: Depolymerization of a product into monomers using a chemical process and then turning them into a new product. For example, chemically recycling plastic bottles Secondary product: Product processed from raw materials that is not a primary product. Services: Products without mass, that is, intangible products as opposed to goods. (Continued )

—Cont’d System boundaries: The denominations of which entities are inside the system and which are outside. Tonne of oil equivalent (toe) is defined as the amount of energy released by burning one tonne of crude oil. It is approximately 42 GJ. Toxicity is the degree to which something is able to produce illness or damage to an exposed organism. There are four different types of toxicity; human toxicity, terrestrial ecotoxicity, marine aquatic ecotoxicity and fresh water aquatic ecotoxicity. Toxicity is measured in terms of dichlorobenzene equivalents. Transparency (information): Open, comprehensive, and understandable presentation of information. Upstream (in the life cycle): Backwards in the life cycle, toward the raw material extraction and production of the product(s). Volatile organic compounds (VOCs), formaldehyde for example, form a broad category of volatile chemical compounds, some of which pose a health hazard. The presence of VOCs in the atmosphere can also lead to greenhouse effect, ozone-layer depletion, and acidification. Water footprint: The water footprint measures the amount of water used to produce each of the goods and services we use. It can be measured for a single process, such as growing rice, for a product, such as a pair of jeans. ISO 14046:2014 specifies principles, requirements, and guidelines related to water footprint assessment of products, processes and organizations based on the LCA. Only air and soil emissions that impact water quality are included in the assessment, and not all air and soil emissions are included.

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3.7 Clarification Concerning Some Terms The following information is deliberately superficial and it is the responsibility of the reader to study more in-depth his (her) own problem. Note: A defined word may have several senses according to the context. We quote a few standards, but in fact they are numerous depending on the concerned countries,

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the related products or goods, the actual or potential applications, disposal, and so forth.

Further Reading Biron, M., 2017. Industrial Applications Renewable Plastics. Elsevier Ltd.

of

4 Easy Measures Relating to Improved Plastics Sustainability Sustainability results from a subtle balance of multiple entangled parameters taking part in the various phases of the lifetime of the product under consideration. Fig. 4.1 suggests some eventual ways to be followed to succeed in creating innovative sustainable products. Of course, in addition, sustainable products must satisfy sustainable requirements in addition to functional requirements. So, it is necessary to keep that in mind during all the steps of the design. Fig. 4.2 schematizes the intricate combination of sustainable and functional requirements. Considering the processing parameters only, favorable features for sustainability include, but are not limited to:

• The stabilization of the process depends on the reliability of the machinery, the accuracy and efficiency of the control software, the accuracy and consistency of the temperatures, etc. A better stabilization leads to a better quality and a reduction of off-specs and waste. In addition, it is also possible to decrease the wall thickness and, consequently, the resin consumption due to a narrowing of weight dispersion.

• Cycle times depend on the dry cycle times of the used machine, the efficiency of the cooling, and the tool design.

• The energy consumption depends on the machine type, namely hydraulic, electric, or hybrid, and on the energy recovery systems.

• Green energy is a brilliant way toward sustainability, but be sure of the energy type of the use phase.

• The changeover systems and preset functions of software systems allow for the productivity to be increased.

• Automation and in-line integration are unique solutions to boost global productivity as far as

peripheral operations or manufacturing steps are suppressed.

• New techniques can drastically modify the end processing cost. Sustainability forms a coherent package meaning that a good option for a defined step may be inadequate for the total life cycle of the studied product and the converse is also true. Of course, the reader must check the suitability of this information for their own case.

4.1 Overview of Pace of Change in the Plastics Industry Solutions must be considered early on, as far as a question is complex and requires hard upstream research and the implementation of important logistical measures. Some examples give a rough idea of the downtimes:

• Novamont is generally recognized as a pioneer in the sector of starch-based biodegradable materials. It started its research activity in 1989. 26 years later its production capacity for Mater-Bi is around 120,000 t/year.

• Cargill started its polylactic acid project in 1989. 25 years later its production is significant, but remains in the area of specialties, and a lot of research is necessary to expand the application field.

• In the 1980s, Imperial Chemical Industries developed a poly(3-hydroxybutyrate-co-3hydroxyvalerate) obtained via fermentation that was named “Biopol.” It was sold under the name “Biopol” and distributed in the United States by Monsanto and later Metabolix.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00004-5 © 2020 Elsevier Ltd. All rights reserved.

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Minimize Energy

Minimize Waste

Efficient machines

Easy to process materials

Green energy

Expand Management

Shift to Eco-design

Use reliable means

Smart machines

Stringent planning

Smart digitalization

Manufacturing step integration

Real-time control

Limit Emissions

Function integration

Limit emission

3R—Repair, Recycle, Reuse

Ban hazardous emissions

Decontaminate

Use renewable resources

trap and treat

Figure 4.1 Some ways to be followed to succeed in innovative sustainable products.

Reduction of material impact Temperature low, average, height

Time

Minimize manufacturing impact

Optimize end-of-life Mechanical properties Thermal properties

Aging Chemicals Physical properties

Physical aging dynamic, static

—

Electrical properties

Reduce impacts of the

Fire behavior

Material selection

use phase

Reduce impact of distribution

Figure 4.2 Diagrammatic material selection process.

• Coca-Cola introduced PlantBottle technology in 2009 as the first recyclable polyethylene terephthalate (PET) plastic bottle made partially from plants. Since then, more than 18 billion PlantBottle packages have reached the market in 28 countries. The company plans to convert all of its PET plastic bottles to PlantBottle packaging by 2020, that is, 11 years after the introduction of the PlantBottle technology.

• Aliphatic polyketones, under the trade name “Carilon,” developed by Shell, launched in the 1990s and discontinued in the 2000s but made a comeback with a relaunch in 2015. Albeit being considered as an environment-friendly polymer, 20 years after the first commercial

launch (and many additional years after the first research work), the commercialization remains restricted.

• PepsiCo began to incorporate postconsumer recycled content into its (PET) plastic in 2004. On average, up to 10% postconsumer recycled PET (rPET) is incorporated into its primary soft-drink containers in the United States. In Canada, 7UP bottles were the first 100% postconsumer content bottles for a carbonated soft drink. PepsiCo aimed to increase the US beverage-container recycling rate to 50% by 2018.

• In 1950 the total production of plastics was about 1.7 million tons, that is, the magnitude order for renewable plastics today. 60 years

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later, the total production of plastics is about 300 million tons, that is to say, about 175times more.

• According to C. Musso, PhD (McKinsey), new polymers have averaged 11 years to reach 150,000 t/year sales from when the commercial plant became operational. In conclusion, time frames for industrial development are on the order of decades, from 10 to more than 60 years according to the magnitude of the problem. Currently, researchers are working for 2050 and beyond.

4.2 Decrease the Material Impact on the Product Sustainability Satisfying sustainable requirements needs some measures of good sense that are easy to apply, but others require deep changes in society’s ways of thinking, behavior, and even way of life. It is useful to remember that:

• Products must be compliant with mandatory laws and regulations, and environmental trends must be anticipated

• Sustainable products must be technically viable

• Sustainable products must be economically competitive

• Deep changes in the plastics industry need time periods on the order of some tens of years Materials being an important share of plastics products, it is of prime importance to diminish their impact on the environment. Several quoted measures meet the requirements examined in the functional part of this chapter, optimization of material consumption, for example, while others are more specifically linked to environmental requirements or trends.

4.2.1 Avoid, Minimize, or Ban Hazardous Materials; Obey Health and Safety Concerns, Regulation Compliance Some chemicals are banned in general or in particular for certain applications. The ban may be

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global, regional, local, or even dictated by application sectors and even private companies. The following is a limited and incomplete reminder. The design, processing, and application of plastics and composites are professional activities needing specific skills and involving industrial and financial risks, health hazards, toxicity, fire hazards, regulation compliance, and so forth. Standards, directives, regulations, approvals, laws, codes, among others, depend on the regions of processing, commercialization, use, application, and disposal. Beware of names and acronyms that can cover different requirements according to countries or industrial sectors. For example, for the same part, the requirements can be different in the country of processing and in the country of commercialization. The reader must search the suitable standards, regulations, directives, approvals, laws, and so forth, related to their own case and is solely responsible for the chosen solutions. It is the responsibility of the reader to search, study, and verify the compliance of the chosen solution with processing rules, safety precautions, health hazards, existing national and corporate laws and regulations emitted by the countries of processing, commercialization, use, and application, and disposal. Regulations and specifications including general regulations related to industrial and commercial activities concern workers at all steps of the part life, users, and all people involved in handling, processing, storage, disposal, among others. Government and private agencies have specifications and approval cycles for many plastic parts. It is the responsibility of the reader to determine the appropriate use of each product, processing method, and the compliance with processing rules, safety precautions, health hazards, existing national laws and regulations emitted by the countries of processing, commercialization, use, application, and waste. Without entering into detail, let us recall some examples. These are far from representing the whole extent of the problem.

• The obligation to respect limits of residual monomer rates. For example, after the application of urea-formaldehyde resin, the residual rate of formaldehyde is limited according to national regulations.

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• The use of heavy metals and halogens is more and more disputed.

• Solvents, for example, styrene, are subject to increasingly severe legal requirements. Regulations are becoming increasingly complex, which has led to the launch of new tools to help designers to “de-risk” their materials and processes. For example, Granta Design (https://www.grantadesign.com/) has made additional improvements to its Granta MI (Material Intelligence): Restricted Substances software. Risks associated with restricted substance regulations such as the European Union’s REACH include legal liability, noncompliance costs, redesign, product recalls, and inability to service products due to material obsolescence. In-house information managed in Granta MI is then linked to a regularly-updated database of 8000 1 substances and 100 1 international regulations that restrict their use. Software tools enable users to apply the resulting knowledge-base to analyze risk for specifications, materials, and processes, and also for designs and products. The new software includes updated data on regulations including the IARC Monographs (International Agency for Research on Cancer) on the Evaluation of Carcinogenic Risks to Humans and the EU RoHS2, China RoHS2, CoRAP (Community rolling action plan; http://echa.europa. eu/), and the CLP Regulation (classification, labeling, and packaging; http://echa.europa.eu/) lists.

4.2.2 Optimize Material Consumption Using Simulation and Modeling Tools Environmental goals meet some traditional design goals, researching the minimal weight of material, assuming the required functionalities, and minimizing the risks of misconception and manufacturing failures. Simulation and modeling tools optimize design and save time, weight, and energy. Part design is a difficult exercise carried out by skilled technical staffs and leading to technical and economic consequences. Designers, mold makers, and engineers, through simulation setup, modeling, and the resulting interpretation, can easily test

design efficiency and changes linked to wall thickness, gate location, material, geometry, and, more generally, they can evaluate the manufacturability of plastic materials. Software provides simulation and modeling tools for:

• • • •

plastic part design mechanical performance analysis development of preprocessing models injection molding and a wide range of specialized process applications such as gas-assist, coinjection, etc.

• filling, heating, and cooling of plastic materials

• fiber orientation and breakage in plastic part designs

• failure analysis and optimization studies • optimization of noise, vibration, and harshness performance

• curing of thermosets, etc. Software can help:

• Avoid costly mold reworking by ensuring that molds will work right the first time to avoid time-consuming, costly, and unnecessary reworking.

• Optimize feed system design including sprues, runners, and gates to balance runner systems; optimize gate type, size, and location; determine the best runner layout, size, and crosssectional shape.

• Estimate cycle time, clamp tonnage, and shot size by quoting tooling projects quickly and accurately; size the injection molding machine for a given mold, optimize cycle time, and reduce plastics material scrap, etc. Solutions depend on the specific conditions of the real case study, varying with the used grade, part geometry, molding tools, tolerances, and so forth. Consequently, software editors, independent organizations or societies, and plastics producers propose more or less specialized software, services, and guides. Table 4.1 displays some examples without claiming to be exhaustive and without any guarantees.

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Table 4.1 Examples of Computer-Aided Design Software. Society or Brand Name

Website

Abaqus Software (Dassault Syste`mes)

http://www.3ds.com/products-services/simulia/overview/

Altair Engineering

http://www.altair.com

Ansoft (Ansys)

http://www.ansys.com/

Ansys

http://www.ansys.com

Astek

http://www.groupeastek.com

Autodesk

http://www.autodesk.com

Cetim

http://www.cetim.fr/

Cimpa (EADS)

http://www.cimpa.fr

Dassault Syste`mes

http://www.3ds.com

DeltaCad

http://www.deltacad.fr/

ESI

http://www.esi-group.com/

Flowmaster

http://www.mentor.com/products/mechanical/flowmaster-landing/

Genoa

http://www.ascgenoa.com

Hyperworks

http://www.radioss.com/

Intes

http://www.intes.de/

LS-Dyna

http://www.ls-dyna.com/

Marc

http://www.mscsoftware.com/product/marc

Mentor Graphics

http://www.mentor.com

Moldflow

http://www.autodesk.com/products/simulation-moldflow/overview

MSC Software

http://www.mscsoftware.com

Nastran

http://www.mscsoftware.com/product/msc-nastran

Principia

http://www.principia.fr/

Radioss

http://www.radioss.com/

Samtech

http://www.plm.automation.siemens.com/en_us/products/lms/ samtech/index.shtml

Simulia

http://www.3ds.com/products-services/simulia/

Solid Edge

http://www.plm.automation.siemens.com/en_us/products/solid-edge/ index.shtml

SolidWorks

http://www.solidworks.com/

Modeling and simulation adapted to the actual processing method speed up design, trials, and enhance processes. They are broadly used to design parts, molds, and dies allowing to:

• Save material weight • Determine the manufacturability of parts • Avoid potential downstream problems

• Avoid various defects and weaknesses frequently encountered when designing parts and molds such as, for example: • Air traps located in areas that fill last and result in voids and bubbles inside the molded material, incomplete filling (short shot), or surface defects such as blemishes or burn marks. Software eases modifications of the filling pattern by reducing the

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injection speed, enlarging venting, or placing venting at the right place in the mold. • Warpage and sink marks that can be analyzed and reduced to acceptable levels by modification of wall thickness, ribs, bosses, and internal fillets. • Voids caused by localized shrinkage of the material at thick sections without sufficient compensation when the part is cooling. Additional redesigning can avoid these defects. • Weld lines or knit lines and meld lines formed when two melt fronts run into each other or join together. These defects can be improved by redesigning, relocation of holes, or inserts in the part.

• Improve part performance and durability • Rapidly study multiple options, which speeds up and enhances designing

• Reduce the number and, of course, the cost of trials

• Save processing energy • Reduce part cost by optimizing the consumption of the material for a required performance level, etc.

4.2.3 Avoid Nonrenewable Natural Resource Depletion Using Renewable Materials Most plastics are fossil polymers and oil renewal takes far longer than the human time scale. Innovative plastics are produced with biomass or are polymerized from monomers extracted from biomass. Biomass can be used in different manners from all-natural routes to renewable products being copolymerized, alloyed, or mixed with synthetic ones. There are numerous examples such as, for example:

• • • • •

in combination with oil-based monomers, to synthesize conventional polymers. In the real life, natural-sourced levels can range from 20% and less to nearly 100%. For an identical formula, properties of natural and fossil polymers can be slightly different. For dissimilar formulae, properties are generally dissimilar. Compound formulations must be adapted to the used polymer. Fibers have a similar effect in natural and fossil polymers. For some technical properties, natural fibers are not as well performing as glass fibers. Be cautious with some preconceived notions such as “natural polymers are environmentfriendly.” It is not systematic, but depends on the farming and processing conditions. In fact, naturalsourced polymers present advantages concerning crude oil depletion, but other environmental advantages may be doubtful and must be carefully studied, with one pollution type possibly being replaced by another type. Life cycle assessments (LCAs) depend on the methods of production of raw materials, the processing methods, the type of the used energy, logistics and transport issues, among others. The following data are not rules, but are just a few examples. Results are briefly expressed as ratios concerning nonrenewable energy, the greenhouse effect or carbon dioxide (CO2) emission, pollution [of sulfur oxides (SOx), CO2, carbon monoxide (CO), nitrogen oxide (NOx)] emissions, acidification and carcinogenicity indicators, water emissions (phosphates, nitrates), terrestrial ecotoxicity, and human toxicity. Table 4.2 shows examples of the differences between a renewable PE and a fossil PE on the one hand, and a glass and a natural fiber on the other hand. The renewable PE has beneficial energy demand and global warming potential (GWP), but the other items are detrimental from an environmental point of view. The natural fiber has a unique balance of eco-performances except for water pollution with phosphates during the cultivation.

Renewable polymers with synthetic ones Renewable fibers with synthetic matrices Renewable matrices with synthetic fibers Renewable polymers with synthetic additives Renewable additives with synthetic polymers

Finally, it is also possible to extract monomers or oligomers from biomass and use them, alone or

4.2.4 Use Recycled Materials and Waste Most plastics are fossil polymers and recycling saves:

• oil used as a feedstock for the production of virgin polymers

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Table 4.2 Life Cycle Assessment Comparison. LCA Comparison of Renewable PE and Fossil PE PE Fossil

Renewable

Fossil energy demand (MJ/kg PE) 85 15 Global warming potential (kg CO2eq/kg 0 to 1.8 –2 to 0 PE) Acidification potential (kg SO2eq/kg PE) 0.01 0.037 Eutrophication potential (kg PO4eq/kg PE) 0.001 0.018 Photochemical ozone creation potential (kg 0.0006 0.0033 C2H4eq/kg PE) Water consumption (m3/t) ~3.5 ~4500 LCA Comparison of a Natural Fiber and Glass Fiber Glass Fiber Natural Fiber (NF) (GF)

% of Renewable/Fossil 18 –111 370 1800 550 128,571 NF/GF, %

Data

Data

Energy use (MJ/kg)

48.33

3.64

8

COD to water (mg/kg)

18.81

2.27

12

SOx emissions (g/kg)

8.79

1.23

14

BOD to water (mg/kg)

1.75

0.36

21

Particulate matter (g/kg)

1.04

0.24

23

Carbon dioxide emissions (kg/kg)

2.04

0.66

32

NOx emissions (g/kg)

2.93

1.07

37

CO emissions (g/kg)

0.80

0.44

55

Phosphates to water (mg/kg)

43.06

233.6

543

• difference between the energy consumed for the production of virgin polymers and the energy consumed for recycling It is worth noting that:

• By changing the assumptions in environmental studies, results may be different.

• Recycling is a general term for recovering several types of products. So, various studies lead to different figures, but all studies find that recycling is always beneficial from an environmental point of view. For example, Table 4.3 displays some data of:

• Fossil resource depletion • Greenhouse gas (GHG) emissions

• Global warming GWP100 • Acidification • Eutrophication expressed in percent savings versus the use of new PE. Other different data may be found in the literature. In these examples, all savings are higher than 50%. Obviously, there are some limitations to recycled material uses:

• First of all, recycled plastics as all virgin plastics, must obey national, regional, global directives, rules, regulations, and other requirements related to the aimed parts, subsets, and devices. Countries to be considered include those of production, transformation, use, and disposal.

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Table 4.3 Examples of Greenhouse Gas (GHG) Emissions and Fossil Resource Consumption. Saving (%) Fossil Resource Depletion PE, recycled

Fossil resource

90 95

GHG Emissions PE, recycled

GHG emission

67

PP, recycled

GHG emission

68

PS, recycled

GHG emission

75

GWP PE, recycled

Global warming GWP100

73

Acidification PE, recycled

Acidification

84

Eutrophication PE, recycled

Eutrophication

87

GHG, Greenhouse gas; GWP, global warming potential; PE, polyethylene; PP, polypropylene.

• Properties may be more or less different to those of homologous virgin materials requiring thicker part walls or a higher weight of material, thus, leading to heavier parts. Mechanical, physical, optical, thermal, chemical, and dynamic properties may be more or less different. Rheology may affect processing, which mitigates the beneficial effects of recycled materials. Odor, taste, and cosmetic features may be altered.

• In addition, specific requirements concern specifically recycled polymers including limitations of regrind (the least risky form of recycled plastics), but many other rules or regulations exist. Once again, it is the responsibility of the reader to search the ins and outs concerning their own case. Recycled material levels in products are often limited or banned. For example: • Producers suggest the use of 20% 50% of regrind. • Underwriters Laboratories (UL) accepts: 2 No regrind for thermosets, thermoplastic elastomers, and recycled materials. 2 Regrind up to a maximum of 25% by weight with the same grade of virgin

thermoplastic at the same molder facility without further testing. 2 For regrind levels exceeding 25% in the same virgin thermoplastic, UL requires a special evaluation of the relevant performance tests such as mechanical, flammability, and aging tests. For example, a WRAP project demonstrates that rPET can be successfully used in the production of new retail packaging. Product trials were carried out with Coca-Cola Enterprises, Marks and Spencer (M&S), and Boots—in conjunction with plastic recycling specialist Closed Loop London—covering sourcing, production, processing, and testing as well as consumer acceptance. The trials showed that it is possible to package food, beverages, and beauty products in containers containing up to 50% recycled material without compromising performance, storage stability, or visual appeal. The ultimate measure of the project success is that both M&S and Boots are now using rPET in their product lines and Coca-Cola is planning to carry out further trials using rPET. The Coca-Cola trials showed that using rPET reduced the amount of energy needed for bottle manufacture compared to virgin resin, offering a small saving in electricity costs. rPET can be more expensive if bought in small quantities, but once economies of scale arise, the cost of rPET should be near that of virgin PET. In addition to sustainability enhancement, the use of rPET could be a way to manage fluctuations in resin costs.

4.2.5 Avoid Renewable Material Competing With Food or Causing Deforestation Ethanol and other chemicals coming from corn or sugarcane and other edible sources, compete with food crops and lead to deforestation and pollution due to the use of fertilizers and insecticides. Deforestation is leading to the suppression of living absorbers of CO2. New imbalances have appeared concerning agricultural outlets because of higher values of agricultural production of biofuels and other industrial bioproducts, which compete with food crops. In addition, deforestation increases the gain of new arable soils.

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The large extent of the problem can be measured by some round figures:

• Global consumption of polymer is around 300 million tons

• Global consumption of crude oil for polymer production is around 300 million tons

• Global production of vegetable oils is approximately 170 million tons

• Global production of ethanol is approximately 50 million tons

• Global production of natural rubber is about 12 million tons

• Global production of cereals is about 2500 million tons

• Global production of cotton is about 25 million tons If renewable natural raw materials must replace crude oil, it is necessary to double (and more) the production of oils and ethanol with the risk of intensifying the economic imbalance of the agricultural markets satisfying the fundamental needs for the nourishment of humans and livestock. The use of wild plants, waste of agricultural products, and by-products of other industries are good solutions from this point of view.

4.2.6 Design to Facilitate Maintenance, Repair, Reuse, Refurbishment Contrary to widely held ideas, repair, reuse, and refurbishment are implemented by aeronautics, boatbuilding, and other cutting-edge technologies as well as more common sectors such as packaging, automotive, electronics, or construction. A skilled professional can correctly inspect and repair the most-common plastic parts such as piping, geomembranes, trims, inflatable boats and structures, pallets, containers, inner coatings, and bulk bins by welding or gluing patches after the washing and removal of soiled and damaged parts. The intention of any aircraft airframe repair is to return the structure to its original strength and stiffness as well as to keep within prescribed mass balance limitations and aerodynamic requirements. Sandwich structures are repairable. Composite

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repairs may use bolted or bonded patches. Highly skilled professionals are required. More generally speaking, a key to succeed in plastics part repairing is designing devices to properly, safely, and rapidly disassemble the device under consideration, which:

• Allows for the recovery of plastics parts that can be specifically processed, repaired, or replaced

• Enables the disassembly of parts without further damage to the plastic part under consideration on the one hand and for adjacent parts on the other hand.

• Facilitates maintenance, repair, reuse, and refurbishment.

• Provides easy assembly for reconditioned and new parts.

• Reduces costs. Altered plastics parts can be cleaned, repaired, rebuilt, or replaced using general techniques applied to plastics. The following examples are reminders that must be checked before application to the specific case of the reader. Suitable plastics parts and their composites can be machined by almost all the metal or wood machining methods, after some degree of adaptation of the tools and processes. For example, sawing, drilling, turning, milling, tapping, threading, boring, grinding, sanding, polishing, engraving, planning, laser cutting, hyperbar fluid cutting, and so forth. Some precautions must be taken:

• The low thermal conductivity and the decrease of the mechanical characteristics at elevated temperature limit the machining temperature and it is necessary to cool and reduce the tool feed motion.

• Machining damages the surface, destroys coatings, and gelcoats if they exist and, to avoid the risks of later attack, it is sometimes necessary to apply a new (gel)coat after machining.

• For anisotropic parts, machining can be more difficult or impossible in certain directions. Drilling, for example, can only be done perpendicularly to the layers of a composite.

• Carbon and glass fibers are highly abrasive and quickly wear away high-speed steel tools.

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For intensive use, carbide or diamond tools are preferable. Machining is suited for:

• repairing • manufacturing new parts, prototypes, and low outputs of complex parts made from blanks whose mold or manufacturing could be simplified

• correction of parts with tight tolerances • thick parts Plastic boilermaking, similar to metal boilermaking, allows the realization of simple and developable geometrical parts, by cold or hot forming, machining, and assembly by welding (for convenient thermoplastics) or joining of plates, tubes, and blanks. Thermoplastics can be welded (but thermoset resins cannot) by suitable techniques, and suitable plastics can generally be glued by adhesives or, for thermoplastics, by solvents. Boilermaking is commonly used for the repairing of large vessels, piping, cisterns, tanks, tubing, geomembranes, and others from prototypes up to medium outputs thanks to the use of techniques such as welding (not for thermosetting resins), forming, machining, bonding of sheets, slabs, pipes, blanks, and so forth. Workers must be skilled and the labor costs are high. This processing method is also commonly used to build inflatable boats, protective clothing, and inflatable structures, particularly those made of soft polyvinyl chloride (PVC). The implementation requires good knowledge of materials, great experience, and skilled and careful labor. The mechanical characteristics obtained are often higher than 0.8-times those of the starting semifinished products. The advantages of boilermaking include:

• cheap tools • repairing of extremely long and complex tubing and giant parts such as silos, cisterns, etc.

• repairing of single device

Of course, there are some limitations including, among others:

• parts must be rather simple with restricted shapes • choice limited to specific plastics • mechanical performances lower than those of injected parts

• tolerances can be broad • the workers must be skilled and the labor costs are high Cleaning, painting, and decoration allow to decontaminate, refresh, and protect old plastics parts. Cleaning eliminates surface pollution (dust, lint, mold release residues, greases, fingerprints, etc.). Suitable treatments can eliminate the surface oxidation, among others. Two major cleaning processes are used:

• Solvent cleaning, the oldest method, preferably in the vapor phase. There are severe restrictions on the use of solvents, chlorinated ones in particular, and safety, environmental, and fire risks. Convenient solvents, which must be compatible with the substrate (beware of environmental stress cracking for specific plastics), can dissolve oils, greases, and other organic contaminants. Generally, the parts are then dried to vaporize the solvent, but not in some cases. In these cases, the swelling of the polymer favors the adsorption of primers. Solvents can be applied by: • vapor degreasing • dipping in a simple or ultrasonic bath • wiping, etc.

• Aqueous cleaning in which the application of aqueous acidic or alkaline detergent solutions is followed by normal and deionized water rinses. Strong detergents dissolve greases, oils, and possibly oxides. It is necessary to rinse thoroughly to avoid later attacks. Functional properties must be checked after treatment. Many plastic parts can be painted to:

• improve aesthetics • differentiate productions competitors

from

those

of

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• differentiate parts for safety applications • produce a special effect determined by styling or design

• improve durability, the paint film protecting the plastic from the environment including UV, but excluding heat As for metals, many painted parts have to achieve a color match with other parts. Plastic painting is similar to the process for metals, apart from some particularities of plastics and notably thermoplastics:

• Sensitivity to heat, which can cause physical and chemical alterations during paint drying and hardening.

• Sensitivity to solvents. • Low surface tension of plastics. Wetting of the surface is more difficult as the surface tension decreases. Surface treatments can improve the surface tension and the wettability.

• Smoothness of the surfaces. • Insulating properties limiting or making the use of electrical processes more difficult.

• Migration of additives such as plasticizers, internal mold release agents, etc. Painting defects can appear a long time after painting.

• External mold release agent residues. Obviously, all precautions must be taken concerning health and safety according to laws and regulations including local ones. Surface treatments may be necessary before painting and decoration in order to:

• physically change the surface to permit the

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These processes are aggressive and can be harmful, hazardous, and environment-damaging, requiring safety precautions in respect of local regulations. Some of them are described here as examples: Abrasion: To abrade the surface to eliminate oxides, among others, by mechanical means such as brushing, sanding, blasting, sandpapering, and so forth. Chemical pickling: Chemicals are used to eliminate oxides without etching the bulk material. Chemical etching: Chemicals are used to eliminate oxides, to attack the surface layer of the material, and/or to create reactive sites. The processes depend on the plastics. The most commonly used are:

• Chromic or sulfochromic acid etching, for polyolefins, polystyrene, acrylonitrile butadiene styrene (ABS), polyacetal, polyphenylene ether, etc. These treatments have two effects: • forming surface irregularities for a mechanical anchorage. • creating reactive sites such as hydroxyl, carbonyl, carboxylic, sulfuryl, etc.

• Oxidation by flame treatment for polyolefins: exposure to a flame of methane, propane, or butane and oxygen in excess for a short time (less than 0.2 s) to create oxidation and reactive sites such as hydroxyl, carbonyl, carboxyl, etc. Particularly used for PE and polypropylene (PP).

• Oxidation by ultra-hot-air treatment for polyolefins: exposure to a blast of hot air (roughly 500°C) for a short time to oxidize the surface and create reactive sites such as hydroxyl, carbonyl, carboxyl, amides, etc. Rather similar to flame treatment, it is particularly used for PE and PP.

• Sodium naphthalene etching or Tetra Etch for

• chemically change the surface material to cre-

polytetrafluoroethylene (PTFE): improves the surface roughness and creates unsaturated bonds and carbonyl and carboxyl groups.

ate active chemical sites or a layer of a new material

• Surface grafting of chemical species to

mechanical anchorage of the paint

• chemically change the surface material to enhance the wettability Some processes are usable for metals and polymers; others are specific to polymers or to metals.

improve the chemical bonding: this can be helped by simultaneous gamma or other irradiations. It is particularly used for PE.

• The attack must be superficial and the parts must be thoroughly rinsed to avoid subsequent degradation.

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• Corona discharge: discharge of a high frequency (10 20 kHz), high voltage (e.g., 20 kV), and an alternating current in air at atmospheric pressure. This treatment has two effects: • forming surface irregularities for a mechanical anchorage • creating reactive sites such as hydroxyl, carbonyl, carboxylic, hydroperoxide, aldehyde, ether, ester, etc. This process is not suitable for parts with pronounced three-dimensional (3D) shapes. On the other hand, it is well suited to films and sheets. The corona discharge generates ozone that can harshly attack some polymers.

• Plasma treatment: discharge of a high frequency (kHz to GHz), alternating current in gaseous argon, helium, nitrogen, oxygen, or CF4, NH3, etc., under low pressure. The results depend on the gas used. There are several theories on its effects: surface cross-linking, creation of reactive sites, chain scissions, etc. Plasma is used to treat PE, saturated polyesters, PTFE, etc.

• Metallization can be applied by batch or continuous vacuum metallizing, sputtering, and electroplating.

• UV treatment: exposure to high-intensity UV light promotes chain scissions, cross-linking, and reactive site formation. It is particularly used for PE. The choice of the right paint or decoration material depends on:

• the chemical and physical compatibility with the plastic

• the possibility of obtaining the desired decorative effect

• the preservation of all functional properties during the entire service life

• the suitability for the chosen application technique

• the ability of the plastics to be painted to withstand the heat or UV radiation needed for any subsequent paint curing All processes use chemicals, radiations, heat, and/or electrical treatments, among others, needing trials, testing, and aging before industrialization.

Some standards are being developed for the repair and reuse of used or wasted devices.

4.2.7 Use Reliable Materials and Trustworthy Providers Plastics parts are designed with defined plastics grades and long and costly studies and trials are to be redone if materials or providers are changed. “Equivalent” plastics grades may be “similar” or “approximately the same,” but may differ on specific features and may lead to noncompliant parts or manufacturing troubles. Unsteady raw materials and unreliable providers may lead to faulty quality, waste increase, lower productivity, higher costs, longer delivery times, and more generally, dissatisfaction of the customer.

4.3 Minimize Manufacturing Impact on the Environment Each step of manufacturing consumes energy and resources and generates waste and pollution. Processing methods can mitigate energy consumption and reduce waste and pollution generation. Organizational strategies and careful selection of materials help to minimize these drawbacks. Manufacturing may minimize the environmental impact in multiple ways including:

• Mitigation of waste • Energy management • Integration of manufacturing steps using direct mixing, comolding, overmolding, in-line process, workcells, etc.

• Reduction of the number of subparts • Reduction of the number of used materials • Suppression or reduction of hazardous emissions, etc. For that, manufacturing can capitalize on:

• Energy-efficient machines • Use of compounds that are less energy demanding

• Use of grades that are easy to process • Digitalization and software solutions at all levels

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• Energy saving and green energy use • Innovative processing methods • Avoid, trap, treat, and decontaminate hazardous emissions Some examples, among numerous others, include:

• Mixing one or several solid polymers and additives generally absorbs a high energy more so as the viscosity is higher and dispersion is difficult. Continuous mixing and integration in-line are smart ways to reduce energy consumption.

• Drying hygroscopic polymers before processing requires high energy. A careful management of raw materials can avoid humidity absorption and drying, which saves energy and pollution. Energy saving can result from new drying processes.

• Molding also needs a high energy for pressure increase, heating, cooling, and mechanical work. Energy consumption depends on rheology and the temperatures of the injected polymer and the mold. Energy saving can result from new heating and cooling methods.

• Optimization of running processes including design modifications of machines such as a better efficiency of hydraulic pressure transmission through a reduction of pressure loss in hydraulic circuits, optimization of timing works and valve characteristics, advanced direct-drive technology, new synchronous motors, and a decrease of sliding resistance can bring energy savings of interest, for example, 12% for a new injection machine model compared with the former model of the same class.

• Curing, which is only necessary for elastomers, thermosets, and some thermoplastics, can consume a lot of energy for heating. Stansfield (2006) compares UV and thermal curing of a given coating and claims a cycle time divided by 7 9, a 66% energy saving, and a cost saving of 40% for the UV curing.

• Minimizing wastes saves good products and reduces energy consumption for waste disposal. From a pollution and energy point of view, it is clear that wastes are important, all the more so as the production step is advanced.

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The production energy accumulates at each step and the percentage of right goods decreases. Moreover, the waste disposal will need extra energy.

• Change the processing method: Dawson et al. (2002) compare hydraulic and electric machines for the injection molding of a thermoplastic and claim an 80% energy saving when using the electric machine. SUMITOMO (Model Change of Main Hydraulic Type Molding Machines “FN Series,” March 2005) quotes a 30% 60% energy savings through the optimization of a model or by changing from a hydraulic to an electric machine.

• Change the compound. Special grades (Easy flow, Ultraflow, Easy Processing, etc.,) are the simplest solutions, but it is also possible to modify recipes. For example, Lewan et al. (2004) study, for the extrusion of an EPDM, the simultaneous effects of recipe change, extrusion temperatures, and scroll speed. They claim energy savings of up to 40% and cost savings of up to 66% with a low temperature curing compound extruded and high scroll speeds. Additives enhancing processing can be specific “processing aids” or other additives such as lubricants, plasticizers, soaps and other fatty acid derivatives, mineral additives, organic inorganic additives, and proprietary recipes, etc.

4.3.1 Invest in Efficient Machines Efficient machines can be described by a few words, namely save energy, waste, productivity, time, money, and so forth, due to their performing kinematics chains, higher performances, shorter cycle times, lower energy consumption, higher quality level, maximum precision, extended software support, modular design, integration, and innovative techniques.

4.3.1.1 Injection Machines: A Critical Choice Between Hydraulic, Electric, and Hybrid Models There is not a universal answer to this tricky dilemma. Each solution has its benefits and limitations depending on the part to be produced and the general context. The injection machine market confirms the interest of the three solutions, each one

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being of interest for specific cases. The information listed here is general and may be unsuitable for certain cases.

• Disadvantages: • Lower clamp forces • Higher initial cost • Maintenance can be more expensive

Hydraulic Injection Molding Machines

Hydraulic systems are generally used for thickwalled parts leading to long hold times. The benefits over all-electric (AE) machines may include:

• Sustainability advantages: longer service life, which is good for sustainability

• Other advantages: • Greater clamp force for large parts, larger shot size with better ejection capability

• Better injection rates • Lower initial purchase price

• Sustainability disadvantages: • Hydraulic machines consume large amounts of energy even when idle, which is damaging from a sustainability point of view. Innovative designs can moderate this issue • Possibly less precise than AE presses, but innovative control systems can mitigate this issue

• Other disadvantages: • Noisier than electric versions Electric Injection Molding Machines

The benefits over hydraulic machines may include:

• Sustainability advantages: • Energy savings of between 25% and 50% and even up to 70% • Low waste rates due to precision and repeatability • Shorter start-up time and up to 20% faster cycles

• Other advantages include: • Quieter operation; reduced motor noise below 70 dB

• Higher rapid injection speeds and faster clamp motion • High precision, which is useful for small- to medium-sized parts • No risk of oil contamination, which is useful for medical products, electronics, and cleanroom applications

Hybrid Injection Molding Machines

Hybrid injection molding machines aim to benefit from the advantages of electric and hydraulic machines while avoiding their disadvantages.

• Sustainability advantages: • Energy savings • Low wastes due to precision and repeatability • Other advantages include: • High clamping force of hydraulic machines • Reduced noise of electric machines This allows for better performance for both thinand thick-walled parts. These machines have become increasingly popular over the past few years due to their efficiency and ease of use. Table 4.4 lists, without claiming to be exhaustive and without any guarantees, some examples of builders of injection machines proposing several solutions.

4.3.1.2 Peripherals and Retrofitting Solutions Peripherals may contribute to energy savings, carbon footprint reduction, better sustainability, and also cost savings. Here are a few examples:

• Quick-change systems, especially for short runs, change, and downtimes can erase the intrinsic productivity of the used injection machine because of long idle times.

• Double tempering circuit for short cycles and enhanced quality, for example, the claimed advantages of BFMOLD (WITTMANN BATTENFELD GmbH) include higher productivity through a reduction in cycle times, improvement in surface quality, and less distortion.

• Energy saving solutions for old machines; machine builders propose energy saving solutions for new and used machines. Benefits from a sustainability point of view may include one or more of these features:

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Table 4.4 Examples of Injection Machine Builders. Arburg

www.arburg.com

Asian Plastic Machinery (Chen Hsong Group)

http://www.asianplastic.com.tw/en/products.html

ATEC Plastics

http://atec.lt/

Battenfeld

www.battenfeld-imt.com

Battenfeld-Gloucester

www.cms.battenfeld.com

Billion

www.billion.fr

BMB

http://www.bmb-spa.com/

Borche

http://www.borche.co.uk/

Boy

www.drboy.de

Chen Hsong

http://chenhsong.com/

Coperion

www.coperion.com

Demag

www.sumitomo-demag.com

Dongshin Hydraulics

https://dong-shin.en.ec21.com/

ENAIVIV Machinery Industrial

http://www.enaiviv.com.tw/page-1.html

Engel

www.engelglobal.com

Fanuc

www.fanuc.de

Ferromatik Milacron

www.ferromatik.com

FCS—FU CHUN SHIN Machinery

http://www.fcs.com.tw/eng/

Haitian International Holdings

http://www.haitianinter.com/en/products/

HUARONG Plastic Machinery

http://www.huarong.com.tw/page/features/en/Hydraulic

Husky

www.husky.ca

HW.Tech

www.hwtech.de

HWA CHIN Machinery

http://www.hwa-chin.com/hcse-Plastic-Injection-Molding.html

IMS Deltamatic (Turra)

http://www.omfturra.com/turra/machine.php?lng 5 eng

JSW—Japan Steel Works

http://www.jsw.co.jp/en/products/injection_molding/index.html

Jon Wai Machinery Works

http://www.jonwai.com/

JSW

www.farpi.fr

Shanghai Kawaguchi Machinery Co.

http://kawaguchi.company.weiku.com/

KING’S Machinery & Engineering Corp

http://www.injection.com.tw/en/index.html

KraussMaffei Berstorff

www.kraussmaffei.com

L.K. Machinery

https://www.lktechnology.com/en/industry.php?id 5 3

Lien Fa Injection Machinery

https://www.lienfa.com.tw/en/menu_pro.htm

Mateu y Sole

http://www.mateusole.net/ingles/inyectoras/astron.asp

MEIKI Co.

http://www.meiki-ss.co.jp/eng/mac/main.html

Milacron

https://www.milacron.com/

Miniature Plastic Molding

http://www.minijector.com/

Mitsubishi

www.mhiinj.com (Continued )

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Table 4.4 Examples of Injection Machine Builders.—Cont’d Multiplas Enginery

http://www.multiplas-tw.com/en/product.html

Negri Bossi

www.negribossi.com

Netstal

www.netstal.com

Niigata Machine Techno Company

http://n-mtec.com/en/

NINGBO HAITAI Plastic machinery

http://www.haitai-machine.com/

Nissei

www.nisseijushi.co.jpwww.nisseiamerica.com

OIMA

http://www.oima.it/en-US/Products.aspx? idC 5 61675&LN 5 en-US

Presma

http://www.presma.it/english/index1.html

Romi

http://www.romi.com/en/categoria/plastic-processingmachines-en/

SDT Sodick PlusTech

en.plustech.co.jp

Smargon Plastic Machinery

http://www.smargon.com/Product_18.html

Stork

www.storkspm.com

Sumitomo

www.sumitomopm.comwww.shi.co.jp/plastics

Sumitomo Demag

www.sumitomo-demag.com

Tederic Machinery

http://tederic-cn.com/solutioninfo.aspx?nid 5 170&id 5 17

Toshiba

www.toshiba-machine.co.jp

Toyo Machinery & Metal

http://www.toyo-mm.co.jp/english/pro/

Turra (IMS Deltamatic Group)

http://www.omfturra.com/turra/machine.php?lng 5 eng

U-MHI Platech

http://www.u-mhipt.co.jp/injec_e/

Wabash MPI

http://www.wabashmpi.com/

Welltec Machinery

http://www.welltec.com.hk/product/

Windsor

www.farpi.fr

Italtech (Wintal)

http://www.italtech.it/

Wittmann Battenfeld

http://www.wittmann-group.com/

Woojin Plaimm

http://www.woojinplaimm.com/global/en/product/pd_list.php

YIZUMI Group

http://www.yizumi.com/en/

YuhDak Machinery

http://www.yuhdak.com/en/index.html

• • • • •

Reduced CO2 footprint

Drive energy

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248

258

Cooling and filter motor

283

270

283

Reduced cooling water consumption Reduced heat emission

Total reduction

223

241

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Reduced energy consumption

Extended oil durability, etc.

Other benefits include the fact that, generally, new machines generate lower noise levels and higher productivities. For example, Engel proposes its ecodriveR system claiming, for three different molding cases, energy savings (%) on the order of:

For material handling, according to suitable cases, a central conveying system with vacuum pumps, piping, and so forth, may be the source of significant savings by using energy-efficient motors such as NEMA Premium energy efficiency motors (http://www.nema. org). Conair (http://www.conairgroup.com/) claims

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they cost 10% 15% more than common motors, but are energy efficient when annual operations exceed 2000 hours. For resin drying, the first measure to be applied is a careful storage of resins. If drying is necessary, dryers may also be a significant source of savings if using up-to-date designs. For instance, Conair claims 35% energy savings with its Carousel Plus used to dry an undefined resin. For granulation, Piovan (http://www.piovan.com/ en/the-new-line-of-granulators) proposes energy saving systems that intervene in certain cases to manage the idle periods and optimize consumption. The new range of Piovan high-efficiency granulators guarantees energy savings between 15% and 35% depending on the application. Sidel’s patented eQuick Change system, available as an option on all the latest generations of Sidel blow molders, allows ultrafast connection of the cooling circuit to the mold neck with just one click. All of the piping that feeds the neck circuits with water and the electrical cables for the temperature probes are connected and disconnected in less than five seconds. This leads to a 50%-time savings with respect to the previous quick-change version. In addition to the few quoted examples, many other solutions are proposed by many other machine builders.

4.3.2 Favor Less EnergyDemanding Compounds There are numerous examples of grades of all polymer families designed to improve flow and processability. Some examples include Easy flow, Ultraflow, Easy Processing, among others, grades, without claiming to be exhaustive:

• Akulon Ultraflow (DSM Engineering Plastics https://www.dsm.com/products/akulon/en_US/ cases/akulon-ultraflow.html) is claimed to be able to deliver: • lower energy consumption and, therefore, less pollution and possibly less resource depletion • longer lifetime for machine and molds due to lower mold pressure, which is good for the environment • lower cycle times with a 40% saving in production time compared to other polyamides

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• lower investment in machine and molds • shorter cooling time • Covestro, formerly Bayer MaterialScience, proposes Bayblend, fire retardant blends of ABS and polycarbonate (PC) having a flowability at 260°C between 105 and 195 measured with the same method.

• Solvay Advanced Polymers markets Amodel HFZ A-4133L, a high-flow grade of its Amodel polyphthalamide family. In addition, it is claimed to offer improved mechanical properties versus most high-performance polymers as well as being a cost-effective alternative.

• DuPont Engineering Polymers markets its Zytel HTN53G50LRHF, a stiff superstructural material reinforced with 50% glass fiber having a flow 20% higher than comparable grades and similar high performances. This grade increases opportunities for complex, thinwalled part designs and improves molding productivity. Potential applications cover a wide range of components for automotive, industrial, and consumer goods.

• Lumicene M3427, a Total eco-solution, is a metallocene catalyzed PE based on Total’s proprietary catalyst technology. It provides artificial grass yarns with a lifetime at least 50% longer compared to artificial grass yarn made of octene-based linear low-density PE (LLDPE) that is considered to be the reference on the European market. The yarn increased longevity leads to an annual reduction of CO2 emissions and energy consumption over the lifetime.

• Ultradur High Speed, BASF’s new especially easy-flowing polybutylene terephthalate (PBT), is the company’s first engineering plastic to receive the so-called eco-efficiency label. Studies have demonstrated that products made of Ultradur High Speed are considerably more eco-efficient than products made of a standard PBT. The good flowability of this new material helps to save energy, thus, protecting the environment. Note: The eco-efficiency label is awarded to products or methods that perform better from an environmental and financial standpoint than comparable products or methods.

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An Eco-Efficiency Analysis is certified by the ¨ V). German Technical Control Board (TU

• Manufacturing execution system (MES) con-

• Dow Europe GmbH introduces an enhanced

• Enterprise resource planning (ERP) software

LLDPE resin for high-throughput lamination and protective film applications. XZ 89446.00 LLDPE resin is a higher alpha copolymer specifically designed for high conversion rate processability and improved sealability for blown and cast films. According to the producer, the resin can be used alone or in blends and offers a 2 g/ 10 minutes melt flow index (MFI: 190°C/ 2.16 kg) and a density of 0.916 g/cm3. Its high-throughput processability can offer some advantages when compared to similar MFI resins including equivalent metallocene LLDPE resins. The polymer design of XZ 89446.00 offers several environmental advantages including: • lower energy consumption by enabling processing at lower temperatures • reduction of wear for conversion equipment as a result of processing with lower extruder pressures • higher throughput efficiency with subsequent environmental advantages For blown film lamination applications, XZ 89446.00 can provide improved seal performance with low seal and low hot-tack initiation temperatures. For use in protective film applications such as films used on glass, plastic sheets, appliances, or consumer electronics products, the resin’s higher melt flow offers smoother, flatter film surfaces with good optics, continuous high-quality processing (low gels), and good chemical resistance.

developed for multinational, small, or mediumsized businesses

There are many other examples and high research activity continuously brings new products to the market.

4.3.3 Digitalization and Software Solutions Digitalization and software solutions can be implemented at all manufacturing steps including:

• Embedded solutions integrated to smart or intelligent machines

trolling the activities occurring on a shop floor

4.3.3.1 Smart or Intelligent Machines Shot by shot, intelligent software systems check, evaluate, and compensate for fluctuations of a defined parameter due to material quality and environment variations of a given injection molding machine. This is fully automatic in real-time. For example, the ENGEL iQ weight control software:

• detects and monitors the injected volume and viscosity

• controls the injected melt volume in real-time • automatically corrects the holding pressure Thus weight variations can be mitigated and outof-specification parts are dramatically reduced improving the process stability. In addition, in the case of a restart after a downtime production, the software reduces the level of out-of-specification parts. At K 2019, ENGEL is exhibiting its iQ weight control intelligent assistance system for injection molding processes with a recycled material application, making the great potential that inject 4.0 offers for the circular economy a reality. That is only one example and many other machine builders propose similar systems. In ultimate steps, automation leads to sophisticated and complete production cells ensuring part and insert handling, labeling, transfer, removal, packaging, assembly, and finishing treatments as diversified as the insertion and encapsulation of a sensor or the magnetization of magnetic discs. Examples abound with robots and other appliances that are fully integrated to the control software of injection machines. Production cells are also developing, and without claiming to be exhaustive, a few examples include:

• Lids with printed labels served on the Ferromatik Milacron solution. The complete production cell including in-mold-labeling, quality control, part stacking, and packaging demonstrates the production of labeled

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rectangular lids. After part removal, the lids are transported on a conveyor belt where they are subject to visual quality control. Finally, the lids are stacked and packed in boxes, each containing 1216 lids.

• Arburg (https://www.arburg.com/en/) presents a three-component ALLROUNDER model used to demonstrate the production of a threepart rotary encoder in a single production step. The SELOGICA control system guarantees harmonization of all components.

• Netstal (https://www.netstal.com/) proposes its ELION 2200 using a 64-imp mold to inject closures of high-density polyethylene (HDPE). For quality control purposes, all parts pass through a visual inspection station immediately after molding.

4.3.3.2 Manufacturing Execution System Software MES controls the activities occurring on a shop floor. It begins with the orders from customers. The manufacturing resource planning (MRP) system controls the planning resources and then the manufacturing process in the most effective, low cost, convenient, and high-quality way possible. The MES software receives data and information in real time from robots, sensors, machines, peripherals, machine operators, and other authorized employees. The MES software takes controls into consideration and proposes solutions to critical facts taking place at a plant shop floor including, but not limited to:

• • • • • • • • • • • •

Machine breakdowns Labor absenteeism Setup times Changes to minimize setup times Processing times Changes to minimize process times Quality problems Availability of quality resources Alternative work plans Alternative parts list Changing delivery dates Availability of transport

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The MES software provides the right tools and critical information to the shop floor personnel, allowing for production to be optimized. An efficient MES operates on a real-time basis, allowing an immediate reaction to slow or sharp variance on the shop floor, poor quality, and late deliveries. The offered functions should be at a minimum:

• • • • • • • • • • • • •

Resource allocation and status Operation scheduling Dispatching production unit Document control Data collection Labor management Quality management Process management Exception management Maintenance Transport management Product tracking and traceability Performance analysis

More sophisticated MES can include, without claiming to be exhaustive:

• • • • • • • • • • • • • • • • • •

Planning system interface Visual scheduler eProduction Shop floor control Statistical process control (SPC) Inventory tracking and management Material movement management Support functions of MES Time and attendance Payroll Human resources Job cost Performance management Document management Product data management Bill of material Engineering change control Supply chain management

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The goal of a MES is to improve productivity, reduce cycle time, reduce total execution time for each order, improve quality, reduce scraps and lower end costs, and deliver products timeously. Of course, reduction of waste and energy consumption improve the sustainability. Table 4.5 displays examples of MES software. Some software solutions are sold as base and require the purchase of modules and add-ons. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal or professional advice. The presence or absence of a company is not an indication of quality and many suitable companies are not quoted. Some software solutions are claimed to be special for plastics, but others are general and may be used after some adaptations if necessary. Some plastics machinery builders work with MES software editors. The range of MES software is broad and the

choice must take into consideration the size, the structure of the company, the actual needs and other parameters of the company, and the compatibility with the hardware and other software systems. MESs are increasingly integrated with ERP software suites (see Fig. 4.3). By integrating an MES with ERP software, factory managers can be proactive about ensuring the delivery of quality products in a timely, cost-effective manner. Fig. 4.3 displays the integration of several MESs related to several machines or workshops to an ERP.

4.3.3.3 Enterprise Resource Planning Software ERP software developed for multinational, small, or medium-sized businesses, ready or not

Table 4.5 Examples of Manufacturing Execution System (MES) Software. Aptean

http://www.aptean.com/solutions/application/mes-solutions

BMS Vision, PlantMaster

http://www.visionbms.com/products/our-products/plastics

Bodet Osys

http://www.bodet-osys.com/en/applications/plastics.html

Epicor Mattec MES

http://www.epicor.com/manufacturing/injection-molding-software.aspx

Grass, COAGO MES

http://www.grass-gmbh.de/en/coago-mes-en.html

Honeywell

https://www.honeywellprocess.com/en-US/explore/solutions/industry-solutions/ chemicals/plastics-fibers-and-flat-sheets/Pages/manufacturing-executionsystems.aspx

IQMS

http://www.iqms.com/manufacturing-software/mes-software.html

LeaderMES

http://www.leadermes.com/?gclid 5 COvB_pWPwdECFdRAGwod4XoAbg

Lighthouse

https://www.lighthousesystems.com/industries/plastics-and-rubber

MPDV, Hydra-forplastics

https://www.mpdv.com/fr/solutions/hydra-solutions-pour-tous-les-secteursindustriels/hydra-for-plastics

Ordinal, Coox

http://www.ordinal.fr/en.htm

Plex Manufacturing Cloud

https://www.plex.com/

Pronto Xi

https://www.pronto.net/

SisTrade

http://www.sistrade.com/en/Markets/extrusion-industry.htm

Six S Partners Inc

http://sixspartners.com/industry/plastics-software/

Southern Indiana Plastics, Inc.

http://www.siplastics.com/mattec-system.html

SysconPantStar

http://plantstar.org/

Team-Con

http://www.team-con.de/en/industries/plastic-sheet-production.html

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ERP

MES

MES

MES

Machine 1

Machine 2

Machine X

Peripherals

Peripherals

Peripherals

Figure 4.3 Software architecture.

for the mobile business, cloud, SaaS (Software as a Service), among others, offer one or more of these functionalities, without claiming to be exhaustive:

• • • • •

Accounting

• • • • • • • • • • • • • • • • •

Distribution

Asset management Business intelligence Central management system Customer relationship management and contact management Documents e-Commerce and web

• • • •

Service Supply chain Time tracking Training management

The ERP software may be:

• Installed on a computer of the company, the license giving the user the right to use the software in the licensed environment

• installed at a data center or “hosting center” • deployed on a cloud platform, similarly to hosting, but the servers are virtualized

• SaaS sold on a rental model, typically a given amount of dollars per month per user.

Fixed asset management Human resources Integrated accounting Inventory Invoices Logistics Manufacturing Marketplace and e-commerce Payroll solutions Practice management Professional services management Purchasing Sales Scheduling

Table 4.6 displays examples of ERP software sources. Some are sold as base and require the purchase of modules and add-ons. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal or professional advice. The presence or absence of a company is not an indication of quality and many suitable companies are not quoted. Some software solutions are claimed to be special for plastics, but others are general and may be used after some adaptations if necessary. Some plastics machinery builders work with ERP software editors. The range of ERP software is broad and the choice must take into consideration the size, the structure of the company, the actual needs and other parameters of the company, and the compatibility with the hardware and other software.

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Table 4.6 Examples of Enterprise Resource Planning (ERP) Software. abas ERP

http://abas-erp.com/en/

Aquilon ERP

https://aquilonsoftware.com/

BatchMaster ERP B1

http://www.batchmaster.com/

BatchMaster Manufacturing

http://www.batchmaster.com/

BizAutomation.com

http://www.bizautomation.com/

Carillon ERP

http://www.carillonfinancials.com/

Central ERP

http://www.erpcentral.co.uk/

Composity

http://composity.com/products/cms

Datacor Chempax

http://www.datacor.com/chempax

DEACOM ERP

https://deacom.com/

DTR ERP Aptean

http://www.aptean.com/solutions/business-function/manufacturing

EnterpriseIQ

http://www.iqms.com/products/erp/

Epicor ERP

http://www.epicor.com/manufacturing/injection-molding-software.aspx

Exact Globe Next

https://www.exact.com/

Global Shop Solutions

http://www.globalshopsolutions.com/erp-software-for-manufacturing

Infor M3

http://www.infor.com/product-summary/erp/m3/

Intact iQ

http://www.intactsoftware.com/engineering/

IQMS

http://www.iqms.com/manufacturing-software/

kpi.com

https://www.kpi.com/

Microsoft Dynamics AX

https://www.microsoft.com/en-us/dynamics365/ax-overview

Microsoft Dynamics NAV

https://www.microsoft.com/en-us/dynamics365/nav-overview

MIE Trak Pro

http://www.mie-solutions.com/

NolaPro

http://www.nolapro.com/

OpenPro

http://openpro.com/

Oracle JD Edwards

http://www.oracle.com/us/products/applications/jd-edwards-enterpriseone/ industry-focus/index.html

Plex Manufacturing Cloud

https://www.plex.com/

S2K Enterprise

http://www.vai.net/solutions/s2k-enterprise.html

ProcessPro Premier

http://www.processproerp.com/

Pronto Xi

https://www.pronto.net/

Ramco ERP on Cloud

http://www.ramco.com/erp-suite/

Sage ERP X3

http://www.sage.com/us/erp/sage-x3

SAP Business All-In-One

http://www.sap.com/product/enterprise-management/business-all-in-one.html

SYSPRO

https://www.syspro.com/

T.FAT ERP

http://www.suchansoftware.com/iGreen_TFAT_ERP.html

VISCO

http://viscosoftware.com/solutions/erp-software-for-importers-benefits/

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4.3.3.4 Software Solutions Integrated by Plastics Machinery Providers Integrated software solutions, provided that the providers are well known, can bring:

• Reduced costs; the total cost can be substan-

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maintenance, and, more generally, information transparency.

• The development of intuitive, realistic, easyto-use, striking, real-time interfaces, graphics, synopsis, visualization by aggregating and treating information comprehensibly for making informed decisions at any level and solving urgent problems at the floor shop level.

tially reduced and the invoice amount for the selected machinery provider is increased, integrating the number of peripherals, software, etc., which improves possibilities of bargaining.

• Remote services, technical assistance, trouble-

• Delivery time can be shortened and is less haz-

• End goals including savings in money, time,

ardous if there is only one supplier.

• Integration of business eases communication, and so, increases efficiency with some “gray areas” disappearing and many issues being handled more effectively.

• Supply chain consolidation where the supplier develops an increased understanding of the buyer’s needs. The reduction in supplier numbers creates a more streamlined and efficient supply chain. This can reduce costs through economies of scale and leverage.

• Buyers benefit from the comprehensive knowledge of the machinery provider, on condition this one is at the cutting edge of all the implied technologies. Often, suppliers can help buyers thanks to their broad experience of product design, technology, and ideas. Machine, complete line, peripheral builders, and vendors offer one or more of the features listed below inspired by industry 4.0 philosophy:

• The use of machines, devices, sensors, actuators, software, and workers to harvest, treat, and store a maximum of useful data thanks to connectivity, interoperability, real-time communication via the Internet of Things, mobiles, etc.

• The use of robots doing or collaborating with workers to automate the maximum number of tasks that are hard, expensive, unpleasant, too exhausting, or unsafe for human workers.

• The automation of all suitable tasks, processes, startups, shutdowns, control, monitoring, reporting, administrative, planning, scheduling, decision making, alarms, warnings, preventive

shooting, preventive maintenance supporting customers quickly and cheaply. labor and improvement of productivity and customer satisfaction. The user must select a solution depending on their own case taking into account their actual and forecastable needs, the factory context, habits, knowledge, external context, financial possibilities, brand image, and so forth.

• Communication, connectivity, human interface Of course, the prime requirement is to communicate quickly, easily, and efficiently with operators, workers, managers, and other humans. Also, machines must communicate with each other, and with other auxiliary equipment, other lines, other software, and, more generally, other stakeholders including the after-sales service department in case of a problem, providers, customers, and so forth. Of course, confidentiality and access to data must be secured. Control and quality data, process parameters, and design data can be shared thanks to communicating software. For example, sound transmission loss (STL) or WRL files from any 3D computer-aided design (CAD) application can be transformed into print-ready 3D models with color, material, and support placement information. Data communicated by sensors must autonomously control the processes. Communication can be assumed by all means, specialized or common including internet, Ethernet, and other networks via mobile phones, tablets, PCs, browsers, among others. Quick response (QR) code and smartphone apps help identify spare parts, reliably and quickly. Radio frequency identification (RFID)

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access control systems enable easy identification. Required spare parts can be identified reliably and in integrated online stores, they can then be checked for their availability, and then ordered. Future machines, devices, hardware, and software must be integrated without any problems. e-Services and remote services and resources must communicate clearly and intuitively. Alarms for process and production violations and quality deviations must be communicated quickly, clearly, and globally by email messaging or other exchange procedures with the operators. Modern user interface recalls familiar operating concepts of tablets or cell phones and offers multitouch zoom as well as move and slide functions. View comparisons and process information must display a complete efficiency overview of machines, lines, and process status of the entire line at a glance.

• Data acquisition, control, monitoring Data acquisition depends on sensors, import from other central computer or machine software, human keyboard input, peripheral devices, among others, needing compatibility and communication means. Sensors can be standard or customized providing suitable compatibility and connectivity. Data must be compiled in real-time, treated, analyzed, and stored for reuse allowing to achieve technical works such as, for example:

• To monitor in real time the concerned machine or several lines or other devices

• To monitor line flow and maintain stability • To control specifications for various condition settings

• Decision making • Monitoring productivity • Evaluating actual data and various service functions including, for example, webcam applications

• Evaluate

process trends and modify suitable parameters before machine or line failure

• Data statistical results allowing quality judgments and acceptance criteria to be built

• Alarm workers and managers if necessary, induce maintenance operations and quality control

• Build processes for future productions, presetting conditions

• Use of standard data provided with the machine or line

• Monitoring and controlling all pre- and postmolding process parameters opening the way to efficiency

• Monitoring of machine status, production status, molding cycles, cycle time repeatability, and specification conformity

• SPC charting for both process variables and dimensional measurements, etc. Data are also used for other works as diverse as the following. Energy Monitoring

The Energy Monitoring Module allows for energy usage to be tracked and for opportunities for increasing efficiency and reducing cost to be identified. It is possible to calculate energy diagrams over time and on the basis of freely selectable production parameters as well. This, in turn, makes it possible to find an operating point where the line can be run with optimal resource efficiency in terms of both material and energy consumption. Comparison of actual energy and model energy use allows for the identification of inefficiencies and areas for improvement and cost optimization. Troubleshooting

Troubleshooting can be processed in-house using collected data, specifications, and suitable software or can be remote processed using e-services of the builder or vendor. Historical data, actual data, automated countermeasures, and equipment upgrading reduce possible slowdowns, downtimes, scraps, consumed energy, and raw materials. Some examples, among many others, are quoted here. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal or professional advice. The presence or absence of a company is not an indication of quality and many suitable companies are not quoted. For each company, quoted facts and information are fragmentary and it is the responsibility

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of the reader to study more deeply this tricky file, which partly determines the future of the organization. The information provide here is claimed by providers. Battenfeld-Cincinnati (www.battenfeld-cincinnati.com) presents advanced control and monitoring functions for extrusion lines with BCtouch UX, a step closer to industry 4.0 One main feature of the new system is its operating concept. Modeled on modern communication media, a new platform with intuitive menu navigation has been created. It supports efficient production planning and preventive maintenance intervals, and fulfills requirements for connectivity with servers and mobile appliances. In this way, it also provides the prerequisites for comprehensive process data acquisition and evaluation, and for vertical integration according to the industry 4.0 concept. The user interface recalls familiar operating concepts of tablets or cell phones and offers multitouch zoom as well as move and slide functions. In addition to the central operating terminal, additional terminals can be integrated without any problems along the line. Thanks to a new type of cockpit view, the process status of the entire line can be viewed at a glance. The design of the overview page and the navigation through the menu are derived directly from the line configuration. Additional features of the new operating terminal include the RFID access control system, which enables easy identification by chip card, and a context-sensitive help system. With the new BCtouch UX control, all process parameters are monitored centrally. This enables line operators to not only carry out energy monitoring, but also to calculate energy diagrams over time and on the basis of freely selectable production parameters as well. This, in turn, makes it possible to find an operating point where the line can be run with optimal resource efficiency in terms of both material and energy consumption. Since maintenance intervals for all line components are recorded in the control system, it supports the necessary preventive maintenance actions, thus, increasing line uptime and, consequently, overall efficiency. Fully in keeping with the industry 4.0 concept and the control system’s facilities for communicating with other units, all line and process parameters

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included and evaluated in the system can be centrally tapped into by an ERP system. For this purpose, the Battenfeld-Cincinnati OPCUA server provides a future-proof interface for vertical integration of the line at the customer’s plant. In addition to on-site operation, BCtouch UX also supports an alarm system via the internet or intranet with data of definable line statuses being transmitted to mobile units either by LAN/WIFI or by UMTS/LTE, according to the customer’s choice. ENGEL e-factory provides an individual MES. All data are loaded onto the server by the injection molding machine and evaluated or processed. That can, for example, cast a glance at the running production from time to time from the desk and assess the machine’s susceptibility to failure, capacity, and productivity. Various modules include:

• Planner—intelligent

detailed

planning

of

orders

• Data—start production quickly with appropriate settings data

• Monitor—production status at a glance • Chart—full documentation of process data • Reports—individual statistics and production indicators Husky (http://www.husky.co/EN-US/ShotscopeNX.aspxShotscopeNX) proposes its integrated process and production monitoring system SHOTSCOPE that provides a real-time snapshot of information to help control and improves processes while optimizing factory productivity. This webbased solution lets customers monitor machines or plants from anywhere in the world. The addition of the Energy Monitoring Module allows energy usage to be tracked and opportunities for increasing efficiency and reducing costs to be identified. SHOTSCOPE NX also archives historical data by automatically capturing all process and production information in a permanent record to provide 100% production and process traceability. Benefits include:

• Improved part quality by establishing process control and superior process stability

• Improved cycle time repeatability • Reduced machine downtime

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• Reduced scrap by improving part quality • Boosts plant utilization through simplified reporting and expedited information

• Increases percentage of on-time deliveries through simplified plant scheduling

• Provides the necessary information to make fast, well-informed business decisions SHOTSCOPE NX features include:

• Intuitive shot profile graphs with overlay capabilities

• SPC-analysis, SPC charting for both process variables and dimensional measurements

• Job scheduling/production planning • Preventive maintenance tracking for both machine and mold

• Automatic email messaging for process and production violations

• • • •

Remote Polaris control screen viewing MRP/ERP system data exchange Multiplant monitoring capabilities System security integrates with company network and domain (active directory)

• Historical data Energy Monitoring Module benefits:

• Provides more accurate and timely information for analysis of energy consumption

• Identifies inconsistencies in equipment operation and consumption during start-up and shutdown procedures

• Lowering of maintenance costs and reduction in overall carbon footprint

• Easy identification of inefficiencies by comparing actual energy use to model energy use Jomar (https://jomarcorp.com/) Jomar injection blow-molding machines have the capability to export real-time data directly from the machine to both the customer’s internal staff as well as the Jomar service team. The Jomar service department can troubleshoot the machine remotely as well as perform updates to the machine programmable logic controller. This will drastically reduce the cost of service by potentially eliminating the

need to have technicians that visit the plant and will also reduce possible downtime. The communication is established through an outbound connection across the plant’s LAN. It is isolated from the internet and potential outside influences by a private and secure IP address that is compliant with most firewall protocols and bestpractices for IT security. Kautex proposes its “Kautex Control Easy” software (http://www.kautex-group.com/assets/pdf/EN %20-%20PDF%20Versionen/EN%20Brosch%C3% BCren/Kautex_CP_EN_2012.pdf) Kautex Control Easy is capable of collecting, monitoring, and controlling all pre- and postmolding process parameters, opening the way to efficiency:

• Quick process parameter loading for product changeover

• Remote access via Ethernet/TCP/IP and modem

• Proactive and preventive online maintenance plan

• Process data collection • Continuous exchange with the operators KraussMaffei: Custom-made networking with Plastics 4.0 Under the name Plastics 4.0 (http://www.kraussmaffei.com/imm-en/presse/d/plastics_4_0_k2016. html), the KraussMaffei Group (KraussMaffei, KraussMaffei Berstorff, and Netstal) bundles its solutions into three categories:

• Intelligent Machines represents intelligent, self-optimizing machines, which improve productivity and quality.

• Integrated Production symbolizes seamlessly networked production, in which the individual machines and components communicate with each other and autonomously control the processes accordingly.

• Interactive Services are based on state-of-theart communication technologies in the environment of fast and globally active service. Intelligent Machines

An example from the Intelligent Machines area is the new expanded function APC (adaptive process control) Plus that detects process fluctuations

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that can be caused by changing ambient conditions or fluctuating viscosity, and takes countermeasures automatically. The APC function is suitable for thermoplastics, multicomponent injection molding, and silicone. Integrated Production

The Integrated Production category includes new and intelligent solutions for seamless networking in manufacturing, for example, the CX 300 FiberForm system. All quality-oriented process data, for instance, organic sheet heating curves or injection pressure and mold cavity pressure curves, are recorded in a KraussMaffei database, but are also documented individually using a QR code (that is, a type of matrix barcode or two-dimensional (2D) barcode) on the component. A printer integrated into the machine housing prints the QR codes immediately during manufacturing. This makes it possible to seamlessly trace all product and process data for each component—globally, online via mobile phone, tablet, or PC. The DataXplorer, developed by KraussMaffei, is an additional new system for boosting productivity in plastics processing. It is an open system for detecting, analyzing, and documenting comprehensive process data in injection molding production and up- and downstream processes. The system is used to boost productivity and reduce system downtimes in the long term, while improving quality and providing documentation at the same time. Under the concept of Plastics 4.0, KraussMaffei Berstorff is presenting various tools for monitoring machines, evaluating actual data and various service functions, webcam applications, and a central computer interface standardized for networking machines. Interactive Services

To be able to offer customers professional support quickly and globally, the KraussMaffei Group is developing the e-Service platform, which can be reached at any time using the KraussMaffei websites. It provides the customer with all relevant machine data centrally, providing the easy handling of any service processes. A user-configurable dashboard provides a clearly arranged overview including machine documentation and guides. The customer can access the current machine and production data at any time using the live monitoring function. Information available immediately about the machine history and diagnostic reports enable

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the smooth flow of communication with the aftersales service department in case of a problem, which contributes to finding a solution more quickly. A ticketing and optional remote maintenance system is integrated directly into the platform to optimally design the handling of service cases. There is also the option to transfer the most important information via QR code and smartphone app. In this way, required spare parts can be identified reliably. In the integrated online store, the spare parts can then be checked for their availability and then ordered. KraussMaffei Berstorff (http://www.kraussmaffeiberstorff.com/en/press-releases/d/k2016_ext_exhibits.html) proposes the new BPC Touch machine control system supporting Plastics 4.0. It allows:

• to link the order and production systems • to query order data • to apply presetting data and initiate processes The control system is equipped with a remote maintenance interface for targeted and expanded services. This makes it possible to install other available interactive services retroactively. Negri Bossi (http://www.negribossi.com/wp-content/uploads/AMICO-SYSTEM-2015.pdf) proposes: AMICO Supervision Software including the features:

• • • • • • •

Plant-wide machine status Production control information Down time reasons/Part reject faults Machine alarm tracking Full part trace/Process trending Cycle-to-cycle SPC data Machine efficiency data

The Negri Bossi AMICO Network allows remote diagnostics including:

• Full machine remote control • Real-time machine and component monitoring • Verification of the machine status during an alarm

• Modification of the machine setting parameters • CAN (Control Area Network) components setting/tuning

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• Modification of the machine’s configuration files

• Remote calibration • Knowledge base • Software updating/upgrading Nissei (http://www.en-plasinc.com/equipment/ proposes New nissei/nissei-tact-controller/) Controller TACT (2nd generation) featuring:

• High-speed control cycle, QR, and high repeatability. The system displays its great power, especially in high-cycle molding and small volume precision molding.

• Internal memory for molding conditions; up to 300 molding conditions (standard specification) can be stored in the internal memory. In addition to molding conditions and profile data, image data can also be stored. A variety of molding programs that will meet various molding needs are provided as standard equipment.

• NEX Product Quality Control: Nissei Central

• Simultaneous heating of the temperature of the nozzle and barrel prevents carbonization and deterioration of resin in the nozzle.

• LAN connector provided as standard equipment making it possible to connect the system to the quality/production control system PQ Manager, molding data, and some other auxiliary equipment as well as to another personal computer. ROMI (http://www.romi.com/en/) equips its machines with the new CM20 control panel providing full connectivity and the access to the panel through browser, tablet, or smartphone. It offers an interface with MESs, remote services, and resources for industry 4.0. Sidel (http://www.sidel.com/complete-lines/complete-lines#explorer52017) claims benefits of its smart data solutions helping to make smarter decisions and monitor productivity thanks to:

• Real-time data solutions keep productivity at its best.

Monitoring System (PQ Manager) allows the user to obtain a management system for quality control and analysis of moldings.

• Constant monitoring providing data-driven

• Control specifications for various condition

• Identification of bottlenecks, inefficiencies,

settings including: • 6-velocity, 3-pressure, 3-limit pressure injection process control for wide ranging condition settings. • 4-stage clamping velocity, 5-stage mold opening velocity including a slow speed mold opening mode, and multistage ejection control (selection of ejection operation from among 4 patterns is acceptable).

• Reinforced quality control functions (improved molding quality judgment function). A maximum of 8 items from among 23 molding monitor items can be selected freely.

• The statistical result of molding monitor data can be set as the product quality judgment condition and acceptance criteria.

• Clamping compression molding (CPN2): The

assessments for full traceability and detailed insights. and areas for optimization.

improvement

and

cost

• The information is intuitively displayed to improve reactivity by employees at all levels across the organization.

• Automatic adjustments to equipment and conveyors can prepare the line for new products, and structured data can reduce changeover time by 20%, lowering overall costs. Sidel’s smart data may provide:

• For management: View comparisons and process information for a complete efficiency overview

• For engineering: Access performance details to monitor line flow and maintain stability

clamping compression is conducted right after injection filling. This is effective in releasing stress in products and degassing.

• For maintenance: Fully trace problems to insti-

• The display of 1000 items of operation history

tion to identify out-of-spec values and eliminate inefficiencies

is useful for maintenance and quality control.

gate fast repairs and reduce downtime

• For operations: Monitor all phases of produc-

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Stratasys (http://www.stratasys.com/3d-printers/ design-series/objet260-connex3) proposes Objet Studio Software that makes it possible to build high-quality, accurate prototypes. It transforms STL or WRL files from any 3D CAD application into print-ready 3D models with color, material, and support placement information. With click-andbuild wizards, it can quickly edit trays, change materials and colors, manage job queues, and perform routine system maintenance. Objet Studio features:

• Easy tray setup including multiple models and materials

• Virtual reality modeling language support for easy color assignment

• Automatic support generation • On-the-fly slicing so printing can start right away

• Auto-placement of trays for accurate, consistent positioning

• Multi-user networking Wittmann 4.0 (https://www.wittmann-group. com/) transforms the injection molding machine into a control terminal for robots, peripherals as well as superordinate systems such as the “authentig” MES system from TIG (http://www.tig-mes. com/) including these modules:

• • • • • • • • •

Monitoring: productivity Planning: concise planning Optimizer: optimal planning results Quality: quality production Setup: correct machine settings Connector: data from the machines Production-monitor: transparency Energy: energy optimization Analyzer: making decisions at the push of a button

• Mobile: mobile information Many other machine builders propose their proprietary solution or compatibility with market software.

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4.3.3.5 Target Zero-Defect Manufacturing Obviously, zero-defect manufacturing (ZDM) often means “lowest possible level of defects.” The interest from a sustainability standpoint seems evident, but, as for other parameters, the overall sustainability must be verified because the strategy can induce measures damaging it. Two different examples illustrate the ZDM strategy. Example of Mass-Produced Molded Parts

There are a multitude of propositions from planning (in quantity and on time) up to final testing (quality control) through the injection process and many other steps. Simply to give a rough idea of the interest, the APC machine function (KraussMaffei) obviates or mitigates variations of factors such as ambient temperature, humidity, and batch fluctuations in the material that influence the injection molding process and lead to slight changes in the melt viscosity and, in turn, the component weight. Obviously, the ZDM strategy may open the door to a larger use of recycled plastics. For a defined example related to a short run of injected parts, the gain on the standard deviation of part weights can be as high as 78% saving material, energy, pollution, labor, money, among others. Example of Zero-Defect Manufacturing of Composite Parts in the Aerospace Industry

The ZAero project (http://www.zaero-project.eu/) will provide a solution by developing in-line quality control methods and decision support systems for the key process steps:

• the automated dry fiber placement and automated dry material placement lay-up processes

• infusion and curing processes The processing chain involves four steps:

• An in-line quality control system detecting quality problems and allowing the machine operator to decide to rework or continue.

• Process monitoring during the infusion and curing processes.

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• Collection of defect data to compute the mechanical strength of defective parts.

• Combination and processing of all collected data to build a decision support tool for the operator to help decide about subsequent work. Potential advantages include:

• • • •

reduction or suppression of defects productivity gains due to automated inspection optimized infusion and curing processes optimized decisions

This ZDM process has been selected as a finalist for the JEC Innovation Awards 2019 in the Aerospace category.

4.3.4 Promote Efficient Real-Time Quality Control The earlier an error is detected in the production process, the less it causes increases in energy consumption, pollution, cost, and wastes. It is, therefore, essential to detect errors as early as possible maintaining properties into their respective acceptable values. The benefit of in-line quality control is the detection of errors at their source and even before they occur in the best cases. Modern processing machines embed a lot of hardware and software allowing for the promotion of efficient quality control, leading to:

• rapid corrective actions • off-specs reduction and subsequent waste reduction

• energy savings • better productivity Vision sensors are well suited for dealing with these issues, and in addition, the images can be stored for later use. Vision sensors may be added to old machines or incorporated into new ones. For instance, a vision sensor can check whether an insert has been placed correctly into the mold of the injection molding machine. Having the component in the right position prevents damage to the

tool and, as a result, reduces machine downtime. Detection of false position can prevent mold closing and subsequent damages. Vision sensors can also detect over- or under-filling and eject faulty parts. In bottle blow molding, part weight distribution is often a property easy to measure by direct or indirect means. For instance, Sidel had chosen an indirect in-line measure of the part weight distribution by infrared absorption. Contrary to manual and discontinuous method, a software automatically and continuously monitors and corrects the bottle quality during production.

• First, Equinox automatically measures, thanks to the INTELLIMASS system from Pressco Technology Inc., the infrared light absorbed by PET, which depends on the thickness of the bottle wall. If the system detects variations from the setpoint weight, it activates the correction process without machine shutdown.

• Second, if the weight is beyond the tolerance limit based on the initial setpoint, then the blow-molding machine control algorithm is automatically triggered, and the operator receives a warning about the problem. Two critical parameters that directly influence the material distribution can be adjusted. Changes to pre-blow pressure regulate the overall production on all stations, and modifying the start of pre-blow adjusts individual stations. It takes about two minutes for the process to completely stabilize. If the software is unable to return the base weight curve to within tolerance limits, it automatically lets the operator know which blow-molding station is causing the problem so that the operator can take corrective measures. In most cases, the automatic regulation occurs so quickly that no variation in material distribution exceeds the control limits set for the production mode. In a different field, for extrusion, Dynisco proposes its ViscoSensor Online Rheometer (http:// www.dynisco.com/online-rheometer-viscosensor) specifically designed for the thermoplastics resin industry. The ViscoSensor provides continuous measurements of the melt flow rate or apparent viscosity directly on the manufacturing process

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without an additional waste stream, and with the tested sample being returned to process. Results are directly used for extrusion monitoring. Many other solutions are proposed, compatible with market software or dedicated to proprietary solutions.

4.3.5 Preventive and Predictive Maintenance Maintenance may be divided into:

• Breakdown maintenance: the worse solution leading to breakdowns generating wastes, offspecs, long loss times, etc.

• Preventive maintenance: routine or time-based preventive maintenance are medium solutions mitigating breakdown occurrences, wastes, off-specs, and loss of time.

• Predictive maintenance: the best solution. These techniques are designed to help determine the condition of in-service equipment in order to predict when maintenance should be performed. This approach promises rarer unexpected equipment failures, better efficiency, better productivity, and cost savings because tasks are performed during inactivity periods only when warranted. Maintenance work can be better planned with anticipated spare part supplies, staff arrangements, etc., increasing plant availability. Other potential advantages include increased equipment lifetime, increased plant safety, and fewer accidents with negative impacts on the environment. All machine builders have maintenance in mind and offer preventive maintenance with visit or remote diagnostics:

• identification of wear points and breakdown risks

• recommended corrective actions • refurbishment (reconditioning of equipment) • customized maintenance programs including analysis and maintenance of production equipment and advise on maintenance investments Apart from manufacturing machines, testing machines must also be included in maintenance programs. Undetected false results of specified tests

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can be the cause of downgrading of products causing expected compliant products to be downgraded in off-specs and waste. Among tools used for predictive maintenance, there are, for example:

• Vibration analysis may determine if bearings or components are loose, moving, or wearing

• Infrared thermography can detect hot spots, load imbalances and corrosion, and failures due to excessive heat

• Oil analysis may show increasing metals in oil samples, indicating breakdown of internal parts. Wear particle analysis determines the mechanical condition of machine components, identifies particle size, type, etc.

• Visual inspections For instance, two examples linked to plastics manufacturing include:

• The e-connect.monitor by Engel collects data from a variety of sensors including ultrasonic transducers. Ultrasonic transducers measure actual wear to the plasticizing screw, therefore, eliminating extended downtime for barrel and screw disassembly and inspection. Until now, to assess the condition of a screw on a large injection molding machine, the operator had to schedule two to three workdays of downtime to remove, clean, and measure the screw. However, the new technology allows an Engel service technician to temporarily mount an ultrasonic transducer on the outside of the screw barrel. The device captures ultrasonic signals of the barrel. The data is then uploaded to Engel’s algorithmic software. Customers can access the results and any maintenance suggestions via Engel’s e-connect customer portal.

• Wittmann Battenfeld combines technology with human diagnostic competence. Sensors measure criteria including vibrations, torque, temperatures, air humidity, oil quality, flow quantities, screw function, and other data. Special process control software analyzes the data and then specialists, either at the customer’s plant or at the Wittmann Battenfeld service center, evaluate the data and condition analysis before deciding what type of maintenance might be needed.

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hydropower with about 15% and for nuclear about 2%

4.3.6 Minimize Waste Wastes are doubly penalizing:

• Losses of material, energy, time, money, etc. • Lack of corresponding compliant product. Many points have already been implicitly or explicitly discussed and others are later examined such as:

• Turkey with a medium share including about 45% of natural gas and fossil fuel, about 30% of hydropower, and 23% of coal

• Norway is the champion of hydropower accounting for nearly 100%

• France is the champion of nuclear electricity with 75% 80%, and less than 5% 10% for each other source.

• The use of suitable materials supplied by liable suppliers

• The use of properly maintained intelligent machines

• Rigorous planning for delivery of the correct quantities of compliant products on time using suitable software systems

• Use of efficient real-time quality control and

Environmental effects of energy production estimated by GHG emission intensity (CO2e/GWh) broadly depend on the used production technology, age of production units, and life cycle analysis methods. The data listed below are examples and for a given item, estimates may vary between 10% and 1000% of the quoted figure (tons CO2e/GWh) according to the study under consideration.

monitoring

• Application of predictive maintenance • Integration of manufacturing steps • Employment of skilled people benefiting from competence development, training, and elearning

4.3.7 Use Renewable Energy The use of renewable energy (see also Chapter 1: An Overview of Sustainability and Plastics: A Multifaceted, Relative, and Scalable Concept) saves fossil fuels that are also used as raw materials for plastics polymerization. The environmental benefits depend on the used fuel. Unless energy policies change drastically, the world will continue to depend on fossil fuels until their scarcity and their costs become unbearable. In round figures, shares of various fuels could be:

• fossil fuels on the order of 60% 70%, • renewable origin about 20% • nuclear nearly 15% These estimates cover different spots according to the country, for example, concerning electricity sources:

• China may be the champion of coal consumption accounting for nearly 80% followed by

• • • • • • • •

Lignite and coal: 1000 Oil: 733 Natural gas: 500 Solar photovoltaic: 85 Biomass: 45 Nuclear: 29 Hydroelectric: 26 Wind: 26

However, all studies lead to similar rankings expressed in tons CO2e/GWh:

• Lignite and coal, oil, and natural gas lead to the highest GHG emissions

• Solar has a medium position with a range that could partially overlay the oil source range

• Biomass, nuclear, hydroelectric, and wind lead to low GHG emissions accounting for less than 10% of the first category This example of ranking does not represent the full face of each technology and, for instance, nuclear energy is highly questionable. Turconi et al. (2013) report ranges of CO2, NOx, and acidification potential (SO2 equiv.) quoted in various studies. Fig. 4.4A C shows ranges of CO2, NOx, and SO2 with high emission levels for

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(A) Coal or lignite Oil

Natural gas Solar

Biomass Wind Nuclear Hydropower 0

500

1000

1500

(B) Lignite and coal about

Natural gas Oil Biomass Solar Wind Hydroelectric Nuclear 0

(C)

1

2

3

4

5

Oil

Lignite and coal Biomass Solar

Natural gas Wind

Nuclear Hydroelectric 0

2

4

6

8

10

Figure 4.4 (A) Examples of CO2 emission ranges (kg/MWh). (B) Examples of NOx emission ranges (kg/MWh). (C) Examples of SO2 emission ranges (kg/MWh). Table 4.7 Environmental Benefits of Renewable Energies. CO2 Saving (%)

SO2 Saving (%)

NOx Saving (%)

Hydropower

99

99

98

Nuclear

98

99

99

Wind

98

98

97

Biomass

93

86

57

Solar

90

94

87

Natural gas

30

95

2

Oil

27

226

51

Coal or lignite

0

0

0

electricity derived from fossil sources except for SO2 emission by natural gas. Renewable energies and nuclear power are environment-friendly from both these points of view.

For energy used to produce polymers, Table 4.7 displays savings (percent), linked to the use of coal or lignite, hydropower, wind, biomass, solar, nuclear energy, natural gas, and oil. Savings are

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positive except for SO2 emitted by oil, which is negative, indicating that oil emits more SO2 than lignite. Conversely, CO2 emitted by the use of oil is 27% lower than the level of CO2 emitted by lignite. These data are based on average values and drastically vary according to studies. The reader must be careful because some percentages are not meaningful. In addition, these figures represent only a share of energy consumption and are purely theoretical. In real life, electricity comes from a mix of several sources. Thus, other data may be found elsewhere in the literature including in this book. That being said, hydropower, nuclear, wind, biomass, and solar are beneficial for the environment from these points of view, but other indicators may be detrimental. For instance, dams for hydropower can disrupt and destroy the natural environment and even human habitats.

4.3.8 Integrate Manufacturing Steps Using Direct Mixing, Comolding, Overmolding, In-Line Process, Workcells A one-shot processing suppresses other production step(s) leading to environmental and other benefits:

• In most cases, suppression of the reheating of the suppressed processing step(s) saves the related energy and pollution. In addition, the elimination of the involved thermal degradation improves the quality of end products.

• In most cases, suppression of the second shear step contributes to the reduction of thermalmechanical degradation.

• Suppression of intermediate storage(s) simplifies logistics and the corresponding handling.

• Possibility to adjust formulations and finish treatments in-line to follow the variations of properties and the requirements of the customers. For example, rheology can be monitored in-line, in real time, in real conditions of temperature and pressure or color and can be easily changed according to the needs.

• Reduction of floorspace. • Suppression of corresponding immobilized assets, etc.

Sometimes the capital investment can be higher, but all in all, that technique leads to:

• Energy savings • Time and labor cuttings • Improvement of the performances of the finished products

• Cost saving if the process is adequately chosen for the real requirements Theoretically, all the operation steps can be integrated. The decision must be made according to the available techniques, existing tools and machines, and the size of the run. Some techniques have become routine processes such as wire coating, insert and outsert molding, comolding, overmolding, coextrusion, cross-linking, gauging, and so forth. Fig. 4.5 brings to mind some more or less common in-line operations. All markets benefit, to a greater or lesser extent, from the in-line operations, for example, automotive, packaging, electricity and electronics, appliances, healthcare and medical, industrial, communications, railroad, among others. Manufactured parts are as diversified as, for example, airbag doors, boards, booths, bottles, computer components, conduits, covers, doors, films, fittings, front-ends, joints, molded parts, panels, pipes, profiles, seals, sheets, tailgates, trays, tires, windows, wood plastic composite, and so forth. All polymers are concerned from commodity plastics up to high-tech ones including polyether ether ketone or others, and also conventional rubbers and thermoplastic elastomers.

4.3.8.1 Integrated Compounding In these processes, the compounding rate is synchronized with the molding rate. There are several versions according to the plastic type (thermoplastic or thermosetting resin), reinforcement type, eventual blowing, among others. For example, the LFI-PUR process competes with spray-up and sheet molding compound (SMC). The patented long-fiber injection (LFI) process is a cost-effective method of manufacturing lightweight, long glass-fiber-reinforced PUR parts produced in one work cycle. KraussMaffei developed the LFI process including a head to cut glass-fiber strands (10 100 mm long) from a roving and

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In-line integration

Compounding

Upgrading direct reinforcement

Foaming blowing

Fluid assist processes

Coprocessing

Overmolding

Insert outsert

Reactive compounding

molding

Finishing

Assembly

Control

IMD FIM

Comolding coextrusion

Monitoring

Workcell

Quality

IMC IML

Painting printing marking

Surface treatment

Figure 4.5 In-line integration examples.

deposit them in a mold drenched with polyurethane components. Fibers and PUR are deposited simultaneously into the mold. This technique used with the Baydur polyurethane system and combined with function integration reduces the assembly steps and directly produces large parts leading to:

• Lighter weight parts than those of comparable counterparts polyesters

using

glass-mat-reinforced

• High performances • System cost reduction Typical applications include spa cabinets, agricultural equipment, heavy duty vehicle elements, garage doors, and so forth. Costs savings compared with spray-up and SMC technologies come from a better process efficiency due to:

• Resin material savings by foaming the resin from 30% to 50% while keeping the same level of performance

• A higher productivity and a lesser labor than spray-up (from 4 hours for spray-up to only 10 minutes with LFI technology)

• Lower tooling costs than SMC In addition, the LFI technology can reduce assembly and finishing costs suppressed by in-mold

methods, in-mold coating, and film insert technologies, which yield finished parts out of the mold.

4.3.8.2 Coprocessing: Coinjection and Overmolding Coinjection and overmolding involve several processing options:

• Overmolding of a plastic onto a previously produced part.

• Injection of several materials side by side in the same mold. This is the process used to produce taillights. The thermoplastics must be compatible. It is possible to use molds with moving parts and inject the materials successively, or use simple molds and simultaneously inject the materials.

• Coinjection of a core and a skin of two different plastics. The core can be any plastic, a foam, or a recycled material. The plastics must be compatible.

4.3.8.3 Fluid-Assisted Injection Molding A fluid, gas, or water, allows for the production of hollow parts with internal cavities and common external aspect. Gas-assisted injection molding is a variant of injection molding suitable for producing hollow parts with tailored internal cavities. It is used for

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the manufacture of products such as household appliances and automobile parts. Apart from the injection step itself, which is identical to common injection molding, there are three steps for mold filling and gas introduction:

• The mold is partially filled with the melted thermoplastic.

• Gas is injected into the material through a specialized nozzle. The plastic in contact with the mold is colder and, therefore, stronger; thus, the gas stays in the core of the plastic and presses it against the wall cavity.

• The pressure is maintained until the part is cooled and solidified enough.

• At the end of the cycle, the gas is vented prior to the mold opening. This technique offers extra advantages over common injection such as, for example:

• weight and material savings for the same volume, which is good for the environment

• cost cutting • sink mark reduction • lower residual stresses On the other hand:

• the technique is less widespread • the machinery is specialized 4.3.8.4 In-Line Decoration: FIM, IMC, IML, Among Others In-line decoration and in-mold decoration (IMD) include various techniques such as, for instance:

• • • • • • • •

Film insert molding (FIM) Film profile cladding In mold coating (IMC) In mold labeling (IML) In-mold graining Metal overmolding Textile overmolding Real wood veneer back molding

• Electrostatic fiber coating or flocking, etc. IMD reduces the finishing operations. If the process and its operating conditions are suitable, the demolded parts are finished. FIM—Some examples of IMD with films are quoted below:

• Development of a glossy, aesthetic, and unpainted roof module on the Smart Roadster by DaimlerChrysler AG Smart. The two-piece, removable roof, built by ArvinMeritor is surfaced with a thermoformable three-layer film (Lexan by SABIC Innovative Plastics, formerly GE Plastics) that can be comolded with either thermoplastic or thermoset substrates. The film exhibits 95% gloss retention after the equivalent of 10 years of Florida sun exposure. Weight saving is 50% versus a painted steel roof system.

• Quadrant Plastics Composites is studying three solutions for the decoration of glass mat thermoplastic body panels: • Polymethylmethacrylate (PMMA)-based films (Senotop) already used for the Smart CityCoupe´ roof • PP-based films • Coil-coated aluminum

• Other variations of film decoration are, for example, the rocker molding for the General Motors Chevrolet Trailblazer North Face Edition, a 2-m-long part thermoformed over injection molding because of the relatively low volumes (7000 8000 vehicles per year) and the short development time required.

• Another non-paint approach was developed by Mayco and DaimlerChrysler Corp. consisting of extruding a glossy, colored film. After thermoforming to the part shape, it is placed in an injection mold, and thermoplastic is injected behind it. Cost savings are estimated to be h5 h12 per fascia.

• A prototype heating and ventilation control panel produced by Bayer and Lumitec using a luminescent plastic film system incorporating a special electroluminescent electrode system. The panel can be produced in a single process step using Bayfol films and a PC/ABS blend (Bayblend).

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• Window profile extruder and down-line equipment manufacturers (Aluplast, Greiner Extrusionstechnik, and Fux) designed an inline process of cladding PVC window profiles with decorative films. The PVC profiles are clad directly after calibration, but before coextrusion of elastomer seals. The claimed cost saving is about 30% based on the annual production of 160,000 m of window profile. In-mold graining, developed by Johnson Controls, is a covering process for large surfaces in which an ungrained thermoplastic polyolefin (TPO) foam foil is wrapped onto a carrier and grained in a single process. The TPO foil used in the process can be separated from the carrier material with relative ease to enable the materials to be recycled. The technique is used for a large surface in the production of the door panels for the Opel Astra. “Inmold graining” is also suitable for use in instrument panels. In-mold coating: in the conventional IMC method, the cavity surface of the injection molding tool is first sprayed with a coating and the cavity is then filled with the melted thermoplastic compound. Because the coating and the injection molding are performed consecutively, cycle times are substantially long. Covestro (formerly Bayer MaterialScience AG) proposes a variant of this IMC process, which combines injection molding with reaction injection molding (RIM). In a twostep process, the part is first injection molded and then, with the aid of a turntable mold, is transferred to a second cavity. There, a reactive twocomponent polyurethane system is injected using the RIM process. The PU cures within the cooling time in the closed mold. For car interior applications, for example, the IMC process could be used to apply a decorative finish to parts such as the glove compartment flap, add-on parts for the instrument panel, panels and mirror housings. Lowviscosity systems are used as two-component polyurethane coatings, based on, for example, Desmodur and Desmophen. They cure quickly, can easily be demolded and adhere well to Desmopan thermoplastic polyurethanes, Makrolon PC, and various PC blends like Bayblend and Makroblend. The IMC process can also be used to apply a decorative polyurethane skin at least 1 mm thick to an injection molded substrate resulting in a surface with good adhesion, soft touch properties, and an

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attractive appearance. It could be also used for decorative trim and decorative skins for armrests and door liners. Trays coated with a nonslip finish for the center console are other possibilities. Such coatings could also help dampen troublesome grating noises produced when plastic parts rub against each other. IML is used, for example, by Adolf ILLIG Maschinenbau GmbH & Co for thermoformed cups and lids eliminating finishing steps and allowing for full in-line container thermoforming, filling, sealing, and decoration. The rigidity of plastic labels allows for the reduction of the thickness of the containers and, if using one material only for cups, lids, and labels, their recycling is eased. In-mold flocking by Fiber Graphics combines the flocking or electrostatic fiber coating of a film and FIM. Short fibers (usually 0.5 1 mm long) of nylon, polyester, rayon, acrylic, cotton, among others, are charged with a high voltage and electrostatically applied to the “first surface” of a heatactivated adhesive film. This one made out of PC, ABS, or PC/ABS is formed and incorporated into the mold. During the molding process it directly adheres to the plastic part. Film thickness typically ranges from 0.1 to 0.3 mm. Fiber Graphics IMD considering the “enhanced touch,” targets new surfaces for everyday products such as phones, computer laptops, game controllers for Sony PlayStation and Microsoft XBox, computer mice, aircraft and automotive interiors parts, handles on luggage, writing pen barrels, tool grips, hair dryer handles, edge of lid on a scanner, sporting goods like golf bags or arrow quivers to ease entry of the clubs and arrows and to prevent scratching, parts for helmets either to increase softness or to prevent slipping of parts against each other, mock-ups, and so forth.

4.3.8.5 Printing and Laser Marking Printing

Printing is a well-known technique and current applications use inkjet printers to deposit inks accurately and reliably for coating and decoration of plastic films and parts. The design of the printer, the number, the configuration and orientation of the print heads, the ink type (e.g., UV drying), UV lamps or LEDs, and the cooling device, depend on the application, the size, and shape of the substrate to be printed or coated, the speed line, and

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coverage requirements. In addition, UV LEDs can be used prior to the main cure to “freeze” the drops immediately on impact, enabling the wetting to be further controlled for higher print quality. There are several inkjet technologies including drop-ondemand, continuous inkjet, conductive inkjet technology. The choice depends on the substrate, the quality requirements, the speed. Inkjet is now being deployed as a reliable and robust deposition tool for the coating and decoration of a wide variety of 2D and 3D plastics and films. Printing is also used for technical applications, for example, a project to print organic transistors on plastic for electronic displays and circuits (by Sarnoff Corporation with DuPont de Nemours and Company Central Research and Development). The goal is to develop materials, thin flexible plastic substrates, and methods for continuous highresolution printing. Laser Marking

In-line laser marking competes with inkjet and pad printing. Sabreen (2005) describes the technology and examples of applications including “onthe-fly” laser marking for undercap promotions on linerless beverage closures incorporating laser optimized polyolefin materials. Turnkey systems are capable of marking 1200 closures per minute. Many producers, compounders, and ingredient suppliers such as, for example, BASF, Bayer, Clariant, PolyOne, RTP, Ticona, among others, market special grades and ingredients for laser marking.

4.3.8.6 New Processes, Function Integration Laser Structuring: Integrate Mechanical and Electrical Functions in MIDs by Laser Direct Structuring

The patented Laser Direct Structuring (LDS) technology is an innovative, environment-friendly and precise process for the manufacture of 3D molded interconnect devices (MIDs). The desired interconnect pattern is directly written on the molded part utilizing a LPKF’s (https://www.lpkf. fr/) scanner based MicroLine 3D IR laser system. A laser first “burns” a high-resolution pattern directly onto the injection molded part. This activates a special additive already incorporated into the thermoplastic. Then, the conductive paths are plated using an industry standard electroless plating

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technology. The plating adheres only where the laser has activated the plastic. So, it is possible to achieve conductor track widths of less than 150 200 µm with minute spacings between the conductor tracks. The new technology saves space and weight in mechatronic devices, and integrates collateral, finishing, and assembly operations. Moreover, LDS is a highly flexible technique. The design of the circuit can be changed by reprogramming the computer that controls the laser. Expensive and time-consuming modifications of tooling are no longer necessary. Due to the comprehensive design possibilities of the injection molding, there is a high freedom of shapes for the created 3D circuit carriers. Moreover, mechanical functions such as holders, guides, buttons, plugs or other connection elements, and cables can be integrated. The combination of electronic and precision mechanical functions opens the way to new levels of design freedom, function integration, miniaturization, weight reduction, and of course, environmental and cost savings. Mechanical and electrical functions integrated in MIDs open the way for many potential uses in electrical components for automotive applications, rotary transducers, sensor housings, actuators, control boxes, steering wheel modules and the interconnect devices of locking systems, cell phones, and so forth. Special versions of thermoplastics are developed by producers such as, for example:

• LANXESS proposing various grades of its Pocan polyester for LDS. The Pocan DP 7102 and TP 710-003 are mineral-reinforced PBTs designed for injection molding and extrusion. They allow for the production of warpage-free molded parts with excellent surface quality.

• DSM markets its Stanyl ForTii LDS, a polyamide suitable for lead-free soldering and LDS, offering a high melting temperature, a high glass transition temperature, and a high stiffness across a broad temperature range. Furthermore, Stanyl ForTii shows a comparable thermal expansion coefficient for both the parallel and vertical flow direction and as such can be used in applications where coplanarity is a key issue.

• BASF offers its Ultramid T 4381 LDS, a semicrystalline, partially aromatic high-temperature

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polyamide (PA6/6T) reinforced with 10% fiberglass and 25% mineral fillers and including a metal complex that can be split by a laser. It offers a wide processing window for metallization and excellent mechanical properties. This material has been specifically optimized for LDS (LPKF-LDS) to create injection-molded 3D circuit carriers. Well suited for metallization, it displays good adhesion of conductors and exhibits low warpage. In-Mold Assembly

The goal of in-mold assembly (IMA) is to integrate, inside the mold, the assembly of separate components generally through snap-fits, welding, or adhesive bonding. This can start with a simple overmolding and finish with the complex mechanical assembly of several parts to be matched. IMA confers benefits such as:

• • • • •

Cost saving Simplified logistics

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free-dropped demolding or removal by a robot, filling of the cup, and closing of the lids outside the press area with a closing machine. SwingChutes uses a mechanical, pneumatic and vacuum system to eject parts, assemble cups and lids, insert wet wipes, and close the container. SwingChutes can be incorporated in a wide range of other applications including closures, containers, and housings. Millacron and Foboha market a double turningcube stack mold system producing two parts from two materials, assembled and labeled in one injection machine. Cavity-registered assembly is precise, ideal for packaging, medical, cosmetic, personal care, and optical products. The Skinform technology by KraussMaffei combines injection molding and RIM to manufacture a seat belt buckle lock for a luxury car model. The structural part made out of polyamide is encapsulated in a 0.8 3 mm layer of PU produced by a metering mixer. The Skinform technology is claimed to provide excellent surface quality and saving cost because of the direct assembly.

Labor saving Floorspace reduction. Time saving, etc.

On the other hand, IMA needs:

• Higher tooling costs, 30% 70% more than standard molds.

• High part volumes, 250,000 and more. IMA uses standard multicomponent presses, but needs specialized tooling integrating specific knowhow, automation, robotics, and software ensuring the repeatability and accuracy of the process. In some cases, mold and press builders enter into partnership, for example, Billion, Demag, Engel, Ferromatik, Electroform, Foboha, Gram Technology, KTW, StackTeck, TRW, among others. Among others, a few examples include: Husky patented SwingChutes, an in-mold product handling system for molding hinged, flip-top lids for wet wipes containers that, when compared to conventional systems, can lead to a 10% 15% increase in output and a 15% 25% reduction in floorspace. The conventional process includes

4.3.8.7 Example of Alternative Processing Methods: Thermoformed Bottles Compete With Blow-Molded Ones ILLIG has developed a thermoforming machine, called BF70, to form bottles at rates consistent with a conventional fill and seal line. The BF70 is roll fed with a punching station added to separate the bottles from the web using steel rule cutters. The material used is prestretched and formed using sterile pressure air with contact heating plates heating up the material step-by-step during several cycles. The BF70 unit can hit 30,000 thermoformed bottles per hour. The technology requires an absolute synchronization of the machine and tools and uses moveable lower tool parts to achieve the necessary undercut. The concept is claimed to make bottles indistinguishable from blow-molded ones, but with a 50% weight saving leading to environmental benefits and unique processing cost savings. Obviously, blow-molding equipment makers are not inactive and develop new techniques specially designed for weight savings.

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4.3.8.8 Workcells: Automation and Complete Production Cells Automation leads, in the ultimate steps, to sophisticated and complete production cells ensuring part and insert handling, labeling, transfer, removal, packaging, assembly, and finishing treatments as diversified as the insertion and encapsulation of a sensor or the magnetization of magnetic discs. In workcells, robots and other appliances are fully integrated into the hardware and the control software of the injection machine. Production cells are developing and, without claiming to be exhaustive, a few examples are provided here including those already examined in Section 4.3.3.1.

• Husky (http://www.husky.co/EN-US/) markets complete turnkey workcells optimized to lower energy consumption, increased quality, and reduced waste. Husky’s H-PET AE system is claimed to be an efficient, affordable solution for lower volume preform production with no compromise in quality. An optimized standard auxiliary package for a complete workcell infrastructure and full integration through Polaris Control software is included.

• Frisella

Design (http://www.friselladesign. com/work-cell-for-medical-assembly.html) proposes a multirobot fully automated workcell for the assembly of a plastic medical product. Utilizing rotary indexing, servo actuators and two Epson SCARA robots to load, unload, dispense adhesive, and assemble this five-part device, the result will more than double the production rates while reducing direct labor content.

• Lids with printed labels served on the Vitesse 300 by Ferromatik Milacron (https://www. milacron.com/): see Section 4.3.3.1.

• ARBURG

presents a three-component ALLROUNDER 370 S used to demonstrate the production of a three-part rotary encoder in a single production step: see Section 4.3.3.1.

• Netstal proposes its ELION 2200 using a 64imp mold to inject closures of HDPE. The shot weight is 64 g and the production cycle is 2 seconds: see Section 4.3.3.1. If automation has reached an upper limit for a defined process without hope of new significant

progress, it is necessary to explore innovative techniques allowing to drastically modify the production scenario. For example:

• ENGEL, in the automotive field, presents a new thermoplastic reinforcement technique with glass or carbon fiber fabrics. On an ENGEL duo 2050/500 pico, a steering column is made of PA in a complete manufacturing cell with three robots. This application revolutionizes lightweight design, in particular, as it allows steel and aluminum sheets to be replaced by thin fabrics of glass or carbon fibers embedded in a defined orientation in a thermoplastic matrix of PA or PP.

• ENGEL demonstrates the flow-coating of an injected part with polyurethane on a fully electric ENGEL e-motion 280 t using the ENGEL clearmelt process. This involves back injecting a wood design foil with a thermoplastic carrier and then covering the part with a transparent layer of PUR. The process is characterized, in particular, by a visually impressive 3D effect and excellent scratch resilience. The advantage of the process is that both back injection of the decor foil and flow-coating with PUR occur in a single mold without interrupting the process, guaranteeing an excellent productivity. Fully automated insert placing, take-off, and stacking of the manufactured parts are handled by an ENGEL viper 40.

• KraussMaffei and Evonik Rohm GMBH developed the CoverForm process for “oneshot” injection molded scratchproof parts. A PMMA component is injection molded and a functional protective layer applied in the mold immediately afterwards. A following compression molding sequence spreads the coating evenly over the PMMA surface. This eliminates the need for up to 14 steps normally taken by a conventional value-adding chain, in the production of coated parts. Precise control of the electric injection unit combined with the special compression clamp sequence ensures absolute repeatable micron thickness of the coating made of a solvent-free, acrylate-based, two-component reactive system. A CX 200 750 hybrid injection machine incorporates the latest compression molding

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technology and a metering unit for the reactive system, which has been optimized for the CoverForm process. An integrated robot is used for part removal and handling. Parts manufactured with CoverForm are claimed to have outstanding characteristics such as high resistance to scratching and to certain chemicals. The technology targets the production of automotive parts, medical devices, household appliances, and mobile phones. The process provides producers with the benefits of slashing cycle times compared to traditional methods and producing quality components through a highly stable process.

4.3.9 Integration of Subparts and Reduction of Raw Material Diversity From the beginning of a project, designers must have in mind the reduction of the number of subparts and material types, which facilitates:

• • • • • •

Assembly operations Material supply and storage Subpart storage Handling issues End-of-life disassembly Waste treatment, etc.

In general, other advantages include cost and labor savings, easier planning, and waste reduction. Of course, in all cases, the design team must weigh the actual advantages and drawbacks of alternative solutions. Some benefits of innovative alternatives may lead to drawbacks for some other features. For example, integration may make endof-life disassembly and waste treatment harder.

4.3.10 Potentially Hazardous Releases Possibly Emitted by Plastics When heated such as during processing or high temperature activities (welding, brazing, heat gun treatment, soldering, cutting, sawing, etc.), polymers degrade, producing airborne particulates, gases, vapors, fumes, volatile organic compounds (VOCs), dust, aerosols, and other releases. This

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breakdown is often referred to as thermal degradation. The temperatures at which thermal degradation starts broadly vary due to the many different polymer types, formulations, heating processes, durations of heating, and the presence or absence of oxygen, leading respectively to oxidative or nonoxidative degradation. When polymers undergo thermal degradation, some potentially hazardous chemicals may be emitted, even if visible smokes are not emitted. It is important to be aware of the degradation and use appropriate control measures (e.g., local exhaust ventilation, personal protective equipment, etc.). It is the responsibility of the reader to search for information regarding their own case in terms of health effects, safety issues, prevention and precaution measures available through suppliers, technical centers, professional associations, and so forth. Obviously, the reader must obey health and safety laws, REACH, Control of Substances Hazardous to Health (COSHH), and other regulations or directives adopted by global, regional, or local authorities. It must be noted that requirements are not universal and even an acronym may cover several meanings. Generally speaking, the polymer formulation, the processing temperatures, the residence time, the rate of shear, the cooling rates and the presence of oxygen influence degradation and emissions. The higher the processing temperature, the longer the residence time, and the higher the shear, the more a polymer degrades. The bigger the air-exposed surface to the volume ratio of the part under consideration, the more the polymer degrades. Efficient cooling decreases emissions. Of course, as their general name suggest, antioxidants directly interfere with the thermal degradation process; the rate of degradation decreases because the degradation process is hindered by antioxidants. Other additives can also accelerate or slow the degradation behavior and modify VOC compositions. The composition of emissions depends also on the temperature. The absolute amount and composition of emissions are extremely difficult to estimate since they depend on the local circumstances and interferences between numerous parameters. Other issues may occur during the use phase, for instance, exposure to harmful ingredients of the used plastic grade during the storage of food in plastic packages or chewing of plastic teethers and toys by children. Certain ingredients may be linked

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with possible severe adverse health outcomes such as cancers, birth defects, impaired immunity, endocrine disruption, developmental and reproductive effects, among others. The following information is not a study, but gathers some examples of pollutants, without claiming to be exhaustive. Many other items are related and the reader must study their own case in the framework of the countries linked to processing, storage, trade, use, disposal, and so forth. The goal is only to give a rough idea of the vast extent of the issue. For instance, banned, regulated, or suspect substances include:

• Gases such as CO2, carbon monoxide, hydrocarbons, nitrogen oxides, and sulfur dioxide.

• VOCs, formaldehyde, for example, form a broad category of volatile chemical compounds, some of which pose health hazards. The presence of VOCs in the atmosphere can also lead to the greenhouse effect, ozone layer depletion, and acidification.

• Chlorofluorocarbons

(CFCs), hydrochlorofluorocarbons, hydrofluorocarbons, perfluorocarbons, and other halogenated gases such as halogenated fluorocarbons, perfluorinated carbons, hydrofluorocarbons. Freons are CFCs with molecules having one or more hydrogen atoms replaced by halogens (chlorine and/or fluorine). Formerly used as coolants and expanding agents in insulation foam, they contribute to the depletion of the ozone layer and an increased greenhouse effect. Their use is now regulated or banned in many countries.

• Photochemical oxidants including ozone. • Various tiny solid or liquid particulates such as soot, dust, fumes, or mist. Dust can penetrate into a person’s lungs and pose health hazards. Asbestos is a well-known example. For example, among other things, remember that: • Some VOCs may include toluene, xylene, styrene, naphthalene, ethanol, trichloroethylene and other solvents, etc. Their use is now regulated or banned in many countries. • Not so well-known VOCs may be initiated by photochemical oxidants. • VOCs include various tiny solid or liquid particulates such as soot, dust, fumes, or

mist. Dust can penetrate into a person’s lungs and pose health hazards. Asbestos is a well-known example.

• Other chemicals, more hidden and pernicious, are often neglected such as, for example, plasticizers, organic fire retardants, curing agents, residual monomers, oligomers, bisphenol A, etc.

• Heavy metals including, among others, mercury (Hg), zinc (Zn), copper (Cu), cadmium (Cd), vanadium, and lead (Pb), are harmful if spread in the environment. • Hg is used in catalysts and is released by the combustion of fossil fuels and wastes. Organic Hg compounds act as cumulative poisons that affect the nervous system. • Zn used as a curing activator for rubber and for PVC stabilization. • Cu is used in pigments for plastics and rubbers. • Cd is a cumulatively toxic element. • Pb accumulates in biological systems and is linked to behavioral changes, paralysis, and blindness. It was used as a curing activator or stabilizer for certain polymers.

• Phosphorus derivatives: an excess of phosphorus compounds in surface water leads to eutrophication and algal bloom.

• Some plasticizers, fire-retardants, and other ingredients, sometimes used in significant amounts (tens of percent) have a nonnegligible volatility, more so the more they are incompatible with their polymer host: • Chloroparaffins or chlorinated paraffins that are stable organic compounds resistant to degradation and oxidation. Used as softeners and/or as flame-retardants in plastics and rubbers they are harmful primarily to aquatic life. • Polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs). These biologically persistent organic compounds containing bromine are used as fireretardants in plastics, for example, in housings for electrical equipment. • Polychlorinated biphenyls (PCBs) are biologically persistent organic compounds containing chlorine, particularly toxic to marine life. Sometimes used in rubber seals for

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electrical transformers and capacitors they are now being phased out and disposed of. Once again, these considerations are only a few examples and related legislation continuously evolves with countries, application sector, companies, and so forth, thus, needing complete and upto-date studies by designers and their teams. Example of REACH: REACH is a European directive (Registration Evaluation Authorization and Restriction of Chemicals), but also a Chinese regulation dealing with new chemical substance notification to the Chemical Registration Centre (CRC) of the Ministry of Environmental Protection (MEP). Failure to register will mean a substance cannot be manufactured or imported into the EU market. For chemicals used in significant quantities, industry must ensure that risks to human health and the environment are avoided or adequately controlled. Enterprises that manufacture or import more than a defined quantity of a chemical substance per year will be required to register the chemical in a central database. For high quantities, the submission of a Chemical Safety Report (CSR) is additionally required to document the safety assessment of the substance. The procedure considers several steps:

• Registration: Companies have the responsibility to collect information on the properties and the uses of substances that they manufacture or import at or above 1 t/year. They also have to make an assessment of the hazards and potential risks presented by the substance.

• Authorization: The authorization procedure aims to assure that the risks from substances of very high concern are properly controlled and that these substances are progressively replaced by suitable alternatives while ensuring the good functioning of the EU internal market.

• Restriction: Restrictions are a tool to protect human health and the environment from unacceptable risks posed by chemicals. Restrictions may limit or ban the manufacture, placing on the market, or use of a substance.

• Ban: Use of the concerned chemical is banned.

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Other examples of specific regulations or specifications include RoHS (Restriction of Hazardous Substances) and WEEE (Waste Electrical and Electronic Equipment):

• The RoHS directive restricts certain hazardous substances commonly used in electrical and electronic equipment. Do not confuse the EU RoHS and the Chinese RoHS; both target similar goals, but their approaches are different concerning the product categories, the restrictions, and the application schedule.

• The EU RoHS deals with, among other things: • heavy metals including Hg, Cd, hexavalent chromium and Pb, which are harmful if spread in the environment. • Organic species such as PBBs and PBDEs. These biologically persistent organic compounds containing bromine are used as fireretardants in plastics, for example, in housings for electrical equipment. Numerous other hazardous substances exist and can be involved in other regulations such as, for example:

• Metals: Zn, Cu, vanadium, etc. • Organic species: PCBs (already quoted), toluene, xylene, styrene, chloroparaffins or chlorinated paraffins, naphthalene, ethanol, trichloroethylene and other chlorinated solvents, etc.

• Phosphorus derivatives, etc. Be aware that some countries, departments, or even localities and companies have specific legislations.

4.3.11 Think Retrofitting of Machinery Generally speaking, retrofitting (rebuilding, rehabilitation, refurbishment, updating, etc.) consists of improving existing equipment, currently in service or inactive, using new parts newly developed or made available, to modernize and make more effective old equipment. Retrofitting is also commonly used for software; patches of software being designed to update computer programs and improve them.

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Retrofitting offers environmental advantages including, but not limited to:

• lower consumption of raw materials used for the retrofitted equipment (steel and other materials) versus new equipment

• • • •

benefiting from new technologies

• Prefer local materials and manufacturing means

• Think about the imbalance between production costs and environmental pollution caused by transports

• Prefer environment-friendly transport solutions, etc.

optimization of existing plants improvement of cycle times and productivity availability of more modern equipment for a modest investment

• avoiding disposal of the old equipment, etc. Other benefits may include:

• energy consumption savings • cost savings • higher throughput efficiency with subsequent environmental benefits

• adaptation of a plant for new or changed products

• guarantee of spare parts availability • possible quality warranty by the builder, etc. According to Van Dorn (http://www.sumitomoshi-demag.us/rebuilding.html) a rebuilt press should cost roughly 60% of the equivalent of a new machine.

4.5 Reduce Impacts of the Use Phase According to the manufactured part or product, the environmental cost of the use phase may be much higher than the environmental cost of the production phase. The following of this book deals with some of these points notably linked to lightweighting in automobiles and foam insulation in construction (see chapter 11 among others). For instance, some advantages, without claiming to be exhaustive, include:

• Reduce energy consumption during the use phase

• Favor renewable energy • Reduce consumption of consumable products during use, for example, fuel used for heating of foam insulated buildings

• Minimize hazardous emissions during the storage and use phases, etc.

4.4 Reduce Impact of Supply and Distribution Chains

Other examples include, for instance, common or active packaging for food and other perishable goods.

Parts, raw materials, and the supply and distribution of end products require transport and packaging, leading to environmental issues. Common sense measures and a more sophisticated organization can offer environmental advantages, for example:

4.6 Balancing the Product Durability and Actual Sustainable Benefits

• • • • •

Reduce product volume and weight Reduce packaging weight and volume Use sustainable materials for packaging Think about reusable packaging Optimize the distances between sources and areas of use

The plastics range offers high-performance grades as well as commodities or specific versions. So, it is possible to consider short or long lifetimes for the same end product using cheap or costly plastics, but designers must think about the actual lifetime. For an extreme and exaggerated example, costly long-lasting products are without interest for home waste bags, but packaging of radioactive

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waste needs high-performance materials. It is incorrect to build an LCA on a long lifetime and multiple reuses if it is a single-use product with a short use phase. In suitable cases:

• Design long-lasting products if appropriate • Optimize the balance between environmental impact and actual useful longevity

• Minimize and ease maintenance • Design for reuse, repair, and recycling

• Environmental advantages • Less damage to tools, notably injection

•

• •

4.7 Optimize the End-of-Life A smart waste hierarchy (see Fig. 1.3) is critical from an environmental point of view, needing:

• Integration of wastes into existing and efficient waste streams or the creation of new viable waste streams

• Easy disassembly of used parts • Easy recycling and effective reuse of recyclates • Design of new parts with nontoxic or unbanned materials, which allow for end-oflife recycling and effective reuse

• For repair, recycling, upgrading, etc., check safety and serviceability before reuse or trade

• Promote safe disposal of end-of-life products • As far as possible, ban landfilling

4.8 Competence Development, Training, e-Learning Suppliers of materials, machines, and software, and professional associations, universities, consultants, among others, propose training in all disciplines from basic up to top levels. Claimed general benefits include:

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• •

molds and extrusion dies, leading to longer useful life due to better mold and machine maintenance Reductions in unplanned machine downtime due to a better maintenance of machines, which leads to waste reduction, better productivity, and material and energy savings More efficient troubleshooting, fewer part defects, and improved quality, leading to better productivity Better planning of operations, timeous and quantitative delivery for a higher satisfaction of customers and reduction or suppression of related complaints Optimized cycle times, repeatable and reliable processes. Faster and fewer changeovers, which reduces waste A safer production floor

• Other advantages include: • Lower costs and higher output • Higher profits • More relaxed ambiance

References Dawson, A.J., et al. ANTEC 2002, p. 576. Lewan, M., et al., 2004. Plastics Rubbers Compos. 33 (4), 177. Sabreen, S.R. ANTEC 2005, p. 2875. Stansfield, J. ANTEC 2006, Charlotte, p. 428. Turconi, et al., 2013. Renew. Sustain. Energy Rev. 28, 555 565.

Further Reading Biron, M., 2017. Industrial Applications Renewable Plastics. Elsevier Ltd.

of

5 Eco-Design Rules for Plastics Sustainability Eco-design is a new strategy that requires designing differently, expanding thinking about the total life cycle to gain ground toward advanced sustainability. Of course, sustainability is not a reason to break general and specific laws, policies, directives, and regulations relating to plastics activities. The reader is solely responsible of their own problems and must study the requirements of the countries concerned for formulation, manufacture, commercialization, application, and waste disposal.

Sustainability is a relative and versatile concept related to the weight attributed to its three pillars (economic, environment, and social). There are no perfect answers to this serious problem, but several more or less easy ways can allow improvements in sustainability. Like the other steps of the life cycle, design alone is not representative of the sustainability of the end part. For example, a benefit coming from the selection of a renewable polymer can have a higher negative impact during the use phase, which can lead to net damage during the total life cycle. Fig. 5.1 displays a facet of the means helping to progress toward advanced sustainability due to compliance with the requirements of functionality, economy, regulations, and environment. The entire life cycle must be considered and the best solution depends of the whole context. The sustainability policy being defined, the choice of the polymer family and grade, and the optimization of the drawing of parts are even more critical than for traditional engineering design due to the additional handling of the sustainability of the designed product along its whole life cycle. Obviously, the environmental impact of its possible failure must be considered with its environmental effects in addition to economic features. Like with economic consequences, environmental damages

may be far higher than the environmental cost of the polymer part manufacture. So, a feature as common as weight having an effect on material consumption and possibly processing speed according to the traditional design also has additional environmental effects on transportation and leads to an overconsumption of fuel, thereby emitting more carbon dioxide (CO2) during all the use phase if the part is included in a mobility device. Objective goals and specifications and balance of requirements and performances are sharper than for traditional design. For example, actual lifetime is a major problem; higher performances or better resistance to aging lead to a better sustainability if the parts or goods are effectively used for a longer time. Conversely, additional economic and environmental costs are penalized if the user does not take advantage of the additional lifetime. Of course, the following is just a succinct reminder and eco-design must involve a skilled team using specific tools such as design software including a sustainability add-on. As well, the numerous interactions between parameters must be considered and selection cannot be based on one or even a few indicators. Main interactions include, but are not limited to:

• Weight determining saving or wasting energy during the use phase. Well-known examples relate to automotive and aerospace industries.

• Insulation leading to saving or wasting energy during the use phase. Buildings and cold stores (or hot stores) are representatives of this case.

• Longer useful life improving the sustainability during the use phase and avoiding the fabrication of a replacement product. For example, the production of shuttle packaging may require more energy, but its reuse saves the energy that would have been consumed by the production of the second and next nonreusable packaging.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00005-7 © 2020 Elsevier Ltd. All rights reserved.

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Advanced sustainability

Environmental compliance Regulation compliance Economic viability Functional capability

Figure 5.1 Overview of means helping to progress toward advanced sustainability.

Another problem is the replacement of one pollution type by another, which requires judgment on the advantages and drawbacks of the respective pollutions. For example:

• A renewable polymer based on cultivated plants uses and pollutes water, but saves fossil feedstocks and absorbs CO2 due to the growing of plants; conversely, a fossil polymer saves water, but consumes fossil feedstocks and emits CO2. The preferred solution depends on the environmental context and may change with country and time.

• Nuclear energy drastically reduces CO2 emissions, but may induce nuclear pollution for centuries. For a defined case, the best solution in a defined context can be without interest for another case. For example, the use of green electricity is of interest if green electricity is really accessible.

5.1 Examples of Environmental Traps This section deals with subjectively chosen cases that are not rules; a beneficial step can lead to a reduction in total pollution for the complete life cycle in the best cases or conversely an increase of pollution for other examples. These traps are only a few examples and many other cases may be encountered.

5.1.1 Favorable Example of Automotive Industry: Reduction of Production Impact Matches a Net Impact Reduction Due to the Use Phase Weight saving is a good way for reducing fuel consumption during the use phase. Generally, it is expected that every 10% reduction in vehicle mass improves fuel economy by about 7%. Reducing vehicle mass by 30% directly results in about a

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Table 5.1 Examples of GHG Emissions for Diverse Cars. GHG for Production (kg CO2 equiv.)

GHG for Use Phase (kg CO2 equiv.)

Total GHG (kg CO2 equiv.)

Minimum

2870

15,000

17,870

Mean

4790

44,500

49,290

Maximum

6300

73,000

79,300

% GHG for Production

% GHG for Use Phase

% Total GHG

Car A

5

95

100

Car B

8

92

100

Car C

15

85

100

Car D

25

75

100

GHG, greenhouse gas.

Table 5.2 Examples of Energy Consumption and GHG Emissions for Sustainable and Traditional Houses. Sustainable House

Traditional House

Energy for construction, GJ

1669

1509

50 years energy, GJ consumption

4700

14,500

Total energy, GJ

6369

16,009

370

1010

Energy consumption

GWP, tons of CO2 equivalent Total GWP, tons of CO2 equivalent GHG, greenhouse gas; GWP, global warming potential.

21% miles per galon (MPG) increase. In addition, for a 1 kg primary mass reduction, there is up to 0.5 0.7 kg of secondary mass reduction. Of course, reduced fuel consumption reduces CO2 emissions. Mass reduction has also positive effects on vehicle performance. The lifetime of cars is on the order of between 100,000 miles and 150,000 miles with a fuel consumption on the order of between 8 and 20 L/100 miles, that is to say 8000 L to 30,000 L for the use phase. If 1 L of fuel produces 30 MJ, use phase energy can be appraised to between 240,000 and 900,000 MJ. So, if a 10% weight saving reduces fuel consumption by 7%, use phase energy consumption can be reduced by between 16,800 and 63,000 MJ. Of course, greenhouse gas (GHG) emissions are also reduced. Table 5.1 displays some results of GHG emissions for three cars. Results are broadly spread depending on the retained methods of assessment, type of car,

lifetime hypothesis, etc., but it is sure that use phase is by far of prime importance. In that case, the car emitting the lowest GHGs for production is also the lowest emitter of GHGs for the use phase. That is an example, not a rule and counterexamples may exist.

5.1.2 Counterexample of House Building: Increase of Production Impact Leads to a Final Impact Mitigation due to the Use Phase Among many parameters, a sustainable house (SH) designed to minimize heating and cooling energy uses 4500 kg of polymer in addition to the polymers used in a traditional house. Table 5.2 displays a higher energy consumption for construction of the SH, but a much lower energy consumption during use phase leading to a total saving during the whole life cycle. Life cycle

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Table 5.3 Indicator Examples for Diverse Electricity Generation Modes. Water

CO2 equiv.

Cd

L/MW/h

kg/MW/h

mg/MW/h

Average

3800

430

13

Median

1950

310

1

Minimum

7

1

0.03

Maximum

14,500

1200

50

GHG emissions are in line with the energy scenario. Of course, all the savings are not induced by a higher use of polymers, but relate to the whole solution. Total gains are impressive, about 60% and 63% for energy and global warming potential (GWP), respectively.

5.1.3 Selection of Energy Production Method can Replace a Pollution Type by Another First, it must be pointed out the enormous ranges of three studied environmental indicators according to the type of electricity generation from coal to wind power through to other fossil fuels, hydrogeneration, solar, and nuclear sources, etc. Table 5.3 displays imbalances between averages and medians and a factor in the thousand order between minimum and maximum. Of course, different figures may be found elsewhere and those figures cannot be used to compute technical or economic goals. Second, the selection of the type of generation determines different pollutions. Making a shortcut excessively brief (other pollutions exist):

• Carbon-based fuels (coal, oil, or gas); burning carbon-based fuels produces large amounts of CO2, which causes climate change. They can also produce other pollutants such as sulfurous or nitrogen oxides, which cause acid rain.

• Nuclear power plants do not directly emit CO2, but they may eject waste heat that can result in adverse effects on aquatic life. The emission of radioactivity is the main problem from nuclear plants. Abnormal operation or a tsunami caused by an earthquake (e.g., Fukushima Daiichi nuclear disaster) may result in the release of radioactivity. So the structure of the reactor and its environment become

radioactive. It will require decades of nuclear inactivity and huge labor before the site can be economically dismantled. In normal conditions, the radioactivity of nuclear waste can persist for centuries.

• Large hydropower plants generate very low emissions, but the flooding of reservoirs behind dams and slowing of the flow of rivers below dams can have serious impacts on the ecology around the dam.

• Renewable generators such as wind turbines and solar cells emit no GHGs at the point of generation and very low amounts of GHGs across their entire life cycle, but many renewable sources do not produce electricity predictably or consistently. Electricity generation from wind turbines varies with the wind speed, while the output of solar panels depends on the time of day and the amount of cloud cover. So, these sources have to be coupled with other sources and/or storage devices. These few examples lead to the conclusion that several indicators must be taken into account among the list of main indicators including but not limited to:

• • • • • • • • • •

Energy consumption CO2 and other GHGs, GWP Water footprint Toxicity, unwanted emissions Ozone depletion, photochemical oxidation Photochemical smog Acidification Eutrophication Solid waste emission Other diverse indicators

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5.2 Specific Plastics Design Issues First and foremost, a sustainability attitude jointly entails the design of products of fair marketable quality and an attractive sustainability balance for the entire life cycle. This bipolar requirement must be continuously taken into account. The design of marketable products obeys general principles of plastics parts design taking into account some plastic features that could surprise designers usually working with steels and other metals; the sensitivity to temperature, humidity, creep, stress relaxation, chemicals, and more generally, viscoelasticity. The final choice results from numerous iterations leading to a subtle balance of technical requirements, sustainability considerations, economic constraints, and targeted lifetime. The following proposes some ways of thinking for a systematic design approach helping designers to think about some tracks allowing to build efficient and realistic goals. It is not possible to cover all cases and it is the responsibility of the reader to choose the suitable tracks and to add specific constraints related to their own problem. The reader must build their own scheme corresponding to their own case, general and local contexts, applicable regulations, etc. In addition to general design rules, plastics parts must obey specific plastics rules related to the geometry of the part, technical requirements, aesthetics and other sensorial properties, economics; regulations, health and safety requirements, and sustainability. The main points relate to, but are not limited to:

• • • • • • • • • •

Mechanical loading Heat behavior Low temperature behavior Dimensional stability Electrical properties Fire behavior Sensory properties Economics Lifetime and end-of-life criteria Regulation, health, and safety requirements

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Example of modulus (GPa) versus temperature (°C) (A) 5

0 –40 (B)

300 Example of creep modulus (GPa) versus time (h)

1

GPa

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0 0

h

1000

Figure 5.2 Examples of modulus variations versus temperature (A) or time (B) for two thermoplastics.

Fig. 5.2 shows two surprising behaviors of plastics. Of course, regulations, safety requirements, and specific and general standards applied in various countries to the manufacture, application, and disposal of plastics products must be fulfilled. Economic features are of prime importance as far as plastics are often used to reduce cost of devices usually made of metals or other traditional materials.

5.3 Overview of Material Sustainability Impact Some ways toward better sustainability are common with general rules of design, for example:

• • • • • •

Minimize manufacturing waste Design for production quality control Minimize energy use in production Minimize number of production steps Minimize number of components/materials Seek to eliminate toxic emissions during manufacturing, use, and disposal

• Create a timeless aesthetic • Design for durability

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5.3.1 General Pathway toward Mitigation of Material Impact The following includes measures of common sense and some technical tracks specifically linked to the environment:

• Use materials from reliable providers, which avoids nonconformity, process trouble, production breaks, wastes, etc. All these problems consume materials, energy, labor, and other resources, and emit pollution, which is totally at the opposite of sustainability.

• Minimize the amount of material consumed for a defined functionality; obviously material saving is one of the pillars of sustainability as long as the targeted functionality is provided. The use of CAD software (see Chapter 4: Easy Measures Relating to Improved Plastics Sustainability) allows optimization of used material weight for given requirements. For the case of a product consuming high energy during the use phase, automotive for example, a weight reduction can have direct and indirect benefits such as:

• Fuel economy: Reducing vehicle mass by 30% results in about a 21% MPG increase.

• Secondary mass reduction: For 1 kg primary mass reduction, there is between 0.5 and 0.7 kg of secondary mass reduction.

• Saving of fossil resources relates to the raw material use and fuel savings.

• positive effect on vehicle performance • reduction of CO2 (and other pollutants) emissions due to the lower fuel consumption, for example: The use of 1 L of petrol approximately results in 2.4 kg of CO2 emitted into the atmosphere. The use of 1 L of diesel results in about 2.7 kg of CO2 emitted into the atmosphere. The use of 1 L of fossil fuel and bioethanol blend results in approximately 1 kg of CO2 emitted into the atmosphere. Conversely, for some products, the effect of weight on the use phase is negligible. A weight saving for a TV cabinet induces benefit for transport only.

• Select materials having as low densities as possible for suitable performance. As seen previously, mass reduction for appropriate performance can lead to energy reduction for the use phase. Of course, conversely, an increase of mass due to higher density and lower performance level of an alternative material compensated for by thicker parts leads to an overconsumption of energy and a higher pollution during the use phase.

• Avoid materials that deplete nonrenewable natural resources and choose renewable resources, recycled or reclaimed materials, and waste byproducts. However, the environmental cost of the recycling, reuse, and recovery as well as the quality of the end products must be considered. Use of waste has the additional advantage of creating value for products that would otherwise be expensively processed. For example, the typical new lead battery contains 60% 80% plastic and can be recycled by a permitted recycler under strict environmental regulations. The plastic and lead are reclaimed and sent to a new battery manufacturer. The recycling and reuse by an efficient recycling process can lower the ecological impact by nearly 50%. Today the quality of recycled plastic is the biggest challenge preventing industry from using more recycled materials. So, new approaches of recycling are being developed to open new opportunities. For example, with the aim to improve recycled polypropylene (PP) quality, Procter & Gamble in partnership with PureCycle Technologies and Innventure developed a purification technology that is claimed to be a breakthrough toward the delivery of nearly identical performance and properties as virgin materials by a better removal of contaminants, malodors, and colors from used PP. This purification technology allows for the level of recycled plastics in existing applications to be increased and broadens the application field of recycled PP.

• Of course, avoid or ban materials that damage human or ecological health.

5.3.2 Examples of Impact of Material Selection on Other Parameters The previous overview (see Section 5.3) does not take into consideration the complex possible

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Mechanical Static Impact Creep Relaxation Dynamic

165

Environment

Regulations

Resource depletion Pollution End of life

Safety Health

Ageing

Aspect

Specific

Temperature Light, Sun, UV Water, Humidity Chemicals Lifetime

Geometry Dimensional stability Aesthetics Sensory

Fire Food contact Conductivity Magnetic

Temperature Low High Aging

Economics Cost Profitability

Figure 5.3 Diagrammatic overview of some design issues.

repercussions on the selection of material type, processing, use step, etc. Fig. 5.3 shows examples of possible consequences, but other items are likely to be discerned in specific studied cases.

• Use local materials and production that minimizes transport

• Use lowest impact transport system • Design for second life with a similar or different function

5.3.3 Have an Overall View of Sustainability including Late Phases Design plays a direct role, but also may motivate a user’s sustainable behavior, leading to:

• • • •

Reduce energy consumption during use

• • • •

Design for carbon neutral or renewable energy

Reduce material consumption during use Reduce water consumption during use Design to encourage low consumption behavior of users Reduce product and packaging volume Reduce product and packaging weight Prefer reusable packaging systems

• • • •

Design for reuse of components Design upgradeable products Design for maintenance and easy repair Design for reuse and exchange of products

5.4 Design to Withstand Mechanical Loading Most likely, mechanical loading is the most common constraint along with temperature. Uniaxial loading is the most studied. Multiaxial loadings are rarely treated in the literature, as special tests have to be conducted for their study. Please note that bulk modulus is several times higher than uniaxial modulus.

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Table 5.4 Statistical Analysis of Main Tensile Properties of About 500 Thermoplastic Grades. Yield Strength (MPa)

Strain at Yield (%)

Tensile Modulus (GPa)

Median

70

3

3.55

Minimum

2

0.3

0.001

Maximum

323

75

37

Samples

492

402

552

Please note that mechanical loading can be involuntary, resulting from residual stresses induced by the manufacturing process.

5.4.1 Overview Formerly, it must be noted that actual mechanical behavior is not an intrinsic property, but depends on numerous parameters including, among others, the shape of the part, the processing conditions, and the general historical past of the part. To provide a general rough idea of thermoplastics properties, Table 5.4 displays statistical analysis of tensile properties for about 500 grades including commodities, engineering, and highperforming thermoplastics. Please note that yield strength and tensile modulus of commodity thermoplastics are lower than these medians and consequently, results for actual molded commodity thermoplastics are also lower. Mechanical behavior is time-dependent and temperature-dependent (see Fig. 5.2), resulting in the need to simultaneously consider the three-pillar system, namely load-time-temperature. Fig. 5.4 displays the main ins and outs related to mechanical loading.

5.4.2 Temperature Effect It can be noticed that small temperature changes can lead to significant loading behavior differences. For example, 10°C or 30°C aren’t room temperature for some soft plastics as can be seen for the below examples given to provide a rough idea of the significant differences.

• The tensile strength at 30°C is about 85% of the value at room temperature for a defined soft commodity thermoplastic.

• The tensile strength at 30°C is about 90% of the value at room temperature for a defined hard commodity thermoplastic.

Mechanical loading: the ins and outs

Load nature: tensile, flex, compression, torsion,wear, impact... Time: immediate, short or long term Continuous, cyclic Temperatures: high and low Creep, relaxation, dynamic fatigue Dimensional effects Combination with other parameters Lifetime

Figure 5.4 Mechanical loading: the ins and outs.

For other examples, the decrease can be much lower or even negligible. Low temperatures lead firstly to an increase of modulus and then to the brittleness of a given part.

5.4.3 Loading Type Effect The type of loading is important. For example, for most thermoplastics, tensile and flexural properties are often more or less similar, but compressive or torsional behaviors are different when wear is atypical. Impact resistance is an often-tested special property.

5.4.4 Strain Rate or Time Effect Designers can be tricked by interpretation of standard data. First, test pieces have optimized shapes and are manufactured in the best conditions leading to the highest mechanical properties.

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Second, most loading tests are short uniaxial loadings not representative of high-speed loadings, on the one hand, and creep or relaxation on the other hand. The tensile behaviors listed below are only examples given to provide a rough idea of the huge differences. For a given soft commodity thermoplastic, tensile stresses leading to a 1% elongation at room temperature are about:

• • • •

9 MPa according to standard tensile tests 7 or 8 MPa according to 1 h creep tests

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Table 5.5 Statistical Analysis of Notched Izod Impact Strength (J/m) for about 450 Thermoplastic Grades. Median

93

Minimum

4

Maximum

Nonbreak

Samples

448

Table 5.6 Statistical Analysis of Rockwell M Hardness for about 350 Thermoplastic Grades.

4 MPa according to 100 h creep tests

Median

50

2 MPa according to 50-year creep tests

Minimum

B0

Maximum

125

Samples

352

For other examples, the decrease can be much lower or even negligible.

5.4.5 Impact Behavior Impact tests measure the absorbed energy during a specified impact of a standard weight striking, at a given speed, a test sample clamped with a suitable system. The hammer could be a falling weight or, more often, a pendulum. In this case, the samples can be smooth or notched. The results depend on the molecular orientation and the degree of crystallization of the material in the sample, its size, the clamping system, the possible notch and its form, the mass, and the strike speed. The values found in the literature, even for instrumented multiaxial impact (ISO 6603-2:2000), can only be used to help choose and do not replace tests on real parts. The Izod and Charpy impact tests are mostly used. A defined pendulum strikes the specimen sample, notched or unnotched, clamped with a defined device. The absorbed energy is calculated and can be expressed for notched impacts:

• In kJ/m2: The absorbed energy is divided by the specimen area at the notch.

• In J/m: The absorbed energy is divided by the length of the notch, which is also the thickness of the sample. There is no true correlation between the two methods. The notched impact tests tend to measure the notch sensitivity rather than the real impact strength of the material. It corresponds better to parts with sharp edges, ribs, and so on.

To provide a general rough idea of thermoplastics properties, Table 5.5 displays statistical analysis of notched Izod impact strength for about 450 grades.

5.4.6 Hardness The most usual test methods are:

• • • •

Rockwell R, M, and others Shore A for soft polymers Shore D for hard polymers Ball indentation

There are no mathematical correlations between the various methods. To provide a general rough idea of thermoplastics properties, Table 5.6 displays statistical analysis of Rockwell M hardness for about 350 grades.

5.4.7 Dynamic Fatigue The repetitive mechanical loading and unloading of a polymer leads to a speedier failure than an instantaneous loading. The Wohler curves (or SN curves) plot the level of stress or strain (S) leading to failure after N cycles of repeated loading. Two basic types of tests coexist, namely:

• at defined stress or • at defined strain.

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Results are quite different. Plastics being sensitive to creep, fatigue tests at defined strain are generally less severe than those at defined stress for comparable original stresses. The results depend on the stress type and level, the frequency, the surrounding temperature, and the geometry of the sample. For a pipe made of a commodity soft thermoplastic suitable for 100,000 cycles in defined conditions, the load must be reduced by: 5%

For 500,000 cycles

12%

For 1,000,000 cycles

26%

For 5,000,000 cycles

32%

For 10,000,000 cycles

radiations, etc. Other parameters being unchanged, a loading reduction generally leads to an increase of the lifetime.

5.4.11 Environmental Cost of Reinforcements 5.4.11.1 Fibers To stretch the limits of plastics, fibers are commonly incorporated, leading to general purpose and hi-tech composites. Nanofibers and graphene uses are growing for hi-tech and special compounds. The benefits for functional properties go along with environmental consequences.

• Glass fibers (GFs) are the most commonly used reinforcements, accounting for 95% of the consumption of fibers for plastics reinforcement.

These examples are given to provide a rough idea of the significant differences. Other very different data can be found elsewhere.

• Aramid (AF) and carbon fibers (CF) account

5.4.8 Dimensional Effects

• Natural fibers (NF) such as jute, flax, and so

Obviously, loading modifies the shape of the part according to its nature. For example, a uniaxial tensile stress leads to an elongation in the stress direction and a retraction in the transverse directions. Please note that Poisson’s ratios are inferior to 0.5.

5.4.9 Combination with other Parameters The loading must be reduced in the case of simultaneous exposition to light, UV, water, chemicals, pressure, radiations, etc. For example, for a pipe made of a commodity soft thermoplastic bearing a defined load, the service load must be reduced by:

• • • •

20% for water supply 50% for natural gas 50% for compressed air 55% for liquefied petroleum gas (LPG)

5.4.10 Lifetime Lifetime results from a balance between mechanical resistance and service load of the chosen plastic, temperature, time, creep, relaxation, dynamic stresses, light, UV, water, chemicals, pressure,

for most of the remaining 5%. on are making a comeback due to sustainability requirements. Numerous other fibers have specific uses:

• textile fibers such as nylon and polyester; • industrial fibers such as PE, polytetrafluoroethylene (PTFE), and polyphenylene benzooxazole (PBO: Zylon);

• steel fibers and steel cords; • mineral fibers such as boron, quartz, and whiskers. The performances of a given fiber, its cost, and sustainability requirements drive its use in composites, for example:

• • • •

CFs are used for advanced composites; AFs are used for intermediate composites; GFs are used for general-purpose composites; nylon and other textile fibers are used for flexible composites;

• sustainable fibers are used for economic and environmental reasons;

• steel fibers are used for tires, conveyor belts, electrostatic discharge (ESD) compounds.

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The practical goals of fiber reinforcement are:

• The cost-saving possibilities at constant

FOR

• to increase the modulus and strength; • to improve the heat deflection temperature (HDT);

• to reduce the tendency to creep under continuous loading;

• to save costs by decreasing the material cost used to obtain the same stiffening. Fibers used at levels as diverse as 10% 50% can lead to:

• Environmental behavior changes. • The risk of shortened fiber length due to breakage during processing.

• Anisotropy due to fiber orientation and settling. With some processes, this is an advantage; the appropriate placement of the fibers permits reinforcement at specific points in the right direction.

performances.

• • • • •

• general sustainability features; • high thermal resistance; • insulating properties with unfortunate consequences for electrostatic discharge;

• elastic modulus in the range 50 90 GPa, much higher than polymer, but lower than for CF-reinforced plastics;

• • • •

low coefficient of thermal expansion (CTE); high density; brittleness under high stresses during processing; abrasive properties harmful for tools.

GFs are generally chosen for:

• Their versatility of sizing, which allows for the choice of the right solution for each polymer.

• Their high specific mechanical performances. • Their dimensional stability due to their CTE and low water absorption.

• The low cost of the raw material.

The incombustibility of a mineral material. The chemical resistance of the glass. Their insensitivity to putrefaction. Their thermal conductivity.

Nevertheless, their use in polymers produces some constraints because of:

• The environmental cost that can be overcompensated for by energy savings during the use phase.

• The lack of surface conductivity for electrostatic discharge.

• The need to employ wear-resistant materials for the equipment parts exposed to the reinforced polymer.

• The special design of the processing equipment and parts to eliminate or reduce the settling of the fibers and abrasion wear.

For each type of fiber many variants are proposed. All GFs have in common

Their insulating properties.

Carbon Fibers

The characteristics of CFs vary according to the process and the grades. Intended for highperformance applications because of their cost, CFs have excellent mechanical properties, but are sensitive to impact and abrasion. They are used for their attractive characteristics such as:

• • • • • • • • •

high tensile strength high modulus high creep resistance high fatigue resistance high dielectric conductivity high thermal conductivity lower density than GFs low coefficient of friction low CTE

On the other hand, their drawbacks generally include:

• low impact strength • low abrasion resistance

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• high cost • environmental cost

Examples of energy use (MJ/kg) for the production of NF, GF, CF are respectively:

CFs are used in various forms for polymer reinforcement:

• short fibers dispersed in the matrix • yarns, rovings, stratipregs or prepregs, mats, and 2D and 3D reinforcing structures As for GFs, reinforcement with continuous fibers leads to the highest performances. Compared to short GFs, short CFs yield higher reinforcement ratios for the modulus and tensile strengths, but the impact strength decreases. Natural Fibers

There is renewed interest in NFs as sustainable materials to replace industrial GFs in generalpurpose composites. Several reasons push their use:

• environmental and ecological criteria; • economic considerations, which lead some nations to give priority to local materials;

• local politics promoting agricultural activities instead of industrial means;

• increasing plastic consumption, which needs increasing quantities of GFs. Generally, compared to GFs, natural vegetal (or plant-based) fibers offer advantages, but also drawbacks, for example:

• The outputs are sometimes a little low, which limits development industrialization.

studies

and

• The price is often attractive, but there are exceptions, and the performance/price ratios are rarely favorable.

• • • •

Density is always attractive. Mechanical properties are lower but fair. Recycling is theoretically easier. Long-term effects of temperature, moisture, and light are unfavorable.

• Average

12

35

270

• Standard deviation

8.3

11.6

80

• Minimum

4

13

183

• Maximum

21

51

339

• Samples

5

13

3

Examples of GWP for production of NF, GF, CF are respectively: • Average

1.3

1.6

27

• Standard deviation

NA

0.3

NA

• Minimum

NA

1.2

22

• Maximum

NA

2

31

• Samples

4

6

2

NA: not available

There is lingering doubt over these results and other data can be found in the literature. These results don’t take into account other pollution types such as acidification potential, eutrophication potential, photochemical ozone creation potential, etc., that are sometimes higher for natural-sourced products. In the following example (adapted from S.V. Joshi, Al, Are natural fiber composites environmentally superior to GF reinforced composites? Sci. Direct Compos. A 35 (2004) 371 376) displaying data for GF and NF, respectively, nitrates are about 1700-times higher for NF and phosphates are 5-times higher for NF. All the other results are beneficial for NF. These data relate to a single version of GF and NF and are not rules. They are only intended to give a rough idea of the possible problems. • SOx

9

1.2

(g/kg)

3

1.1

(g/kg)

1

0.2

to

(mg/kg)

1.8

0.4

to

(mg/kg)

19

2.3

• NOx emissions

• Particulate matter

• BOD water

• COD Cost savings of up to 60% are claimed when performances are not essential.

(g/kg)

emissions

water (Continued )

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—Cont’d

• Nitrates

to

(mg/kg)

14

24,000

(mg/kg)

43

234

water

• Phosphates to water

BOD, Biochemical oxygen demand; COD, chemical oxygen demand

5.4.11.2 Natural Mineral Fillers Indicator examples for 1 kg mineral fillers (adapted from www.ima-europe.eu/sites/ima-europe.eu/files/publications/) include:

• Primary

energy

consumption

(MJ/kg)

2.2 2.86

• • • •

Water consumption (L/kg) 1.6 4.6

171

is often low, a few percent, for instance. Examples of the energy used for six CNT samples and seven graphene samples are respectively: • Mean

8400

862

• Median

8400

900

• Standard deviation

133,400

617

• Minimum

480

70

• Maximum

325,000

2000

There is lingering doubt over these results and other data can be found in the literature. These results do not take into account other pollution types such as GWP, acidification potential, eutrophication potential, photochemical ozone creation potential, etc.

GWP (g equiv. CO2/kg) 92 120 Acidification (g equiv. SO2/kg) 0.4 0.6 Abiotic depletion (g equiv. Sb/kg) 0.85 1.04

These data relate to examples only and are not rules. They are only intended to give a rough idea of specific examples. Apart from special uses, natural mineral fillers are generally incorporated at high levels, tens of percent, for example.

5.4.11.3 Cellulose Nanofibers The properties of cellulose nanofibers will provide new opportunities to compete with GFreinforced plastics and manufacture innovative bioplastics in a wide range of applications for a variety of sectors and markets such as the aerospace, automotive, chemical, optics, textile, and forestry industries. Tensile strength of nanocellulose fibers may be 10- to 20-times that of NFs and modulus may be 4to 8-times that of NFs. Pollution due to nanocellulose fiber production hugely differs according to the process used. For example, energy use data can be found in the range of between 110 and 1300 MJ/kg of nanocellulose fibers.

5.5 Plastics Behavior Above Ambient Temperature Formerly, it must be noted that thermal behavior is not an intrinsic property, but depends on numerous parameters including, among others, the shape of the part, the exposition time, the processing conditions, and the general historical past of the part. Fig. 5.5 displays the main ins and outs related to the heat behavior of plastics. Heat: the ins and outs

Minimum, maximum, average temperature Time: immediate, short or long term

Peak, continuous, cyclic Wet or dry ambiance Dimensional stability, thermal expansion

Combination with other parameters

5.4.11.4 Carbon Nanotubes and Graphene Carbon nanotubes (CNT) and graphene are generally more polluting, but their level in compounds

Lifetime

Figure 5.5 Heat: the ins and outs.

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172

A temperature phenomena:

rise

causes

two

different

• Immediate physical effects, that is, the decay of the modulus and other mechanical and physical properties, physicochemical softening, reversible thermal expansion, and, eventually, irreversible shrinkage and warpage. After a return to room temperature, modulus and other mechanical properties recover their initial values.

• Long-term effects, that is, irreversible creep and relaxation for stressed parts, irreversible chemical aging and related degradation of the material with decreases in mechanical properties, even after a return to room temperature. The maximum service temperatures depend on the duration of service and the possible simultaneous application of mechanical stresses or other constraints. For aging studies, temperature can be combined with humidity, which often leads to more severe degradations.

5.5.1 Average Temperature For small temperature variations, it is possible to use an average material temperature determined with respect to time. The average temperature (Tm) may be considered to be the weighted average of temperatures (Tn) in accordance with the proportion of time (Lm) spent at each temperature: Tm 5 T1 L1 1 T2 L2 1 ? 1 Tn Ln For broad temperature variations, a more complex procedure must be formulated taking into account a model of the degradation as a function of the temperature. The Arrhenius equation is one of the best-known models for assessing the lifetime of polymers and is commonly used to predict the combined effects of temperature and time. The Arrhenius relationship is:   2E KT 5 A exp RT where KT is the reaction rate for the process; E is the reaction energy; R is the gas constant; T is the absolute temperature.

Other models are also used, but generally speaking it must be noted that a model is an equation giving a result in all cases. In real life, results can be completely different and the part can fail when the model predicts a longer life (or conversely, a shorter life). The user must be aware of the risks. Conventional heat measurements and arbitrary evaluations include:

• • • • •

continuous use temperature (CUT) Underwriter Laboratories (UL) temperature index HDT Vicat softening temperature (VST) accelerated aging

5.5.2 Continuous Use Temperature The CUT is an arbitrary temperature resulting from general experience and observation. It is the maximum temperature that an unstressed part can withstand for a long time without failure or loss of function, even if there is a significant reduction in the initial properties. This subjective value is not measurable and is deduced from aging test interpretations and information collected in the technical literature. To give some idea, CUTs for thermoplastics are in the range of 50°C 400°C for exceptional families. Please note that samples are unstressed, which is not realistic for numerous applications.

5.5.3 Underwriter Laboratories Temperature Index The temperature index, derived from long-term oven-aging test programs, is the maximum temperature that causes a 50% decay of the studied characteristics in the long term. The UL temperature index depends on:

• the tested grade • the thickness of the tested samples • the studied characteristics Influence of grade For two grades of mineral-filled nylon 66, of the same thickness and for the same properties, the UL temperature indices are 65°C and 80°C.

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For three grades of epoxy resins, of the same thickness and for the same properties, the UL temperature indices are 160°C, 170°C, and 180°C. Influence of thickness UL temperature indices increase with the thickness of the samples. For example, for a defined polymer grade, the UL temperature indices are:

• 200°C for a 2.1 mm thickness • 50°C for a 0.4 mm thickness Influence of the studied characteristics There are three categories of UL temperature indices:

• electrical properties only • electrical and mechanical properties, impact excluded

• electrical and mechanical properties, impact included For the same grade in the same thickness, the three indices can be identical or different. To give a general idea, UL temperature indices of thermoplastics are in the range of 50°C to more than 200°C for exceptional families. Like all the laboratory methods, the temperature index is an arbitrary measurement that must be interpreted and must constitute only one of the elements by which judgment is made.

5.5.4 Heat Deflection Temperature The HDT is the temperature at which a standard deflection occurs for defined test samples subjected to a given bending load and a linear increase in temperature. The stresses usually selected are 0.46 MPa (HDT B) or 1.8 MPa (HDT A) and must be indicated with the results. In any case, a polymer cannot be used under this load at this temperature. Generally, HDTs are in the range of 20°C to more than 400°C for exceptional families. For a given thermoplastic family, HDT is affected by reinforcements, fillers, and plasticizers.

5.5.5 Vicat Softening Temperature The VST is the temperature at which a standard deflection occurs for defined test samples

173

subjected to a given linear temperature increase and a compression loading from a defined indenter of a specified weight. The load used is often 10 N (Vicat A) or 50 N (Vicat B) and must be indicated with the results. In either case, a polymer cannot be used under this compression load at this temperature. For a given thermoplastic family, VST is affected by reinforcements, fillers, and plasticizers. HDT and VST are not strictly linked, but there is a certain relationship, and when HDT is low, VST is also low.

5.5.6 Accelerated Aging Conventional accelerated aging tests consist of exposing defined samples to controlled-temperature air in ovens protected from light, ozone, and chemicals, for one or more given durations. The degradation is measured by the variation at room temperature of one or several physical or mechanical characteristics during the aging. The variations of impact resistance, hardness, tensile or flexural strength, and color are the most frequently studied. Sometimes, properties are measured at the aging temperature, which is a more severe method. Accelerated aging is an arbitrary measurement that must be interpreted and must constitute only one of the elements used in making a judgment:

• Under identical conditions, the properties do not all degrade at the same rate.

• It is impossible to establish a direct relationship between the accelerated aging of a part and its real lifespan. For an unknown polymer, the results of accelerated aging must be compared with those obtained on a known polymer of a similar formula.

5.5.7 Environmental Cost of Stabilizers and Antioxidants First remember that heavy metals including mercury, zinc, copper, cadmium, vanadium, and lead are harmful if spread in the environment. Many regulations deal with their use, ban, and wastes. Examples include, but are not limited to:

• Zinc (Zn) used for polyvinyl chloride (PVC) stabilization and as a curing activator for rubber.

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• Cadmium (Cd) is a cumulatively toxic element. • Lead (Pb) accumulates in biological systems and is linked to behavioral changes, paralysis, and blindness. It was used as a curing activator or stabilizer for certain polymers. Organic stabilizers and antioxidants must be individually studied.

5.6 Low Temperature Behavior Fig. 5.6 displays the ins and outs related to lowtemperature behavior of plastics. A fall in temperature has only physical effects:

• Increase in the modulus and rigidity. The modulus can be up to 100 or more times higher than that measured at room temperature.

• Reduction in the impact resistance; the material can become brittle. For example, commodity thermoplastics can have low-temperatures of service of 2110°C, 210°C, 0°C, or even 20°C.

• Eventually, crystallization for semicrystalline polymers. Apart from mechanical effects, low temperatures reduce degradations by aging and are sometimes

used to store parts (prepreg, thermosets), which lead to longer lifetimes. A temperature decay leads to a retraction according to the CTE. To provide a general idea of minimum service temperatures, Table 5.7 displays a statistical analysis of low-temperature service for about 350 thermoplastic grades. The minimum service temperature is an arbitrary temperature resulting from general experience and observation.

5.6.1 Low-temperature Tests There are many methods to test lowtemperature behavior, but none can be used directly needing careful interpretations. The possibility of using a plastic at low temperature depends on the service conditions including loading and impacts. Some grades can be used at 200°C or less if there are no impacts. Some other plastics can be brittle at ambient temperature like the polystyrene used for yoghurt packaging. It is necessary to distinguish:

• Short-term tests: Brittle point, low-temperature impact test, low-temperature rigidity, and elastic recovery for elastomers such as silicone.

• Long-term tests: Crystallization tests, which make it possible to detect a slow crystallization by the evolution of hardness with time.

5.6.2 Brittle Point Low temperatures: the ins and outs

Minimum, maximum, average Time: immediate, short or long term Peak, continuous, cyclic Impact behavior Dimensional stability Combination with other parameters Lifetime

Figure 5.6 Low temperatures: the ins and outs.

The loose definition of the brittle point is based on a more or less sudden reduction in the impact resistance or the flexibility. The indicated values must be carefully considered.

• Low-temperature impact tests: Cooled samples are subjected to a conventional impact test. Generally, the most often used temperatures are 20°C, 30°C, or 40°C. Table 5.7 Statistical Analysis of Minimum Service Temperatures for about 350 Thermoplastic Grades. Median

240

Minimum

2250

Maximum

20

Samples

362

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• Low-temperature

175

brittleness or toughness: Samples are cooled to a temperature far lower than the supposed temperature of brittleness, and then gradually warmed up. At each selected step temperature, the test specimens are subjected to a specified impact. The temperature at which specimens deteriorate or fail is the “brittle point.” In other tests, the lowest temperature to which specimens can be cooled without deterioration is regarded as the limiting temperature of “toughness” or “no brittleness.”

higher. Often, plasticizers account for several percent of plastics parts, which makes attractive the replacement of fossil plasticizers by renewable ones. In specific cases such as plastisols, high levels of renewable plasticizers allow for a significant renewable content to be obtained. Among the most used plasticizers are:

• Low-temperature flexibility of thin products:

• Petroleum oils. • Low molecular weight (MW) rubbers or plas-

The product is rolled up on a specified mandrel at one or several temperatures.

5.6.3 Rigidity in Torsion: “ClashBerg” and “Gehman” tests These tests are based on the evolution of the static or dynamic torsion modulus when the temperature decreases. Results can be:

• plotted versus the temperature; • expressed as the value of the modulus for specified temperatures;

• recorded as the temperatures for which the modulus is 2, 5, 10, 100, etc., times higher than that measured at room temperature.

5.6.4 Crystallization Test The crystallization test consists of measuring the evolution of hardness at a specified temperature over several weeks. This method is of special interest for those polymers that can slowly crystallize at service temperatures. The combination of low-temperature periods and immersion in chemicals at higher temperatures, leading to chemical uptake, can induce worsening of existing defects by volume increase of solidified chemicals by cooling.

5.6.5 Environmental Footprint of Plasticizers Plasticizers are used to soften polymers and enhance their low-temperature behavior. If they desorb during processing, storage, or service life, the properties come back to that of the unplasticized polymer as far as the plasticizer loss is

• Esters including phthalates (some are banned or restricted), phosphates, sebacates, adipates, azelates, glutarates, etc.

tics (PE, PPO) and liquid rubbers.

• Chlorinated hydrocarbons. Alternatives to threatened plasticizers can be, for instance:

• Petrochemical-derived plasticizers such as • Ester plasticizers, namely adipates, citrates, • • • • •

benzoates, sebacates, azelates, trimellitates, and phosphate esters. Alkylsulfonic phenyl ester such as Mesamoll. Hydrogenated phthalates such as Hexamoll. Polymeric esters. Low MW polymers. Reactive plasticizers.

• Biosourced materials such as • Epoxidized soya bean oil and other epoxi• • • •

dized vegetable oils. Isosorbide esters such as POLYSORB ID. Oil derivatives such as Grindsted SOFT-NSAFE. Citrates such as CITROFOL BII [acetyltributyl citrate (ATBC)]. Succinic acid derivatives.

The used plasticizers have their advantages and drawbacks and have an effect on the environmental behavior of the final compound. Like, for numerous polymer problems, the final choice is a compromise between the different effects:

• Sustainability, environmental effects, toxicity, and environmental risks

• Compatibility with the polymer • Processing and rheological properties

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• • • • • •

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Thermal, electrical, and mechanical properties Fire resistance

Thermal expansion: CTE

Chemical resistance Mold shrinkage

Aging due to heat, humidity, light, and UV Stress cracking of other plastics and discoloration of rubber by contact or proximity

• Contact with food and medical articles • Volume cost

Environment: wet, chemicals

5.7 Design for Dimensional Stability Too little (or too large) a polymer part can disturb a device made by assembling several parts of various materials. Sometimes, the dimension is fair, but a more or less strong warpage prevents correct assembly. These phenomena are the consequences of: the CTE mold shrinkage the anisotropy of fiber-reinforced plastics water uptake, polyamides

particularly

• the absorption of chemicals

known

Warpage, Residual stresses Anisotropy

Some phthalates are banned as plasticizers, especially for PVCs, due to the high outlet for these additives, for carcinogenic, mutagenic, and reproductively toxic effects; pollution of air, water, and land; and greenhouse effect and/or ozone depletion. Some other phthalates are not involved, but there is some confusion between the various phthalates and, consequently, a general bad image initiating a trend for phthalate-free solutions. Regulations, laws, directives, etc., continuously evolve and depend on numerous organizations, varying with country and application field. Consequently, it is the reader’s responsibility to carefully study their own problem considering the countries of production, marketing, and use, the applications, and the waste regulations for the endof-life devices. The facts and figures are provided for information only.

• • • •

Dimensional stability issues

Optical properties

for

Aging, desorption, bleeding

Figure 5.7 Dimensional stability: the ins and outs.

• the desorption and bleeding of humidity or additives such as plasticizers or other low MW organic additives In addition, a wrong drawing can induce warpage of isotropic compounds. Anisotropic variations of the parameters listed above can also be responsible for warpage. Moreover, plastics and rubbers are often simultaneously used with conventional materials, notably metals, whose coefficients of thermal expansion can be 10- to 100-times lower. This can promote high stresses and eventually failure of the device including these different materials. Dimension variations can be immediate (thermal expansion), progressive (water uptake), or delayed after a given time of aging. Fig. 5.7 displays the ins and outs concerning the dimensional stability of plastics.

5.7.1 Thermal Expansion or Retraction The CTE can be volumetric or more frequently linear. It is defined as the fractional variation of volume (volumetric coefficient) or length (linear coefficient) per unit change in temperature. The volumetric coefficient is roughly three-times the linear one. Of course, a temperature decay leads to a retraction. Being thermal dependent, the validity range of test temperatures must be indicated.

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Table 5.8 Statistical Analysis of CTLE for About 200 Thermoplastic Grades. Median

1025/K

9

Minimum

1025/K

3

Maximum

25

10

/K

Samples

30 218

CTLE, coefficients of thermal linear expansion.

Thermoplastics intrinsically have high coefficients of thermal expansion in the order of 1024 to 1025/K. To provide a general idea of thermoplastics coefficients of thermal linear expansion, Table 5.8 displays a statistical analysis for about 200 unfilled grades. These values must be compared to those of other materials.

• • • •

Steel and iron: 1 2 3 1025/K.

5.7.3 Warpage Warpage or distortion can be due to:

• anisotropy • internal stresses • local changes of formulation or processing parameters Colorants, for example, can nucleate the polymer and locally favor shrinkage. Fibers and acicular fillers can accumulate in certain spots of the mold, leading to local decreases of CTE, shrinkage, and increases of moduli, thus, leading to warpage. Calcium carbonate fine powder and other spheroid fillers such as microballoons or glass beads decrease shrinkage and easily flow in the mold, thus, reducing warpage.

Other common metals: 2 4 3 1025/K. Low CTE metals: 0.4 1 3 1025/K.

5.7.4 Water or Chemicals Uptake

Ceramics, oxides, carbides, nitrides, carbon, graphite: 0.2 1 3 1025/K.

All polymers absorb more or less humidity or water in quantities depending on:

The CTE is significantly changed by:

• The temperature, particularly if the glass transition temperature is reached.

• The structure and morphology of the polymer. • The additives eventually used.

5.7.2 Shrinkage Shrinkage after molding is a universal problem depending on:

• The CTE; for given conditions, the shrinkage increases with the CTE.

• The molding temperature; for given conditions, the shrinkage increases with the molding temperature.

• • • •

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The additives. The orientation of the macromolecules. The orientation of fibers or acicular fillers. The crystallinity; a possible crystallization after molding leads to a volume increase that minimizes the total shrinkage.

• The form of the water: humid air, liquid water, pure or polluted water

• The temperature • The recipe of the compound • The crystallinity of the polymer The volume of absorbed water causes a dimensional increase. For example, for a given polyamide, the length increase is about 2.6% for a water content of 8% at equilibrium. Really, the absorption of water is extremely slow and, in the case of atmospheric changes, the equilibrium is not always reached, damping the effects of humidity variations. Chemicals have the same effects, but the swelling can be much higher and absorption rate can be faster.

5.7.5 Aging, Desorption, Bleeding, Releasing of Organic Components Residual monomers, oligomers, organic additives, particularly plasticizers, can degas, more so as the temperature and the airflow rise. Consequently, dimensions decrease. Components can also migrate toward other materials or bleed.

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Released organic components pollute other materials and surroundings.

5.8 Electrical Properties Polymers are generally insulating, but a few are antistatic or conductive; see Chapter 2, Plastics Overview: Outline of the Current Situation of Plastics, for conductive polymers that can behave differently from general insulating polymers concerning environmental, technical, economic, and other properties. Generally speaking, behavior with AC current must be specially studied. Fig. 5.8 displays the main ins and outs related to the electrical behavior of plastic. Traditional polymers are naturally insulating, but can be made more or less conductive. They can be characterized, among other test methods, by:

• • • •

The volume resistivity and surface resistivity The dielectric strength The arc resistance

5.8.1 Volume Resistivity: ASTM D257 and IEC 93 The volume resistivity is the electrical resistance of a polymer sample of unit area and unit thickness when electrodes placed on two opposite faces apply an electrical potential across it. The volume resistivity is expressed in ohm cm (Ω cm). The classification of polymers varies depending on the country and application. Each case must be examined in its context and the data listed below are only examples:

• Insulating polymers: Resistivity higher than 109 Ω cm.

• Conductive polymers: Resistivity lower than 105 Ω cm.

• Polymers for electrical heating: Resistivity lower than 102 Ω cm.

To provide a general idea of thermoplastics volume resistivities, Table 5.9 displays a statistical analysis for about 560 grades including 416 insulating ones.

The high voltage arc tracking rate

5.8.2 Surface Resistivity: ASTM D257 and IEC 93

Electrical requirements

The surface resistivity is the electrical resistance between two electrodes placed on the same face of a polymer sample. The surface resistivity is expressed in ohms (or in ohms per square). The classification of polymers depends on the country and application. Each case must be examined in its context and the data listed below are only examples:

Insulative, conductive Environment: dry, wet... Temperature Fire regulations Current frequency Aging

• Insulating polymers: Resistivity higher than

Lifetime

1012 ohm per square.

Figure 5.8 Electrical behavior: the ins and outs.

• Dissipative polymers: Resistivity in the range of 105 up to 1012 ohm per square.

Table 5.9 Statistical Analysis of Volume Resistivities for All-Purpose and Insulating Grades. All Grades 13

Insulating Grades 1014

Median

10

Minimum

1021

109

Maximum

1018

1018

Samples

566

416

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• Antielectrostatic

parts for coalmines: Resistivity lower than 109 ohm per square.

• Conductive polymers: Resistivity lower than

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For example, certain conductive thermoplastics may be insulating after dynamic loading. A few plastics can have piezoelectric properties.

10 ohm per square.

5.8.3 Dielectric Strength The dielectric strength is the maximum voltage before breakdown divided by the thickness of the sample. It is expressed in kV/mm. Data depend on the test conditions.

5.8.4 Arc Resistance The arc resistance is the time necessary to make the polymer surface conductive by the action of a high-voltage, low-current arc. It is expressed in seconds.

5.8.7 Conductive Polymers: Sustainability Considerations A few polymers, of natural or synthetic origin, are inherently antistatic such as, for example, cotton, wood fibers, polyamides 11 or 12, and others. For more conductive polymers, a lot of solutions are well known or newly developed, opening the way to better performing versions. Solutions include, but are not limited to:

• conductive carbon blacks • metal powder and nanopowders • inherently dissipative or conductive polymers (ICP)

5.8.5 High Voltage Arc Tracking Rate Plastics can be sensitive to tracking appearing when a high-voltage source current creates an unwanted path across the surface of a plastic part. High voltage arc tracking rate (HVTR) is denoted as the rate, in millimeters per minute, that a tracking path can be produced on the surface of the material under standardized test conditions. A note is made if ignition on the material takes place. The results of testing the nominal 3 mm thickness are considered representative of the material performance in any thickness. HVTR range can be less than 10 to more than 150 mm/min. Apart from these electrical properties, electricity & electronics (E&E) are also subjected to fire and service temperature laws, standards, and regulations such as UL 94 fire ratings, UL temperature index, and many other international, national, regional, or application sector specifications.

5.8.6 Frequency, Temperature, Moisture, Physical, and Dynamic Aging Effects All electrical properties may be modified by the current frequency, the actual temperature and moisture content of the plastic, historical heat, and mechanical aging.

• CNT, fullerenes, and graphenes • conductive fibers, microfibers, and nanofibers • conductive coatings such as indium tin oxide, etc. Some solutions can be banned or limited by health and environmental regulations. These heterogeneous solutions lead to highly diverse pollutions and this facet of each solution must be studied from a sustainability standpoint, even if the addition level of conductive component is low. For instance, Fig. 5.9 shows examples of energy use for 18 conductive components (the y-axis is logarithmic). The range is as broad as from 100 to more than 100,000 MJ/kg. Even for a 2% level of a component needing 100,000 MJ/kg, the embodied energy of the final compound is significantly impacted. In addition, lower or higher data may be found in the literature. The resistivity of the final material depends on:

• • • • • • •

The component used Its level; roughly about 1% 100% for ICP The grade of the polymer The compounding method The ambient temperature and humidity Aging The possible dynamic stresses, etc.

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1,000,000

Energy, MJ/kg

100,000

10,000 1000 100 10 1

Figure 5.9 Energy use for various conductive solution systems.

Generally speaking, the environmental cost includes all facets of pollution such as energy consumption, resource depletion, emission of GHGs, NOx, SO2, and waste disposal, etc. Especially for metal conductive fillers, be cautious of the final density:

Fire behavior Fire retardancy

Fire regulations, approved labs

• The density of metals is high, leading to conductive compounds heavier than general purpose (GP) grades.

• The strength of metal-filled grades is generally

Specific tests

Aging

lower than the strength of GP grades. Waste management

As a consequence, for the same functionality, parts are heavier needing more energy for handling and for the use phase if appropriate.

5.9 Fire Behavior: Some Ins and Outs In the United States alone, it is estimated that there are approximately 400,000 residential fires each year, 20% involving electrical distribution and appliances and another 10% concerning upholstered furniture and mattresses. These fires kill about 4000 people, injure another 20,000 people, and result in property losses totaling about US$4.5 billion. Across Europe, fires kill about 5000 people. This brief overview shows the need for fireretardant (FR) plastics in such sectors as E&E, building and construction, automobile, transportation, etc. Moreover, it is pointed out that the use of flame-retardant materials had cut fire deaths by 20% in the past few years, although there is a marked increase in the number of electric and electronic devices in every home.

Figure 5.10 Fire behavior: the ins and outs.

Polymers can burn easily or with difficulty, their behavior depending on the polymer and the formulation, particularly the addition of an FR modifying fire behavior and environmental, technical, economic, and other properties. Fig. 5.10 displays the main ins and outs related to the fire behavior of plastics. Due to their organic nature, plastics have specific fire behavior depending, initially, on the nature of the polymer. Apart from inherently fire-resistant polymers, the only other solution is the addition of FR additives to conventional plastics, a market with annual growth rates exceeding those of plastics. Flammability and smoke-generating characteristics of plastics, regulations, standards, and a variety of laboratory tests have been developed to quantify these properties. Agencies within the federal government and other countries or regions as well as outside organizations such as the American Society for Testing Materials, the Underwriters’ Laboratories, Inc., and many industrial corporations

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have contributed to new test development. Currently, a large number of procedures for defining many aspects of flammability are available for setting up safety and acceptability standards. For example, a single laboratory proposes 101 standards and methods for fire testing. The individual tests are generally intended to predict the behavior of a material during experimental burning or during exposure to intense heat, as in a burning building or aircraft. Laboratory conditions and procedures are legion, but very few experiments are run in real conditions. The correlation of laboratory test data with actual fires remains controversial. The major contribution of the tests is to rank the various materials relative to each other and to the particular specifications. Often, plastics parts have long lifetimes, so fire resistance must withstand the use conditions during long periods and certain standards such as UL 94 fire rating including tests after accelerated aging. Worldwide, national, and local regulations; national and international standards; corporative and company specifications; safety requirements; and application sector rules and practices are numerous, evolutionary, and often mandatory. So, they must be applied in the various countries implied in the manufacture, application, and disposal of plastics products.

In addition, please note that certain tests required for fire agreement must be run by accredited certifiers. It is the responsibility of the reader to search the specific rules applicable to their own problem.

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• Building: ASTM E84, ASTM E1354, UL 2043, NFPA 286, 16 CFR 1209 and 16 CFR 1404, ASTM E970, NFPA 90A.

• Mass Transit: ASTM E162, ASTM E662, 49 CFR 238, BSS 7239, EU Norm 45545.

• Electricity and electronics: Numerous UL standards are well known, but many other requirements, compulsory or voluntary, may apply.

• Material handling and storage: UL 2335, FM 4996, NFPA 13, etc. Once again, these are only examples and many other requirements can be mandatory or voluntary. The tests listed below are only a short panel of examples, but many other testing methods are used around the world. Generally speaking, they relate to:

• the tendency for combustion; UL 94 ratings and oxygen index, for example

• the smoke opacity • the toxicity and corrosivity of the smoke Official organizations must be consulted before use.

5.9.1 UL 94 Fire Ratings The UL 94 fire ratings (see www.ul.com) provide basic information on the material ability to extinguish a flame, once ignited. The positioning of the sample (horizontal (H) or vertical (V)), the burning rate, the extinguishing time, and dripping are considered. Briefly, the main categories include:

• 5VA surface burn: This is the highest (most For example, the building, transportation, electricity and electronics, marine, material handling, and other industries have specific regulations and test standards that vary by country. Please note that regulations may affect only a share of users (e.g., children) or can affect other items than the plastic part. For example, the use of plastic pallets may, in certain cases, require a sprinkler system for warehouses. For instance, without claiming to be exhaustive, a few examples include:

• Aerospace:

Federal Aviation Regulations (FAR) part 25 including FAR 25.853.

flame retardant) UL 94 rating. Vertical burning stops within 60 s after five applications of 5 s each of a flame, no drips allowed, and plaque specimens may not develop a hole.

• 5VB surface burn: Vertical burning stops within 60 s after five applications of 5 s each of a flame, no drips allowed, and plaque specimens may develop a hole.

• V-0: Extinguished after 10 s, no drips after two applications of 10 s each of a flame.

• V-1: Extinguished after 30 s, no drips after two applications of 10 s each of a flame.

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• V-2: Extinguished after 30 s, flaming particles or drips permitted after two applications of 10 s each of a flame.

• HB: Burning horizontally at a 76 mm/min maximum rate. The UL rating depends on the exact grade and the sample thickness. For the same grade of polyphenylene sulfide, the UL ratings are:

• V-1 for a 1.6 mm thickness • V-0 for a 6 mm thickness

5.9.2 Oxygen Index The oxygen index is the minimum percentage of oxygen in an atmosphere of oxygen and nitrogen that sustains the flame of an ignited polymer sample. Generally, oxygen indices range from 15 to 60 and more, for example, 95 for PTFE. There is no true link between UL 94 rating and oxygen index, but a plastic with a low oxygen index cannot satisfy the requirement of UL 94 V-0. To provide a general idea of thermoplastics oxygen indexes, a statistical analysis for about 36 grades displays:

conditions of active burning and their decomposition in the presence of flame. The instrumental observations from this test compare well with the visual observations of the smoke generated by plastic materials when added to a large, freely burning, outdoor fire. The usefulness of this test procedure is in its ability to measure the amount of smoke obscuration produced in a simple, direct, and meaningful manner under specified conditions. The degree of obscuration of vision by smoke generated by combustibles is known to be affected by changes in quantity and form of the material, humidity, draft, temperature, and oxygen supply. Federal Aviation Administration standard (FAR 25.853) defines fire, smoke, and toxicity (FST) requirements.

5.9.4 Cone Calorimeter Cone calorimeter is used to study the fire behavior of small samples of various materials in condensed phase. It gathers data regarding the ignition time, mass loss, combustion products, heat release rate, and other parameters associated with burning properties. Optional devices can include:

• Carbon

dioxide

and

carbon

monoxide

analyzers.

• Integrated fume cupboard. • FTIR toxicity test system.

• Median • Minimum

17

• Maximum

96

5.9.5 Ignition Temperature

• Samples

36

Flash ignition temperature is the lowest temperature at which a material supplies enough vapor to be ignited by an external flame. For example, for a given grade of polyacetal, the flash ignition is at 320°C and for self-ignition it is at 375°C.

30

5.9.3 Smoke Opacity, Toxicity, and Corrosivity Smoke opacity is measured by optical density. For smoke density, according to ASTM D2843, a specimen is burned in a special chamber under continuous ignition. The generation of smoke causes a reduction in the intensity of a light beam. This is measured through the duration of the test and results are expressed in terms of maximum percent light absorption and a smoke density rating. The procedure is intended to provide a relative ranking of the smoke production under controlled standardized conditions. This test method serves to determine the extent to which plastic materials are likely to smoke under

5.9.6 Rate of Burning For example, Federal Motor Vehicle Safety Standards (FMVSS) 302—Flammability of Interior Materials—Passenger Cars, Multipurpose Passenger Vehicles, Trucks, and Buses specifies burn resistance requirements for materials used in the occupant compartments of motor vehicles. Its purpose is to reduce deaths and injuries to motor vehicle occupants caused by vehicle fires, especially those originating in the interior of the vehicle from sources such as matches or cigarettes.

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The test is conducted inside a test chamber where the test specimen is mounted horizontally. The exposed side of the test specimen is subjected to a gas flame from underneath. The burn distance and the time taken to burn at this distance is measured during the test. The burning rate is expressed in mm/min. For example, a given grade of polyacetal burns slowly at rates around 50 mm/min for a 1 mm thick horizontal sample.

5.9.7 Glow Wire Test The glow wire test (IEC 695-1) simulates the thermal conditions that may be produced by incandescent sources of heat and ignition in order to evaluate the fire hazard. Values vary with the thickness of the specimen, and are expressed in degrees Celsius. For example, a given grade of polyacetal passes the test at 550°C, at a thickness of 1 mm.

5.9.8 Fire Resistant Polymers: Sustainability Considerations Main mechanisms of fire proofing include:

• Gas phase radical quenching where halogenated FRs release hydrogen chloride or hydrogen bromide in the presence of antimony trioxide or antimony halides. These react with reactive H and OH radicals, which mitigate the overall reactivity.

• Endothermic degradation of additives such as magnesium and aluminum hydroxides.

• Thermal shielding (solid phase) due to the char created by intumescent additives. For instance, nonhalogenated inorganic and organic phosphate FRs generate a polymeric layer of charred phosphoric acid.

• Dilution of gas phase by inert gases produced by thermal degradation of some materials FR solutions can be categorized into:

• Halogen-containing FR (HCFR) solutions: the oldest route and often used, but the less environment-friendly.

• Halogen-free FR (HFFR) solutions: the most recent and ecologic ways.

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From a practical standpoint, FR additives may be categorized through multiple routes as seen in the examples in Fig. 5.11. Of course, sustainability impacts are broadly dependent on the selected routes, some being globally or regionally banned or restricted. In addition, please note that the design of a device can protect plastic parts through a nonflammable shield of metal, stone, or other material. This solution is used, for example, in the design of composites for railway applications including stainless steel faces. Also be suspicious of hidden pollutants. Theoretically, the molecule of polyphenylene sulfide (PPS) only contains carbon, hydrogen, and sulfur, but, in fact, chlorine content can be higher than those required by some specifications. Therefore some PPS producers (e.g., Ticona, Polyplastics) have developed grades of PPS resins (Fortron, DURAFIDE) that enable significant reductions of chlorine level, while also featuring high mechanical strength and toughness. These new PPS resins can satisfy the UL 94 V-0 flammability rating.

5.9.8.1 Inherently FR Polymers The list below and Fig. 5.12 display some families of polymers having a higher oxygen index that common polymers, making them inherently more or less fire resistant. Some contain zero or very little halogen for suitable grades. Others contain halogen in their molecule.

• Halogen containing: • Fluorinated ethylene propylene (FEP) • Perfluoroalkoxy (PFA) • Polytetrafluoroethylene (PTFE) • Polychlorotrifluoroethylene (PCTFE) • Polyvinylidene chloride (PVDC) • Ethylene monochlorotrifluoroethylene (ECTFE)

• Chlorinated PVC (PVCC) • Polyvinyl chloride (PVC) • Polyvinyl fluoride (PVF) • Halogen free (see Fig. 5.12): • Polysulfones (PSU, PES, PPSU) • Polyamide-imide (PAI) • Polyetherimide (PEI) • PPS • Thermoplastic polyimides • Polyether ether ketone • Liquid crystal polymers (LCP) • Polybenzimidazole (PBI)

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Halogen free

Halogen containing

Halogen free polymer(s)

Halogen containing polymer

Chlorinated additives

Halogen free recipe

Phosphorous containing

Halogen free polymer

Brominated additives

Phosphorous free

Phosphorous additives

Phosphorous additives

Mineral fillers (siloxane treatment)

Mineral fillers (siloxane treatment)

Nano additives

Nano additives

Synergists

Synergists

Expandable graphite

Expandable graphite

Proprietary additives

Mineral fillers (siloxane treatment) Synergists

Expandable graphite Proprietary additives

Proprietary additives

Figure 5.11 Examples of halogen-free and conventional FR routes. FR, Fire retardant. PBI PEI PPS PAI MF LCP PSU PEEK Nonflame resistant

Figure 5.12 Oxygen index examples.

For example, inherently FR Ultem resin grades offer full FST compliance, and allow for the production of lightweight aircraft interior parts.

5.9.8.2 FR Additive Solutions FR solutions are categorized into:

• HCFR solutions: The oldest route and often used, but the less environment-friendly.

• HFFR solutions: The most recent and generally more ecologic ways.

Fig. 5.11 shows some examples of halogen-free and conventional FR routes. Generally speaking:

• Halogenated FRs (Br- or Cl-containing) may include some advantages, namely: • Lower cost • Wider processing window • Good FR efficiency • Good physical properties retention • Well-known technology

• Non-halogenated FRs may include some advantages, namely: • Lower corrosivity • Lower smoke generation • Lower toxicity • Environment-friendly Among other factors, HFFR solutions can be based on:

• Phosphorous additives. When subjected to heat, they react to form polymeric phosphates

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that build a hard, glassy layer on the surface of the plastic. This inhibits access of oxygen to the combustible material and prevents flammable gases from being released. As a result, the plastic chars rather than burning. Among others, are: • Phosphate ester plasticizers, ammonium polyphosphate, etc. • Metal phosphinates • Organic phosphonates • Organic phosphinates • Polymeric FR (FRX polymers), a phosphorus-based system bound onto the polymer. It is claimed to be nonvolatile and nonmigrating. The plastics have high limiting oxygen indexes according to FRX polymers • Red phosphorous Some phosphorus additives are banned by some regulations, standards, or private specifications requiring halogen-free and phosphorus-free additives:

• Nitrogen-based FRs such as melamine compounds. The mechanism of fire retarding is not fully understood and probably is a combination of effects. Inert nitrogen is released and stable barrier layers of “char” are built on material surfaces. Melamines and derivatives such as melamine phosphates, melamine pyrophosphates, and other products combining with nitrogen and phosphorous derivatives lead to synergistic effects.

• Metal hydroxides such as aluminum and magnesium hydroxides have several effects. When heated, they release large volumes of water vapor that inhibit oxygen access to the surface and dilute any released flammable gases. Also, they decompose endothermically, which means that they adsorb heat, thereby cooling the material. Metal hydroxides include aluminum trihydroxide (ATH) and magnesium hydroxide (MDH) as the most used, but aluminum oxide hydroxide is also quoted.

• Intumescent materials, for example, ammonium polyphosphate, are chemicals that produce a bulky porous ceramic coating that covers the material surface, preventing it from burning. These materials release large amounts

185

of inert gases and a thick viscous liquid, which together form a foam. This foam loses its organic constituents when hot, leaving a hard, ceramic foam coating.

• Nano fillers: • Nanosilicates, nano-oxides such as, for example, MARTINAL & MAGNIFIN CHAR Flame Retardant Grades marketed by J.M. Huber Corporation (www.huber.com) (previously launched by Albemarle) and based on nanotechnology. • Multiwalled carbon nanotubes are claimed to be efficient in PE cables and PUR foam. • FlexB by Auterra (www.auterrainc.com/ previouslyApplied NanoWorks), a boronbased HFFR additive. • Nanocomplexes such as Fe-montmorillonite

• Expanded graphite: Limiting oxygen index (LOI) and thermal gravimetric analysis (TGA) show that the incorporation of expanded graphite in PP including intumescent flame retardant (IFR) would impart extra flame retardancy and thermal stability to the virgin formulation PP-IFR.

• Siloxanes for mineral filler treatments or as FR additives: Siloxanes can improve the compatibility of mineral FR with the polymer matrix and improve the performance for a given loading level or allow a higher filler loading for the same performance level. An FR effect is claimed in particular cases.

• Metal-functionalized silsesquioxane (Me-POSS): The combustion behavior of thermoplastics containing dimeric and oligomeric Al- and Znisobutyl silsesquioxane are claimed to be improved. Al-POSS or Zn-POSS modified PP show that the presence of Al-POSS leads to a decrease in combustion rate with respect to neat PP, resulting in a decrease of heat release rate (243% at 10 wt.% Al-POSS loading) as well as a reduction in carbon monoxide (CO) and CO2 production rates. Al-POSS favors the formation of a moderate amount of char residue.

• Others: • Boron compounds function in a similar way as phosphorous FRs.

• Zinc borate works by a variety of mechanisms including synergistic effects with ATH.

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• Tin derivatives, ammonium salts, molybdenum derivatives, and magnesium sulfate heptahydrate are more or less used. • Zinc and tin compounds are added to PVC to reduce smoke emission and increase the effectiveness of other types of FR. • Inorganic complexes or compounds such as, for example, Kemgard products, flame retardant/smoke suppressant additives including zinc molybdate, calcium zinc molybdate, zinc oxide/phosphate, zinc molybdate magnesium silicate, and zinc molybdate/MDH. It must be noted that the efficiency of each method is linked to the nature of the plastic resin and to the other components of the compound formulation. Of course, these techniques have generated a multitude of proprietary additives.

5.9.8.3 The Top Solutions: Halogenated Flame Retardant and Fire, Smoke, and Toxicity Grades Ready-to-use HFFR compounds are one of the easiest solutions, but grades are limited to the most used resins for the electrical and electronics, building and construction, and automobile industries, etc. The most common are polyamides, thermoplastic polyesters, polyolefins, acrylonitrile-butadiene-styrene (ABS) and polycarbonate alloys, and polyphenylene oxide, but the plastics range is fast developing. Low smoke zero halogen or low smoke free of halogen (LSZH or LS0H) compounds are used for cable jacketing in the wire and cable industry. LSZH are thermoplastic or thermoset compounds that emit limited smoke and no halogens when exposed to high sources of heat.

5.9.9 General Collateral Effects from a Sustainability Standpoint FR formulations require the selection of suitable polymers and additives having effects on technical properties and consequences on the drawing and properties of parts, aging, lifetime, and modification of economics. Of course, the choice of special chemical entities leads to changes in sustainability features, but in many cases, there are insufficient data for well-founded assessments.

FR compounds must obey general guidelines of plastics dealing with health, safety, fine dust clouds that may form explosive mixtures with air, etc. In addition, they can require more specific attention. Due to the diversity of solutions, there is not a universal response to the sustainability concerns. Accordingly, only some incomplete comments can be made, unsuitable in certain cases, and it is the responsibility of the reader to choose suitable ways to study their own problem, building their own solution corresponding to their own case while meeting general and local contexts, appropriate regulations, etc. Generally speaking, the environmental cost of FR compounds includes all facets of pollution such as energy consumption, resource depletion, emission of GHGs, NOx, SO2, and others, waste disposal, etc. Be cautious of the final density; there are exceptions, but generally, on average:

• The density of FR grades is higher than the density of GP grades

• The strength of FR grades is lower than the strength of GP grades. As a consequence, for the same functionality, parts are heavier requiring more energy for handling and for the use phase if appropriate. Halogenated additives are expected to be harmful to health and the environment, and their use has been restricted or sometimes banned according to the considered region. Because of their toxicity and persistence, the production of some additives is to be eliminated under the Stockholm Convention, a treaty to control and phase out major persistent organic pollutants. As other compounds, halogenated polymers and FR versions need general precautions including, for example, among others, ventilation, personal protective equipment, safe handling procedures, safety practices linked to fume exposition, fire hazard, inhalation, and skin and eye contact. In the case of fire, the thermal decomposition of FR compounds can release hazardous gases, fumes, and particulates including, but not limited to, CO, CO2, carbonyl fluoride, carbonyl chloride (phosgene), hydrogen chloride, hydrogen fluoride, hydrogen bromide, perfluoro isobutylene, nitrogen, phosphorous, and sulfur derivatives, etc. Firefighters

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must use suitable extinguishing media and wear protective equipment including, if necessary, a self-contained breathing apparatus. A few phosphorous-based compounds show moderate or high persistence and aquatic toxicity. Red phosphorous is highly flammable and toxic to aquatic organisms. It may form toxic phosphine gas during combustion. Certain zinc derivatives such as zinc borate are generating concerns on toxicity and aquatic toxicity. Antimony trioxide is ranked as a possible carcinogen by the International Agency for Cancer Research (IARC) and the European Union. Nanomaterials are emerging and their behaviors concerning humans and the environment are not known. Regulations depend on the country and are rapidly evolving. Consequently designers, employers, users, and other players must continuously study regulations and the risks arising from the application of new technologies. Risks include among others, but are not limited to, the inhalation of the material and emitted products, absorption through the skin, contact with the skin or eyes, ingestion, fire and/or explosion (ultrafine dust), hazardous chemical reactions, and damaging of installations by nanomaterials (corrosion, etc.). This superficial glimpse is not a study, but it only aims to alert the reader to some potential limitations of FR compounds.

5.9.10 A Glimpse on General Behavior of Biopolymers PLA- and starch-based thermoplastics (TPS) behave as common fossil polymers and their fire resistance may be generally improved by similar methods. A few examples, not rules, give a rough idea:

• Common polylactic acid (PLA) has a LOI of about 20% and is not UL rated.

• FR compounds have LOIs of about 20% to 39% with V-2 to V-0 UL ratings.

• Common TPS have LOIs of about 20% to 23% and are HB or not UL-rated.

• FR TPS have LOIs of about 29% to 32% and some grades may reach a V-0 UL rating. Of course, the reader must study their own case collaboratively with their suppliers and customers,

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and check the compliance with suitable laws and regulations.

5.10 Sensory Issues: Optical Properties, Aesthetics, Odor, Taste, Touch The user/plastic part interface was sharply oriented to direct functionalities such as toughness, durability, cost, and so on, but, more or less recently, new concepts have been devised concerning sensory properties and secondary or indirect objectives such as appealing marketing features, new safety concepts, or more generally, interactions between the user or the environment and the plastic part or the system including plastic parts. Today the concerned properties exceed the optical properties including features as diverse as aesthetics, color, transparency, gloss, haze, surface aspect, touch, odor, noise/vibration/harshness, acoustics, and taste transfer contributing to make a plastic part attractive, unappealing, or repulsive. As with other properties, sensory characteristics degrade by aging, which can limit the lifetime of plastics parts still having satisfactory mechanical or other functional properties. Special formulations require the selection of suitable special polymers and additives having effects on technical properties and, consequently, on the drawing and properties of parts, aging and so lifetime, and modification of economics. Of course, the choice of special chemical entities leads to changes in sustainability features. Some examples concern the sense satisfaction, the best known being the aspect, or the use of the user’s senses to achieve the targeted aims, the latest and the most promising way to enhance the capability and attractiveness of all devices. Fig. 5.13 displays the main ins and outs related to sensory properties of plastic parts. The market appeal of plastics is of prime importance for numerous applications such as packaging, automotive, and appliances. Color, transparency, gloss, haze, touch, acoustics, odor, and taste transfer contribute to make a plastic part attractive, unappealing, or repulsive. Sensory perception is often subjective, which means that instrumental measurements may be insufficient, ineffective, or even misleading. People

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Sensory requirements

Visual aspect color, transparency, gloss, mat, haze

Physical aspect: sharkskin, defects, warpage

Touch NVH—noise, vibration, harshness Odor Taste transfer

Figure 5.13 Sensory issue examples.

panels or skilled individuals such as “noses” for smells, odors, flagrances, etc., can supplement traditional testing.

5.10.1 Complementarity of Instrumental Measurements and Sensory Panel Evaluations Analysis instruments have neither brains nor psychological faculties, but they are never in a good or bad mood, tired, ill, or show other human hazards. They are perfect to identify or quantify chemical entities or physical properties, but are unable to make the link between the obtained results and the satisfaction or dissatisfaction of plastics parts users. Sensory evaluation by people panels aims to fill this gap. Sensory evaluation was defined by the Sensory Evaluation Division of the Institute of Food Technologists (1975) as “the scientific discipline used to evoke, measure, analyze and interpret those reactions to characteristics of foods and materials as perceived through the senses of sight, smell, taste, touch and hearing.” The complex sensation that results from the interaction of our senses is used to measure product quality in programs such as quality control and new product development. Later, ASTM established the Subcommittee E18.05 on Sensory Applications, which focuses on test methods for the evaluation of molded polymer in terms of its perceived odor and the transfer of package-related odors or flavors, or both, to the food being packaged.

This evaluation may be carried out by panels of a small number of people or by several hundred depending on the type of information required. Sensory analysis panels can be grouped into four types, namely highly trained experts (1 3 people), trained laboratory panels (10 20 people), laboratory acceptance panels (25 50 people), and large consumer panels (more than 100 people). The first and simplest form of sensory analysis is made by the researcher who develops the new product making their own evaluation to determine the interest of designed product. Skilled laboratories and consumer panels develop sensory analysis in a more formal and scientific manner. The subcommittee E18.05 has published several standards that deal with odor/taste:

• ASTM E1870, Standard Test Method for Odor and Taste Transfer from Polymeric Packaging Film—This standard deals with rigid containers and closures in terms of their perceived odor and the transfer of package-related odors or flavors to the food being packaged.

• ASTM D1292-15, Standard Test Method for Odor in Water—This test method covers the determination of the odor of water. The odor intensity may be expressed in terms of odor intensity index or threshold odor number.

• ASTM

E460-12, Standard Practice for Determining Effect of Packaging on Food and Beverage Products During Storage—This practice is designed to detect the changes in sensory attributes of foods and beverages stored in various packaging materials or systems, or both. It is not a practice intended to determine shelf life. This practice may be used for testing a wide variety of materials in association with many kinds of products.

• ASTM E2454-05 (2011), Standard Guide for Sensory Evaluation Methods to Determine the Sensory Shelf Life of Consumer Products.

• ASTM E2609-08 (2016), Standard Test Method for Odor or Flavor Transfer or Both from Rigid Polymeric Packaging.

• ASTM STP 434, Manual on Sensory Testing Methods—Sensory testing is concerned with measuring physical properties by psychological techniques. As part of the field of

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psychometrics, sensory methods are used for measurements that cannot be made directly by physical or chemical tests.

• ASTM STP 758, Guidelines for Selection and Training of Sensory Panel Members. For people being used as a measuring instrument, it is necessary to control all testing methods and conditions rigidly to overcome all kinds of extraneous influences caused by psychological factors. All precautions must be taken to provide the best physical and mental conditions of the panelists and minimize the influence of the testing environment affecting their sensory evaluations. According to ASTM STP 758, “Within both discrimination and descriptive sensory methods, performance records should be maintained for each panelist and should be periodically reviewed by the panel leader. The performance of each panel member should be compared with the performance of the panel as a whole. Panelists whose performance has declined should be interviewed by the panel leader in an attempt to determine the cause. Wherever possible, assistance should be offered in an attempt to restore performance.” Instrumental and panel sensory analyses complement each other:

• Instrumental analysis leads to precise data for each feature (odor, taste, vision, etc.,) by the use of traditional physicochemical instruments or more specific devices such as electronic nose, electronic tongue, and visual analyzer.

• Sensory panel evaluation leads to human evaluations expected to be representative of the satisfaction or dissatisfaction of plastics parts users.

5.10.2 Visual Aspect Color may be obtained by adding colorants to compounds or by encapsulating the part with a continuous film of another colored or printed polymer using in-mold decoration (IMD), painting, multilayer sheets for thermoforming, etc. Color ages as other properties. Discoloration comes from overheating, light exposure, irradiation, or chemical attack, etc. Clarity and transparency are intrinsic properties of polymers, but can be degraded by certain additives or enhanced by adding clarifiers.

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Haze is the cloudy appearance of a transparent polymer caused by light scattering. Haze may appear after long exposure to moisture. Refractive phenomenon causes visual distortion; the refractive index of polymers is generally between 1.35 and 1.65. Matting may be obtained by adding special mineral fillers, another secondary polymer that is miscible to a greater or lesser degree with the main polymer, or proprietary additives. Glossy polymers may be obtained by mold polishing, postmolding into perfectly polished molds, lay out of films, IMD, film insert molding (FIM), in-mold coating, painting, etc. The choice of a solution depends on numerous parameters concerning the nature of the polymer, the processing constraints (notably heat exposure and mixing technology), endproduct aesthetics, the durability under service conditions of the end product, relevant regulations, and cost. Traditional characterization of plastics parts uses color matching cabinets, photocolorimeters, brightness meters, yellowing index, light transmission, and refractometers. Contrary to photocolorimeters and spectrophotometers that measure an average color and do not actually assess what the human eye sees in the object, Alpha MOS (www.alpha-mos.com) proposes its visual analyzer that performs an overall visual evaluation of the different colors and shapes. This evaluation is closer to consumer’s vision due to a high-end technology based on in-depth image analysis.

5.10.3 Physical Aspect The manufacture of plastic parts is a complex process, which may lead to various physical defects that can be seen immediately after manufacturing or after a more or less long aging time. Some defects are clearly unacceptable leading to the rejection of those parts as waste, while others lead to a poor visual aspect and a bad image of the product. Table 5.10 describes some defects without claiming to be exhaustive.

5.10.4 Touch Touch can be as varied as rubber-like, metallic, or mimicking cloth, wood, leather. Touch also

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Table 5.10 Examples of Physical Defects. Bleed, migration

To give an undesired color by contact with water, solvent, oily products, or other adjacent materials

Bloom

A visible exudation or efflorescence on the surface of a material

Chalking

Powdery residue on the surface of a material often resulting from degradation

Concentricity

Shape in which various cross sections have a common center

Crater

A small, shallow surface imperfection

Crazing

Tiny cracks near or on the surface of plastic materials. Fine cracks may extend in a network on or through a plastic material

Discoloration

Any change from the right color, often caused by overheating, light exposure, irradiation, or chemical attack

Fish eye

Defect in transparent or translucent plastics materials appearing as a small globular mass and caused by incomplete blending of the mass with surrounding materials

Flash

Extra plastic attached to a molding along the parting line; generally, it must be removed before the part can be considered finished

Flash line

A raised line appearing on the surface of a molding and formed at the junction of mold faces

Flow line or weld line

A flow line is a mark on a molded part resulting from the meeting of two flow fronts during molding. Generally, this spot has weaker mechanical properties

Flow marks

Wavy surface appearance of an object molded from thermoplastic; caused by improper flow of the resin into the mold

Granular structure

Nonuniform appearance of finished plastic material

Orange skin

Unintentionally rough surface resembling orange peel

Parting line

Mark on a molding where halves of mold met in closing

Resin pocket

Accumulation of resin in a small, localized section visible on molded surfaces

Shark skin

A surface irregularity of a thermoplastic part in the form of finely-spaced sharp ridges caused by a relaxation effect of the melt

Sink mark

A shallow depression or dimple on the surface of an injected part due to collapsing of the surface following local internal shrinkage. May also be a nascent short shot

Stress crack

A crack, either external or internal, in a plastic caused by tensile stresses less than its short-time mechanical strength

Sweating

Exudation of small drops of liquid, usually a plasticizer or softener, on the surface of a plastic part

Thermal stress cracking

Crazing or cracking, which results from overexposure to elevated temperatures

Weld lines

A mark on a plastic part caused by incomplete fusion of two streams of molten polymer

Weld mark

A mark on a molded plastic piece made by the meeting of two flow fronts during the molding operation

depends on surface properties such as hardness and surface texture, for example, smooth, highly polished, ground, grained, or textured. Now a soft touch is particularly in fashion.

Touch may be modified by overmolding, surface treatments, FIM, etc. Touch may be degraded by tack or stickiness of the plastic surface, scratches, cracks, and so on.

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5.10.5 Odor and Taste Properties and Transfer

now emerging. Amongst these sources are fuel tank slosh noise caused by fuel wave motion inside the tank and fuel pump noise. Generally speaking, conventional plastics have sound and vibration dampening properties that conventional metals do not. But plastic parts can also initiate unwanted noises by vibration. For example, certain automotive parts can vibrate at frequencies of engine rotation. Plastics rubbing on other plastics or various materials can also emit annoying noises. The noise testing seems easy at a first glance, but, in fact, is highly complex due to its dependence of the frequency, the mode of propagation (air, transmission by solids, etc.), the psychological aspects entering in the perception of noise, the diversity and heterogeneity of the standards, the application to specific areas such as automotive, building, aeronautic, household appliances, air conditioning, and others. Noise measurements must be carried out by skilled laboratories or staff due to the need for the use of special devices such as reverberant chamber, progressive wave tube arrangement, anechoic or semi-anechoic chambers, high precision acoustic power generators, etc. Measurement methods are as varied as sound power levels, sound energy levels, sound transmission loss, acoustic sensitivity, impact sound insulation, emission sound pressure levels, impact sound insulation between rooms, transmission of indoor sound to the outside, buzz, squeak and rattle testing, an automotive acoustic test for determining fit and wear of vehicle components as they are perceived acoustically and many other methods and procedures. The brief sampling (see Table 5.11) of ISO standards for general applications and SAE standards for automotive and transportation markets displays the diversity of measurements, methods, and application areas.

FOR

Some virgin plastics and recycled grades may develop unpleasant odors during and after processing or after aging. To avoid or reduce this, it is necessary to choose odorless grades or to add deodorants or specific fragrances marketed for polymers. Bactericides or preservatives avoid the growth of microorganisms, fungi, and so on, limiting emissions of related odors during service life. Odor and taste can be tested by traditional physicochemical instruments (e.g., gas chromatography and gas chromatography/mass spectrometry) by specific electronic instruments called e-nose and e-tongue (e.g., Alpha-MOS, www.alpha-mos.com; Electronic Sensor Technology, www.estcal.com/; Sensigent, www.sensigent.com) or by evaluation panels. For evaluation by panels, ASTM edits E1870-11 Standard Test Method for Odor and Taste Transfer from Polymeric Packaging Film. This test method is designed for use by a trained sensory panel experienced in using an intensity scale or rank ordering and familiar with the descriptive terminology and references associated with packaging materials. Data analysis and interpretation should be conducted by a trained and experienced sensory professional. This test method should be considered as a screening technique for suppliers and end-users to use in assessing the flavor impact of packaging films. The application of this test method will result in a performance score or rank data. The determination of the suitability of a packaging film for a particular end-use should be based on a set of predetermined criteria including the performance score or rank score. Information obtained from the transfer tests can also be used to evaluate the origin of any transferred tastes or odors. The focus of this test method is the evaluation of a plastic in terms of its perceived inherent odor and the transfer of package-related odors, flavors, or both, to water and other model systems (bland food simulants).

5.10.6 Noise, Vibration, Harshness For example, considering the automotive industry, for 20 years, exterior noise emissions of personal cars have been reduced by 8, mainly due to regulations evolution. As interior noise is decreasing as well, some secondary emission sources previously masked by the most dominant sources are

5.10.7 General Collateral Effects of Colorants from a Sustainability Standpoint Regulations, laws, directives, etc., continuously evolve and depend on numerous organizations, varying by country and application field. Consequently, it is the reader’s responsibility to carefully study their own problem considering the country of production, marketing and use, the applications, and the waste regulations for the end-oflife devices, and of course, the environmental cost.

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Table 5.11 Examples of ISO and SAE Standards Dealing With Noise/Vibration/Harshness. Examples of ISO Standards ISO 1996-1:2016

Acoustics—Description, measurement, and assessment of environmental noise— Part 1: Basic quantities and assessment procedures »

ISO 2671:1982

Environmental tests for aircraft equipment—Part 3.4: Acoustic vibration »

ISO 3382-1:2009

Acoustics—Measurement of room acoustic parameters—Part 1: Performance spaces »

ISO 3382-2:2008

Acoustics—Measurement of room acoustic parameters—Part 2: Reverberation time in ordinary rooms »

ISO 3382-3:2012

Acoustics—Measurement of room acoustic parameters—Part 3: Open plan offices »

ISO 3744:2010

Acoustics—Determination of sound power levels and sound energy levels of noise sources using sound pressure—Engineering methods for an essentially free field over a reflecting plane »

ISO 534715:1993 1997

Methods for the calibration of vibration and shock pick-ups—Part 15: Testing of acoustic sensitivity

ISO 67213:1994 2015

Plastics—Determination of dynamic mechanical properties—Part 3: Flexural vibration—Resonance-curve method »

ISO 10140-3:2016

Acoustics—Laboratory measurement of sound insulation of building elements—Part 3: Measurement of impact sound insulation

ISO 10846-2:2008

Acoustics and vibration—Laboratory measurement of vibroacoustic transfer properties of resilient elements—Part 2: Direct method for determination of the dynamic stiffness of resilient supports for translatory motion »

ISO 10846-3:2002

Acoustics and vibration—Laboratory measurement of vibroacoustic transfer properties of resilient elements—Part 3: Indirect method for determination of the dynamic stiffness of resilient supports for translatory motion »

ISO 10846-4:2003

Acoustics and vibration—Laboratory measurement of vibroacoustic transfer properties of resilient elements—Part 4: Dynamic stiffness of elements other than resilient supports for translatory motion »

ISO 10846-5:2008

Acoustics and vibration—Laboratory measurement of vibroacoustic transfer properties of resilient elements—Part 5: Driving point method for determination of the low-frequency transfer stiffness of resilient supports for translatory motion »

ISO 11201:2010

Acoustics—Noise emitted by machinery and equipment—Determination of emission sound pressure levels at a work station and at other specified positions in an essentially free field over a reflecting plane with negligible environmental corrections »

ISO 11202:2010

Acoustics—Noise emitted by machinery and equipment—Determination of emission sound pressure levels at a work station and at other specified positions applying approximate environmental corrections »

ISO 11204:2010

Acoustics—Noise emitted by machinery and equipment—Determination of emission sound pressure levels at a work station and at other specified positions applying accurate environmental corrections »

ISO 11820:1996

Acoustics—Measurements on silencers in situ »

ISO 15665:2003

Acoustics—Acoustic insulation for pipes, valves and flanges »

ISO/TS 15666:2003

Acoustics—Assessment of noise annoyance by means of social and socio-acoustic surveys »

ISO 15712-2:2005

Building acoustics—Estimation of acoustic performance of buildings from the performance of elements—Part 2: Impact sound insulation between rooms » (Continued )

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Table 5.11 Examples of ISO and SAE Standards Dealing With Noise/Vibration/Harshness.—Cont’d ISO 15712-4:2005

Building acoustics—Estimation of acoustic performance of buildings from the performance of elements—Part 4: Transmission of indoor sound to the outside »

ISO 17201-3:2010

Acoustics—Noise from shooting ranges—Part 3: Guidelines for sound propagation calculations »

ISO 18233:2006

Acoustics—Application of new measurement methods in building and room acoustics »

ISO 18437-4:2008

Mechanical vibration and shock—Characterization of the dynamic mechanical properties of viscoelastic materials—Part 4: Dynamic stiffness method »

ISO 18437-5:2011

Mechanical vibration and shock—Characterization of the dynamic mechanical properties of viscoelastic materials—Part 5: Poisson ratio based on comparison between measurements and finite element analysis »

ISO 26101:2017

Acoustics—Test methods for the qualification of free-field environments »

Examples of SAE Standards J1030

Maximum sound level for passenger cars and light trucks

J1060

Subjective rating scale for evaluation of noise and ride comfort characteristics related to motor vehicle tires

J1074

Engine sound level measurement procedure

J1096

Measurement of exterior sound levels for heavy trucks under stationary conditions

J1160

Operator ear sound level measurement procedure for snow vehicles

J1161

Operational sound level measurement procedure for snow vehicles

J1169

Measurement of light vehicle exhaust sound level under stationary conditions

J1207

Measurement procedure for determination of silencer effectiveness in reducing engine intake or exhaust sound level

J1281

Operator sound pressure level exposure measurement procedure for powered recreational craft

J1287

Measurement of exhaust sound pressure levels of stationary motorcycles

J1400

Laboratory measurement of the airborne sound barrier performance of flat materials and assemblies

J1470

Measurement of noise emitted by accelerating highway vehicles

J1477

Measurement of interior sound levels of light vehicles

J1490

Measurement and presentation of truck ride vibrations

J1492

Measurement of light vehicle stationary exhaust system sound level engine speed sweep method

J1637

Laboratory measurement of the composite vibration damping properties of materials on a supporting steel bar

J1782

Ship systems and equipment hydraulic systems noise control

J1805

Sound power level measurements of earthmoving machinery—Static and in-place dynamic methods

J184

Qualifying a sound data acquisition system

J192

Maximum exterior sound level for snowmobiles

J1970

Shoreline sound level measurement procedure for recreational motorboats

J2005

Stationary sound level measurement procedure for recreational motorboats (Continued )

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Table 5.11 Examples of ISO and SAE Standards Dealing With Noise/Vibration/Harshness.—Cont’d J2103

Acoustics—Measurement of airborne noise emitted by earthmoving machinery— Operators position—Stationary testing condition

J247

Procedure and instrumentation for measuring acoustic impulses from deployment of automotive inflatable devices

J2521

Disc and drum brake dynamometer squeal noise matrix noise test procedure

J2531

Impulse noise from automotive inflatable devices

J2625

Automotive vehicle brake squeal test recommend practice

J2694

Antinoise brake pads shims: T-pull test

J2747

Hydraulic pump airborne noise bench test

J2786

Automotive Brake Noise and Vibration Standard Nomenclature

J2805

Measurement of noise emitted by accelerating road vehicles

J2825

Measurement of exhaust sound pressure levels of stationary on-highway motorcycles

J2846

Laboratory measurement of the acoustical performance of body cavity filler materials

J2883

Laboratory measurement of random incidence sound absorption tests using a small reverberation room

J2889

Measurement of minimum noise emitted by road vehicles

J2920

Measurement of tire/pavement noise using sound intensity

J3002

Dynamometer low-frequency brake noise test procedure

J3013

Friction material elastic constants determination through FRF measurements and optimization

J336

Sound level for truck cab interior

J34

Exterior sound level measurement procedure for pleasure motorboats

J377

Vehicular traffic sound signaling devices (Horns)

J47

Maximum sound level potential for motorcycles

J57

Sound level of highway truck tires

J671

Vibration damping materials and underbody coatings

J88

Sound measurement—Off-road work machines—Exterior

J903

Passenger car windshield wiper systems

J919

Sound measurement—Off-road work machines—Operator—Singular type

J919

Sound measurement—Off-road work machines—Operator—Singular type

J986

Sound level for passenger cars and light trucks

FRF, Frequency response function.

Formulations require the selection of suitable polymers and additives having effects on technical properties and in consequence on the drawing and properties of parts, aging and so lifetime, and modification of economics. Of course, the choice of special chemical entities leads to changes in sustainability features, but in many cases, there are insufficient data for well-founded assessments.

Special compounds must obey the general guidelines of plastics dealing with health, safety, and fine dust clouds that may form explosive mixtures with air, etc. In addition, they can require more specific attention. Due to the diversity of solutions, there is not a universal response to the sustainability concerns. Accordingly, only some incomplete comments can be made, unsuitable in certain cases,

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and it is the responsibility of the reader to choose suitable ways to study their own problem, building their own solution corresponding to their own case while meeting the general and local contexts, appropriate regulations, etc. Generally speaking, the environmental cost of special compounds includes all facets of pollution such as energy consumption, resource depletion, emission of GHGs, NOx, SO2, and others, waste disposal, etc.

5.10.7.1 Colorants and Pigments Lead- and cadmium-based pigments have been used extensively due to their relatively low cost coupled with their good fastness properties and reasonable processability. However, to respond to social and environmental concerns and regulations many manufacturers eliminate the lead and cadmium pigments. Partial ban is the most common, for example:

• Specific regulations can ban a substance for specific applications and its use can be authorized in other applications. Good examples are food contact polymers where some substances are totally or partially banned.

• In the same country, a chemical family can bring together authorized and banned entities.

• In different countries, a substance can be banned or not, or of restricted use.

• A level threshold can limit the use of a given additive, for example, several heavy metals. Certain elements or molecules are not banned, but the pressure of public opinion arouses suspicion, leading to their replacement as a precaution. This the case for PVC in automobile or medical applications. Heavy metals including mercury, zinc, copper, cadmium, vanadium, and lead, are harmful if spread in the environment. The authorized levels are linked to the considered region, the scrutinized material, and the targeted application. The literature displays examples of authorized levels as diverse as:

• • • •

Lead (Pb): 1000 ppm, 300 ppm, or less Cadmium (Cd): 100 ppm Mercury (Hg): 1000 ppm or 0.5 ppm Hexavalent chromium (Hex-Cr): 1000 ppm, 60 ppm, or 10 ppm

Other different data may be found in the literature.

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5.10.7.2 Titanium Oxide In addition to a rigorous selection of polymers and additives and a careful processing, white fillers and optical brighteners that absorb UV and reflect them in visible light can make a compound brighter with a purer white color. Photostable titanium dioxide (TiO2) grades are top-of-the-range white fillers combining whitening and opacifying properties with an efficient absorption of UV rays. A perfect appealing look can be optimized by a harmonious equilibrium between glossy and mat characteristics. Of course, TiO2 impacts the environment as can be seen through a few examples of environmental indicators:

• For one case, cumulative energy demand is 93 MJ/kg TiO2. This example demands double the energy of the average renewable plastic, but stays at the top end of the range. It requires approximately the same energy as the average fossil plastic.

• Using two examples, total CO2 emissions are 5.3 and 7.5 kg CO2/kg TiO2. These examples emit more than six-times the CO2 emission of the average renewable plastic and are above the top end of the range. They also emit more CO2 than the average fossil plastic, but stay at the top end of the range. Of course, two examples are insufficient to make a rule.

5.11 Design for Aging, Weathering, and Light and UV Behaviors Weathering covers different situations:

• Climate varies according to region and time for a given area.

• Exposure mode including direct or indirect light, sunlight duration, irradiation angle, etc.

• Other combined factors include humidity, rain, ozone, stress, etc.

• Pollution, namely acid rain, industrial pollution, etc. Some studies have shown that degradation due to weather could be stronger in moderately sunny industrial areas than in very sunny, but less polluted regions.

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Light can also be artificial with more or less broad-spectrum including UV rays.

(f1) footnote indicates that the material has met both UV and water exposure or immersion requirements as called out in UL 746C.

• (f2): Subjected to one or more of several

5.11.1 Overview of Light and Ultra Violet Resistance Polymers are organic materials and are sensitive to natural or artificial UV sources. This is of primary importance for outdoor exposure of unprotected parts and for some industrial applications such as electrical welding, photocopiers, light exposure devices, etc. Additives such as special fillers (e.g., suitable carbon blacks), UV stabilizers, and so on can enhance the basic resistance of a matrix to UV. Under quite precise conditions (angle of incidence, positioning, temperature, water vapor, surface water, etc.), tests can be done by exposure:

• to the natural light of the sun; • to the radiation of lamps, xenon lamps (Xenotest, Weather-Ometer), or others. Regarding outdoor suitability, UL consider a material suitable for outdoors if it has gone through testing in accordance with UL 746C, the Standard for Safety of Polymeric Materials—Use in Electrical Equipment Evaluations. Exposure may be UV light exposure for 720 h of twin-enclosed carbon or 1000 h of xenon-arc Weather-Ometer conditioning, and/or water exposure or immersion for seven days at 70°C. The material is tested before and after exposure to these conditions for flammability, mechanical impact, and mechanical strength. The results may lead to one of the outcomes describe here:

tests, namely UV, water exposure or immersion in accordance with UL 746C, where the acceptability for outdoor use is to be determined by UL. The (f2) footnote indicates that the material has only met or has been tested partially for UV or water exposure or immersion. The problem of light sources is obviously crucial for accelerated light aging tests. Table 5.12 [P. Gijsman, Polym. Degrad. Stabil. 46 (1994) 63] illustrates the influence of the source on the degradation. Unfortunately, the acceleration factor is not the same for all properties. In this example, the elongation at break (EB) after natural exposure is about 9 times the EB after artificial exposition. At the opposite, for the Oxygen absorption, the same ratio is approximately 1/4. The effects of light aging firstly affect the surface, appearing in several ways:

• (f1): Suitable for outdoor use with respect to exposure to UV light, water exposure, and immersion in accordance with UL 746 C. The

• Surface degradation, chalking, crazing, cracking, hardened surface layer, etc.

• Mainly for clear grades, aspect modification, loss of gloss and discoloration, chalking, yellowing, browning, etc.

• Decrease of the mechanical properties that can lead to inability to the function.

• Retraction, loss of mass. • Embrittlement. • Desorption and consumption of protective additives leading to an acceleration of the aging.

• Modification of flow properties and other characteristics, which may prevent recycling.

Table 5.12 Examples of Property Variations after Irradiation. Natural Light

Xenon Lamp With Anti-UV Glass

Duration Factor

Duration (h)

15,000

1500

10

Elongation at break (%)

700

80

Oxygen absorption (mmol/kg)

300

1400

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The degradation depends on:

• The nature of the polymer, its color and opacity, the presence of impurities and structural irregularities, and the use of protection additives.

• The nature of the spectrum (UV are the most aggressive) and the angle of the rays. The solar spectrum varies with geographical locations, the period of the year, and the local circumstances. In general, spectrum begins around 300 nm. The overall intensity, already highly variable, cannot be a sufficient criterion since only a small portion of the spectrum is known to be aggressive. The intensity of radiation for each of the wavelengths is extremely important.

• The thickness of the test piece or part. Irradiation damages the exposed surface, but warming damages the part more or less deeply.

• The ambient temperature and the temperature of the part itself, which heats up because of the absorption of light energy. For example, for the same polymer and air temperature, black samples have a surface temperature of 50°C versus 33°C for white samples.

• Moisture of air, rain, sea spray, and acid rain that add their hydrolytic action to the action of UV.

• The presence of ozone and air pollutants. • The possible mechanical stresses applied to the samples, which favor cracking, creating new surfaces for light attack and new sites for oxygen uptake. These elements contribute to the acceleration of degradation. The interpretation of natural or artificial exposures is difficult because of:

• Climate diversity. • The risks of industrial or domestic pollution in real life.

• The lack of correlation between artificial and

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Weathering is difficult to quantify because the weather covers a complex, variable, and poorly defined context. Exposure conditions vary greatly geographically and even locally by:

• Annual hours of sunshine, from less than 1200 to more than 4000 h/year;

• Energy of irradiation. For example, natural radiation energy may be 85 kLy in Central Europe, 140 kLy in Florida, and 190 kLy in Arizona;

• • • • •

Spectral composition; Average and extreme temperatures; Humidity, rain, sea spray, and acid rain; Ozone; Industrial pollution, etc.

For the United States only, are three climate examples:

• Miami: Mean temperature of 24.4°C, total annual precipitation averages of 1420 mm, and hours of sunshine per year of 2943.

• Barrow (Alaska): Mean annual temperature of12.5°C and total averages of 114 mm.

annual

precipitation

• Yuma (Arizona): Annual average temperature is 23.4°C, total annual precipitation averages of 80.6 mm, and hours of sunshine per year of 4127. So, it is impossible to determine standard conditions; some polymers can be resistant to UV and behave properly in a dry and sunny climate, but on the other hand, polymers sensitive to hydrolysis, age quickly in a hot and humid climate. With regard to time alone, it should be noted an induction period during which the loss of property is low or negligible. Then the degradation is accelerating more or less brutally (curve in “knee”). So, extrapolation of lifetimes must be cautious.

natural aging.

• The different degradation kinetics of the various properties. For example, the half-life of a given PA exposed to artificial UV light is 6000 h based on brilliance or 11,000 h based on tensile strength.

5.11.2 Elements of Weathering Appraisal Table 5.13 approximately classifies some thermoplastics on the basis of their inherent weather resistance. Formulation can greatly improve this

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Table 5.13 Ranking Proposal for Light Resistance. Good behavior Fair behavior

Limited behavior

PVDF

Table 5.14 UV Resistance of PP Compounds: Examples of Color Effect.

PTFE

Color

Relative Resistance to UV

PC

Natural

1

PET

Red

1

PMMA

Magenta

1

PPE

Blue

1.8

PVDC

Yellow

2

PS

White

2.3

ABS

Red

2.8

POM

Brick red

3.3

PA

Blue

3.5

PE

Green

3.5

PP

Black

12

PVC ABS, acrylonitrile-butadiene-styrene; PC, polycarbonate; PE, polyethylene; PET, polyethylene terephthalate; PMMA, polymethylmethacrylate; POM, polyacetals; PPE, polyphenylene ether; PA, polyamide; PP, polypropylene; PS, polystyrene; PTFE, polytetrafluoroethylene; PVC, polyvinyl chloride; PVDC, polyvinylidene chloride; PVDF, polyvinylidene fluoride.

ranking using anti-UV, fillers absorbing light, surface coatings. So, the ranking of compounds may be extremely different. For example, PVC can get a 10-year warranty for outdoor applications, painted PPE can be used for car bodies, and ABS protected by a polyvinylidene fluoride (PVDF) film is proposed for outdoor applications. Those results cannot be directly applied to real cases.

5.11.2.1 Effect of Color For a natural PP taken as base 1 for UV resistance under specified conditions, the different colored compounds prepared from this PP have relative UVresistances in the range of 1 12 (see Table 5.14). One can be surprised by relative resistance differences for the same color, for example, 1 2 2.8 and 3.3 for red colors or 1.8 and 3.5 for blue colors. Obviously, there are other parameters relating to the color:

• The three red grades are in the range of 1 3.3 because of the use of different pigments.

• The white grade has a good rank because it is obtained with an opaque pigment that stops the radiation at the surface, avoiding the degradation of the deeper layers.

• The two blues behave differently because the used pigments are different.

• It should be noted the outstanding behavior of black PP.

5.11.2.2 Effect of Anti-UV Additives Table 5.15 displays property retentions after 1 year of exposure for stabilized and unstabilized polymers; UV protections are effective, but do not systematically improve all properties. For example, for white polycarbonate (PC), elongation at break is drastically increased when tensile strength and impact resistance are not significantly changed. Table 5.16 displays another face of UV protection efficiency concerning embrittlement times of PP protected with six different systems. The efficiency factor linked to unstabilized PP varies from 1.06 to 5.2. [N.S. Allen, et al., Polym. Degrad. Stabil. 61 (1998) 183.]

5.11.3 Examples of Published Assessments Relating to Light and UV Behavior of Compounds The following information is not a scientific or technical study, but a jumble of more or less vague facts and figures that are not comparable (see Section 5.11.3). The following results relate to a few grades tested or basically assessed under particular conditions and undefined criteria of

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Table 5.15 Examples of Property Retentions after 1 Year of Exposure. Retentions (%) Location PC

Unstabilized

Tensile Strength

Elongation at Break

Arizona

7

Stabilized PC-white

Unstabilized

97 Florida

Stabilized PE

Unstabilized

Impact

Florida

Stabilized

96

22

91

93

78

85

56

59

52

76

78

95

Table 5.16 Embrittlement Times of PP Protected With Six Different Systems. UV Protection System

Embrittlement Time (h)

None

384

A

408

1.06

B

912

2.4

C

1032

2.7

D

1512

3.9

E

1944

5.1

F

2004

5.2

Efficiency Factor

PP, polypropylene.

satisfaction. Of course, they cannot be generalized. As already said, it is essential to check the used grade in convenient conditions.

5.11.3.1 Polyolefins and Derivatives Polyolefins generally resist hydrolysis well, but are more or less naturally sensitive to light and UV. They must be protected by efficient protective systems. Polyethylene (PE) must be protected by the addition of anti-UV and other protective agents and/or by 2% 3% of an adequate carbon black. In such cases, after weathering of test bars for several years in various climates, the retention of tensile strength is generally good, but the elongation at break retention can be as low as 10%. PP must be protected by the addition of anti-UV and other protective agents and/or by 2% 3% of a suitable carbon black.

After weathering of test bars (3 mm thick) for 1 year in a sunny climate, the retention of properties is, for example:

• 56% for tensile strength, 59% for elongation at break, and 62% for impact strength for a natural unstabilized grade.

• 76% for tensile strength, 78% for elongation at break, and 95% for impact strength for a natural UV-protected grade. Polymethylpentene (PMP) must be protected by the addition of specific anti-UV and other protective agents. Cyclic olefin copolymers (COC) is proposed in light and UV stabilized grades. Ethylene-vinylacetate copolymers (EVAs) are naturally resistant to light, UV, ozone, and weathering and, even more, they can be protected by the addition of specific anti-UV and other protective agents. Under identical conditions, the lifetimes of films exposed outdoors are 3 years for a protected EVA versus less than 1 year for an LDPE film. Increasing vinyl acetate content generally improves light, UV, ozone, and weathering resistance. Ethylene-vinyl alcohol copolymers (EVOH) is sufficiently resistant to light and UV to be used in packaging, but it is sensitive to water and must be protected. Ethylene-methacrylate ionomers (EMA) ionomers must be protected for long exposures to light and UV such as in exterior automotive parts.

5.11.3.2 PVC and Other Chlorinated Thermoplastics PVC resists hydrolysis well, but is naturally sensitive to light and UV. It must be protected by the

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addition of anti-UV and other protective agents. Well-optimized compounds and grades stabilized against heat, UV, light, and weathering resist weathering and long warranty periods can be allowed, for example, 10 years and more. For protected white rigid PVC, after natural weathering for 3 years in Michigan, the retention of impact strength is 68% and the yellowness index increases by 5%. Chlorinated PVC (PVC-C) resists hydrolysis well, but is naturally sensitive to light and UV. It must be protected by the addition of anti-UV and other protective agents. In these cases, PVC-C can be used for long-lasting exterior parts. Chlorinated polyethylene (CPE): Suitable compounds exhibit good property retention after 6 years of exposure in Arizona, for example:

• 120% for 100% modulus; • 110% for tensile strength; • 90% for elongation at break, which is the most sensitive property to UV and weathering. PVDC resists hydrolysis well, but is naturally sensitive to light and UV. It must be protected.

UV light can, therefore, be compared with that of ABS. Intense UV radiation or outdoor weathering can damage the rubber component, leading to yellowing and reduced impact strength. Finished parts made from MABS in pale transparent colors are particularly susceptible to color change on weathering or heat aging. MABS is, therefore, preferably used in indoor applications. Styrene acrylonitrile (SAN) resists hydrolysis well, but may be sensitive to light and UV. It must be protected by the addition of anti-UV and other protective agents. Acrylonitrile styrene acrylate (ASA) resists hydrolysis well, and is naturally much less sensitive to light and UV than ABS. Retention of mechanical performances is far better and yellowing is far lower. Even after long-term weathering, suitable ASA grades do not show the greying typical of even UVstabilized ABS. ASA has applications in exterior parts for automotive construction. ASA may be alloyed with polycarbonate. Acrylonitrile EPDM (terpolymer ethylene, propylene, diene) styrene and acrylonitrilechlorinated polyethylene-styrene are more resistant to weathering than ABS; EPDM and CPE being more weather resistant than polybutadiene.

5.11.3.3 Styrenics PS resists hydrolysis well, but is naturally sensitive to UV, light, and weathering, especially when alloyed with a UV sensitive rubber such as polybutadiene. It must be protected by the addition of anti-UV and other protective agents and/or by a suitable carbon black. After weathering, the retention of properties for test bars (3 mm thick) is, for example:

• 85% for tensile strength after 6-month outdoor exposure in Los Angeles for a protected GF reinforced grade.

• 89% for tensile strength after 12-month outdoor exposure in Los Angeles for another protected GF reinforced grade. ABS resists hydrolysis well, but is naturally sensitive to light and UV, more so as the amount of polybutadiene increases. It must be protected by the addition of anti-UV and other protective agents or by an outer film of UV-resistant polymer such as PVDF. Methylmethacrylate-acrylonitrile-butadienestyrene (MABS) has a butadiene-containing elastomer component. Its behavior on exposure to heat or

5.11.3.4 Polyamides PA6 or PA66 (polyamides) is naturally sensitive to light and UV. It must be protected by the addition of anti-UV and other protective agents. After weathering of test bars (3 mm thick) in a sunny climate, the property retentions are, for example:

• 50% for tensile strength and 3% for elongation at break after 6 months for a natural unprotected grade.

• 32% for tensile strength and 2% for elongation at break after 5 years for a natural unprotected grade.

• 99% for tensile strength and 38% for elongation at break after 6 months for a UVprotected grade.

• 89% for tensile strength and 22% for elongation at break after 5 years for a UV-protected grade. PA11 and PA12 must be protected by the addition of anti-UV and other protective agents. Optimized PA12 grades are resistant to weathering and suitable for many exterior applications.

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Resistance to weathering can be further improved by suitable UV stabilization and pigmentation with carbon black. This allows for use in applications under climates with high UV radiation. For two grades of PA12, one in natural color, the other in black, the half-life of 1-mm-thick test bars based on:

• Gloss would be in the range of near 1 year (natural color) to nearly 3 years (black sample).

• Tensile impact strength would be in the range of near 1 year (natural color) to much more than 5 years (black compound). Transparent PA exhibits generally fair resistance to weathering. Some UV-stabilized grades can satisfy stringent specification requirements, harsher than f1 according to UL 746C and are, therefore, suitable for use in exterior applications. Even after 20,000 h of exposure to xenon light at 65°C with dry/water cycling, no noticeable change can be seen in the mechanical and optical properties (transparency, color) of suitable UV-stabilized grades. By comparison, some general-purpose transparent PA grades have half-lives based on tensile strength on the order of more or less 1000 h.

5.11.3.5 Thermoplastic Polyesters Polyesters are sensitive to hydrolysis and UV. They must be protected by the addition of anti-UV and other protective agents. Generally, black grades are more resistant than neat ones. In these cases, after weathering of test bars for 1 year in various sunny climates, the retention of tensile strength or notched impact strength is generally good. For 3-year outdoor exposures of 3-mm-thick samples, the retention of tensile or impact strengths can be, for example:

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5.11.3.6 Polymethylmethacrylate The weathering resistance is one of the most interesting features of polymethylmethacrylate, along with its transparency. The inherent UV resistance can be further improved by the addition of protective agents. Optical properties are not greatly affected by long outdoor exposures. For example, after 3-year exposure in a sunny climate, the light transmittance of given grades is superior to 90%, and the yellowing and haze are slight. For 3-mm-thick samples exposed in the same conditions, the retention of mechanical performances can be, for example:

• 70% 85% for tensile strengths. • 40% 70% for elongations at break. • 70% 90% for impact strengths. 5.11.3.7 Polycarbonate Polycarbonates (PCs) are inherently sensitive to hydrolysis and UV. They must be protected by the addition of anti-UV and other protective agents. Generally, black grades are more resistant than neat ones (but they lose their transparency). In these cases, after weathering of test bars for 1 year in various sunny climates, the retention of tensile strength or notched impact strength is generally good. For a 2-year outdoor exposure of transparent PCs, the retention of impact strengths can be, for example:

• 4% for an unstabilized grade. • 100% for a UV-stabilized grade. Under the same conditions, the optical properties after exposure are:

• Unstabilized grade: 82% for transmittance,

• 50% 97% for natural unreinforced polybuty-

20% for the haze, and 20 for the yellowing index.

leneterephthalates (PBTs), depending on the UV stabilization.

• UV-stabilized grade: 87% for transmittance,

• 65% 97% for black unreinforced PBTs,

15% for the haze, and 6 for the yellowing index.

depending on the UV stabilization.

• 84% 100% for black reinforced PBTs, depending on the UV stabilization.

Different data can be obtained with other grades under different conditions.

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5.11.3.8 Polyacetal

5.11.3.11 Cellulosics

Polyacetals (POM) are UV sensitive and must be protected by the addition of anti-UV and other protective agents. Generally, black grades are more resistant than natural ones. In these cases, after weathering of test bars for 1 year in various sunny climates, the retention of tensile strength or notched impact strength is generally good. For 3- and 10-year outdoor exposures of 3-mmthick samples, retentions of tensile strength and elongation at break can be, for example:

Cellulosics are inherently moisture and UV sensitive, requiring efficient stabilization. cellulose acetate (CA) is particularly sensitive to water and weathering.

• Nearly 100% of tensile strength for UVstabilized acetals.

• 45% 75% for elongation at break, depending on the UV stabilization.

5.11.3.9 Polyphenylene Ether Polyphenylene ether (PPE) is moderately UV sensitive and must be protected by the addition of anti-UV and other protective agents. Generally, black grades are more resistant than natural ones.

5.11.3.10 Fluorinated Thermoplastics Perfluorinated thermoplastics are not sensitive to moisture or UV. Generally, stabilization is not needed. For PTFE, after 1-year outdoor exposures of 3mm-thick samples, retentions of tensile strengths and elongation at break are near 100%. After 15-year outdoor exposures of 0.1- to 0.15mm-thick films in a sunny and humid climate, the retentions of tensile strength and elongation at break are in the range of 91% 125% without visible change. Ethylene-tetrafluoroethylene (ETFEs) are inherently insensitive to moisture and UV. Generally, stabilization is not needed. However, GF-reinforced grades can be altered by long outdoor exposures. PCTFEs are insensitive to moisture and UV. Generally, stabilization is not needed. ECTFEs are inherently insensitive to moisture and UV. Generally, stabilization is not needed. PVDF is inherently insensitive to moisture and UV. Generally, stabilization is not needed. PVFs are inherently resistant to weathering. After 6 years of outdoor exposure in a sunny climate, retentions of properties are about:

• 80% for tensile strength. • 55% for elongation at break.

5.11.3.12 Polysulfone PSUs are inherently UV sensitive and must be protected by the addition of anti-UV and other protective agents. Black compounds are generally more resistant.

5.11.3.13 Polyphenylene Sulfide PPS are inherently resistant to UV, weathering, and hydrolysis. Black compounds are the most UVresistant. The mechanical characteristics of a PPS grade remain fair after an exposure of 10,000 h in a Weather-Ometer.

5.11.3.14 Polyetherimide PEIs are inherently resistant to UV and hydrolysis.

5.11.3.15 Liquid crystal polymer Typically, LCPs have good weatherability. In a series of experiments, certain LCPs are slightly altered by 1 year of outdoor exposure with a light surface chalking, but after a 2000-h exposure in a Weather-Ometer, retention of mechanical properties is superior to 90%.

5.11.3.16 Polybenzimidazole The resistance of PBI to weathering is estimated by certain sources to be limited.

5.11.3.17 Alloys ABS/PC: Sensitivity to heat, UV, light, and weathering, requires efficient protections for outdoor exposure (stabilized grades are marketed). ABS/PA: Sensitivity to heat, UV, light, and weathering, requires efficient protection for longterm outdoor exposure (stabilized grades are marketed). ASA/PC alloys are appreciated for their behavior and low yellowing with UV, light, and weathering, but UV protection is needed for long-term outdoor exposure (stabilized grades are marketed).

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ABS/PA: Sensitivity to heat, UV, light, and weathering, requires efficient protection for longterm outdoor exposure (stabilized grades are marketed). PP/PA: Sensitivity to heat, UV, light, and weathering, requires efficient protection for outdoor exposure (stabilized grades are marketed). Thermoplastic polyester alloys exhibit a certain sensitivity to heat, UV, light, and weathering, requiring efficient protection for outdoor exposure (stabilized grades are marketed). ABS/PVC: Sensitivity to heat, UV, light, and weathering, requires efficient protection for outdoor exposure (stabilized grades are marketed).

5.11.3.18 TPE and Thermoplastic vulcanizate Styrenics thermoplastic elastomer: Styrenebutadiene-styrene (SBS), as well as all elastomers rich in double bonds, are not suited to exposure to light, UV, and ozone, whereas styrene ethylene/ butylene styrene (SEBS) shows good behavior. Thermoplastic olefin (TPO) resists hydrolysis well, but is naturally sensitive to light and UV. It must be protected by the addition of anti-UV and other protective agents and possibly by a small percentage of an appropriate carbon black. PP/EPDM-V (Terpolymer ethylene, propylene, diene, vulcanized) resists hydrolysis well, but is naturally sensitive to light and UV. It must be protected by the addition of anti-UV and other protective agents and possibly by a small percentage of an appropriate carbon black. Thermoplastic elastomer (TPE)/PVC resists hydrolysis well and is naturally sensitive to light and UV, but special grades are marketed with sufficient weathering resistance to allow exterior applications in the automotive industry and construction. Thermoplastic polyurethanes (TPUs) are naturally sensitive to light, UV, and hydrolysis, but special grades are marketed. Specific grades target applications in tropical climates. Copolyester TPEs (COPEs) are naturally sensitive to light, UV, and hydrolysis, but special weathering-resistant grades are marketed. Polyester-esters are more UV-resistant, but more sensitive to hydrolysis. Polyether block amides (PEBAs) are naturally sensitive to light, UV, and hydrolysis, but special grades are marketed. Half-lives corresponding to a

203

50% decay of elongation at break after Xenotest exposure are roughly:

• 5 months for UV-stabilized grades with 25 40 Shore D hardness;

• 6 months for UV-stabilized grades with 55 70 Shore D hardness.

5.12 Lifetime and End-of-life Criteria Fig. 5.14 displays some ins and outs linked to lifetime.

5.12.1 Overview Actual lifetime is not an intrinsic feature, but depends on the essential properties required for the targeted applications and varies according to the set level of properties retained as end-of-life criteria. Lifetime mainly results from:

• The plastic behavior versus required mechanical constraints, temperature, creep, relaxation, dynamic stresses, light, UV, water, chemicals, pressure, radiations, aesthetics, etc.

• The end-of-life criteria including technical, sensory, and physical features.

• The degradation level considered as acceptable, etc.

Lifetime Aged properties End of life criteria Environment of application: temperature, humidity, chemicals, UV, radiations... Modeling Formulation Protective skins Device design minimizing aggressive factors

Figure 5.14 Lifetime: some ins and outs.

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204

That is a common source of dispute between plastic parts providers and users. Generally speaking, converters define a lifetime for a set of conditions and end users apply conditions “near” those defined by the converter. This can lead to thermal or mechanical overloading, which is damaging for the polymer and can significantly shorten the lifetime. Most common traps are the thermal overloading and the application of loads overpassing the yield point, but many other causes include, but are not limited to weathering, UV exposure, chemical environment, dynamic constraints, combination of stresses, etc. Part drawing is a significant factor because it can play the role of stress concentrator or a high thickness can mitigate the penetration of light and UV in depth. Designers using polymer materials are increasingly requiring assurance of product lifetime, particularly for components that cannot be easily inspected or replaced or that may fail in service, leading to disastrous hazards. Whilst the life expectancy of products in nondemanding applications have traditionally been predicted from previous in-service experience, the use of plastics in long-term or critical applications requires a far better understanding of the failure mechanisms and the use of accelerated aging conditions to generate data usable in predictive models. From a sustainability standpoint, an actual lifetime increase is of prime importance mitigating resource depletion, pollution, waste disposal, and end cost. Lifetimes are rigidly linked to end-of-life criteria, which leads to two major issues.

and reinforcements, the processing parameters, and the recycled polymer use. To reach the same lifetime, it is often possible to choose between different technical routes. For example, it is possible to choose opposite strategies such as, on the one hand, a cheap polymer and expensive protective agents or, on the other hand, an expensive compound without the use of additives. All properties including sensory properties degrade during aging, which may limit the lifetime of plastics parts still having satisfactory mechanical properties. A multitude of properties are not previously listed, but may be occasionally encountered such as, for example, without claiming to be exhaustive, biological degradation, high energy radiation resistance, thermal conductivity, antimicrobial behavior, microwave transparency, plating, painting or printing ability, X-ray opacity, and sterilization resistance. Biological degradation is not a common form of degradation as the most commonly used traditional thermoplastics are resistant to microbiological attack. Until recently, the only cases of biological attack influencing the lifetime of plastics were related to certain polyurethanes and some low MV additives in PVC. However, some biodegradable plastics are developing and biodegradation needs more in-depth considered. Some standards deal with biological resistance, for example:

• All the selected properties age at different rates

action of microorganisms: methods for determining the deterioration of plastics due to the action of fungi and bacteria and soil microorganisms. The aim is not to determine the biodegradability of plastics. The type and extent of deterioration may be determined by (1) visual examination, (2) changes in mass, (3) changes in other physical properties.

and the lifetime is reached when one (or several) properties leads to a part failure. Mechanical performances and high and low temperature behaviors are rarely forgotten, but aging of some other characteristics are sometimes neglected. For example, without claiming to be exhaustive, sensory properties, electrical and fire behaviors, weathering, chemical issues, and microbiological degradation.

• Other points difficult to control are the end-oflife criteria because the actual conditions of use are unknown or specifications for use may not be followed by the user. For given conditions of application, the lifetime depends on the used polymer, the used additives

• ISO 846 (1997) Plastics—Evaluation of the

• ASTM

G29 2 16—Standard Practice for Determining Algal Resistance of Polymeric Films.

Last but not least, longer lifetimes lead to better sustainability due to the mitigation of resource depletion, energy and pollution savings, cheaper end-of-life costs, and reduction of the recycling or

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205

disposal issues. Of course, the lengthening should not be a marketing tool, but must be real.

Of course, the risk of deviation increases with the number of steps.

5.12.2 Accelerated Aging and Modeling

5.12.3 Smart Design and Mitigation of Aggressiveness of Surroundings are Benefiting from a Sustainability Standpoint

For long lifetimes, testing in actual conditions is not useable and it is necessary to run accelerated testing in more severe conditions and run mathematical models with the obtained results to predict the lifetime in actual conditions. Be careful about the accelerated aging conditions; more severe conditions can activate chemical reactions different from those observed at service conditions, which can lead to false predictions. For example, degradation at 150°C of commodity plastics is not of the same nature as the degradation at room temperature. Kinetics may change during long-term tests in steady conditions. For example, aging kinetics can suddenly evolve with abrupt changes, thresholds, knees or sudden failures, and so on. Generally speaking, it must be noted that a mathematical model is an equation giving a result in all cases. In real life, results can be completely different and a part may fail when the model predicts a longer life or, conversely, the part may remain operational when the model predicts a shorter life. The user must be aware of these risks. So, certain predictions can be disastrous, leading to completely false estimations. In optimistic cases, modeling can save time and money by reducing trials and property testing. The mathematical laws binding the variation of one property and a parameter such as time suppose that the property continuously evolves without abrupt changes. Thresholds, knees or other sudden failures, and so on must be specifically modeled. So, for a single case, it is necessary to use several different models. A simple scheme includes three steps:

• The first step will model the first smooth phase of kinetics.

• The second step will model the first “accident” (knee or other abrupt change of kinetics).

• The third step will model the second smooth phase of kinetics.

Smart design can minimize the intensity of aggressive factors. For example, a device can be set up further from the heat source or a plastic part can be hidden by another device or part to obviate light or UV degradation, etc. Polymers can be protected due to a smart formulation including protective additives or by shielding with another material, metal, or other polymer, resistant to the aggressive factor. Protective additives can be, for example, processing stabilizers, antioxidants, light and UV stabilizers, UV absorbers, hydrolysis stabilizers, fire retardants, antirodent and antivermin agents, etc. Coatings, films, overmolding or comolding with another plastic, surface treatments, painting, and metallization isolate the plastic core from surroundings allowing for surface properties to be obtained that are completely different from those of the core and vice versa. Two inherent problems for coatings are the permanent cohesion between the treated part and the coating and the abrasion and wear of thin films and coatings occurring in service. Other parameters being unchanged, a loading reduction generally leads to an increase of the lifetime. The environment of service plays a major role in an effective lifetime. Generally speaking, a longer lifetime goes with a better sustainability provided that the methods used have an acceptable environmental cost. Without claiming to be exhaustive:

• Other parameters being unchanged, a mechanical loading reduction generally leads to an increase of the lifetime, thus, improving sustainability.

• Mitigation of high temperatures improves sustainability.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

• For cold temperatures, a lowering of the temperature can lead to two opposite consequences. On the one hand, a possible decrease of impact resistance, and on the other hand, a slowing of chemical aging.

Regulations, directives, standards, approvals, health, safety requirements

Country of fabrication, sale , use, disposal...

• Humidity can speed up the aging of certain

Banned materials

polymers as far as the temperature is higher.

• Generally, chemicals speed up aging, but

Fire behavior

sometimes some chemicals protect polymers from oxygen.

Pollution

• Environmental stress cracking speeds up the degradation of sensitive polymers.

Health safety

• Weathering and UV exposure speed up aging according to the type of polymer used. It must be noted that weathering is highly dependent on the country of service.

• High energy radiations speed up degradation, but are used to cure certain polymers.

5.13 Regulation, Health, and Safety Requirements The following is a limited and incomplete reminder. The reader must search the suitable standards, regulations, directives, approvals, and laws related to their own case and is solely responsible for the chosen solutions. Design, processing, and application of plastics and composites are professional activities needing specific skills and involving industrial and financial risks, health hazards, toxicity, fire hazards, regulation compliance, etc. Standards, directives, regulations, approvals, laws, and codes depend on the regions of processing, commercialization, use and application, and disposal. Beware of names and acronyms that can cover different requirements according to countries or industrial sectors. For example, for the same part, requirements can be different in the country of processing and in the country of commercialization. It is the responsibility of the reader to search, study, and verify the compliance of the chosen solution with processing rules, safety precautions, health hazards, existing national and corporate laws and regulations emitted by the countries of processing, commercialization, use and application, and disposal.

General and specific regulations and requirements

Figure 5.15 Regulations, standards, directives, approvals, laws, etc., some ins and outs.

Regulations and specifications including general regulations related to industrial and commercial activities concern workers at all steps of a part’s life cycle, users, and all people involved in handling, processing, storage, and disposal, etc. Of course, in addition to rule compliance, prototypes and tests under operating conditions are essential. Fig. 5.15 displays some ins and outs related to plastic regulations, standards, directives, approvals, laws, etc. Government and private agencies have specifications and approval cycles for many plastics parts. For instance, for the United States, a few examples of US agencies include, without claiming to be exhaustive:

• Underwriters’ Laboratories (UL) for electrical devices

• Military (MIL) for military applications • Food and Drug Administration for applications with food and bodily-fluid contact

• United States Department of Agriculture for plastics in meat and poultry equipment

• National

Sanitation Foundation Testing Laboratory, Inc. for plastics in food-processing and potable-water applications

• USP-US Pharmacopeia Convention (www.usp. org/)

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• • • •

FOR

PLASTICS SUSTAINABILITY

Federal Aviation Administration FAR US Fire Administration US Department of transportation, National Highway Traffic Safety Administration that issue FMVSS

• And many others Generally speaking, be aware of the points listed below, among others:

• International or national standards can be mandatory or not.

• Two standards or specifications can seem similar, but some details can be different and results can be different.

• Always check for compliance and approval from appropriate agencies.

• Corporate associations also have their standards and specifications such as the building or medical sectors.

• A name or acronym can relate to several standards, regulations, directives, approvals, laws, etc. For example, REACH may be an European

207

Directive, but also a China regulation dealing with new chemical substance notification to the Chemical Registration Center of the Ministry of Environmental Protection for new chemicals irrespective of annual tonnage, that is, chemicals other than the approximately 45,000 substances currently listed on the Inventory of Existing Chemical Substances Produced or Imported in China.

• Private companies can also have specific standards and specifications such as, for example, automakers and aircraft manufacturers.

Further Reading Biron, M., 2014. Thermosets and Composites. Elsevier Ltd. Biron, M., 2015. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2017. Industrial Applications of Renewable Plastics. Elsevier Ltd. Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Plastics Additives & Compounding, Elsevier Ltd. Plastics News.com, Crain Communications. Reinforced Plastics, Elsevier Ltd.

6 Environmental and Engineering Data to Support Eco-Design for Plastics Eco-design takes advantage of standardized data avoiding some traps. As engineering data, environmental indicators must be intelligently used avoiding artificial bias.

6.1 Overview

general rules linked to technical data and rules linked to polymers. In real life, materials are not perfect but result from a subtle balance of the technical and economic requirements which determine the real part and product features and in conclusion the business success. Of course, like all human activities, the properties suffer from some uncertainty and even sometimes from errors.

Among other criteria, sustainability includes:

• Environmental requirements • Function ability of parts and products • Competitiveness Environmental indicators have been developed to complement and enrich the large collection of standards dealing with technical characteristics of plastics. Competitiveness results from the economical optimization of environmental and technical features of the designed parts or devices during all their lifetime. Eco-design or environmentally conscious design (ECD) or sustainable design targets the reduction of adverse environmental impacts of a product throughout its entire life cycle. This can involve balancing the environmental aspects of the product with its intended use, performance, cost, marketability and quality, and choosing methods to meet legal and regulatory requirements in the most environment-friendly way. The following section deals with:

• Usual environmental indicator data linked to plastics.

• Usual engineering indicator data for plastics design.

6.2 Be Cautious of Some Traps Concerning Standards Standards are irreplaceable but their use must be well understood and cautious, taking into account

6.2.1 General Boundaries of Standards The field of standardization and certification is very broad, complex, and rapidly changing. The following information is not exhaustive and standards evolve every day. Consequently, the reader must consult dedicated websites such as https://www.iso.org/, https:// www.astm.org/, http://ulstandards.ul.com/, among others, to update the following information and to explore more in depth particular aspects of its problem. Properties depend on the exact grade, thickness, color, surrounding conditions and procedures, and the history of the part under consideration. Standards and procedures must be clearly specified. All the properties are influenced by the polymer and the actual additives used with the plastic matrices, notably the reinforcements but also stabilizers, plasticizers, hardeners, chain extenders, colorants, and others. Property measurement standards only allow comparisons: the test specimens are produced under the best possible conditions, the deleterious factors are isolated to avoid any synergy, the duration of tests is inevitably limited, and so forth. In real life, this is practically never the case and the results found in the literature will have to be verified, checked, interpreted, and corrected with safety margins.

Concerning results found in the literature, including this book, do not forget that a same generic name may hide several measurement methods more

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00006-9 © 2020 Elsevier Ltd. All rights reserved.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Lack of satisfaction

Frequency

Satisfaction

Initial

Aged

0

100

200

300

400

500

Property

Figure 6.1 Weak points and user’s dissatisfaction.

or less similar (or dissimilar), surrounding conditions may differ, and, unfortunately, typographical errors are not excluded.

Failure of parts is led by the ratio of the actual mechanical (or other) stress on every point of the part versus the mechanical stress at break of the weakest point.

6.2.2.1 Failure Onset: Weak Points and Average Properties For new parts, the local values of a property at any point of the part are subjected to a dispersion in the bulk of the part and to another dispersion between different parts. Moreover this double dispersion is enlarged by aging and service life. According to the material and the process, macromolecular and reinforcement orientations can dramatically change the properties depending on the direction of constraints versus that of processing. Consequently, an actual property at a spot of a part can be far from the property measured on laboratory samples. Weakest values, lower than the average value generally provided by producers, are initiators of failure. Fig. 6.1 schematizes an example for a theoretical property. The onset of satisfaction (200 in this theoretical example) is totally satisfied at the initial stage. After aging, the average value is good enough (240) but there is a lot of data lower than the satisfaction onset, which leads to potential risks of failure. It is necessary to improve the aging resistance or the average initial property and its dispersion to enhance the values after aging. Theoretically, it may also be

Frequency

6.2.2 Real Cases Are Not Ideal Standardized Cases: Take Into Account the Statistical Distribution of Properties

Sigma=2 Sigma=4

Property

0 30

40

50

60

70

Figure 6.2 Normal distribution and standard deviation. The black curve displays a standard deviation of 2 versus 4 for the red one, which leads to a significant difference for the property level suitable for a same frequence of failure.

possible to lower the acceptable aggressive constraints during the service life if the customer agrees. If not, it is possible to shorten the predicted lifetime with possible marketing consequences. Weak points are often located at interfaces between reinforcements and matrix, joining between two different subparts, weld lines, sharp angles, voids, and so forth.

6.2.2.2 Do Not Confuse Local and Bulk Properties: Take into Account the Statistical Distribution of Properties The numerous parameters involved during the development of polymers and additives, plastics processing, use of parts and products lead to a statistical distribution of the properties. Of course, the data dispersion increases with the complexity of the material and geometry.

6.2.2.3 Means are False Friends The common characterization of properties by their average value hides the weak points and leads to a false safe feeling. The statistical treatment of

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Table 6.1 Tensile Strength of Various Materials. Material

μ (MPa)

σ (MPa)

Cv (%)

95% Confidence Interval

Steel

527.9

1.161

0.2

526
530

Polycarbonate

59.18

0.3217

0.54

58.5
59.8

PMMA

77.62

2.606

3.4

72.4
82.8

PMMA, Poly methylmethacrylate.

experiments allows computing the lowest properties of weak points that are not visible. Fig. 6.2 displays the frequency versus the values of a theoretical property for two materials having the same mean property (50) with a standard deviation of 2 and 4, respectively. To have less than 1/10,000 failure, it is necessary to limit the service stress to 42 in one case and 35 in the other case. Table 6.1 compares the statistical distribution of the results of strength at break of a steel and two thermoplastic materials:

• average μ • standard deviation σ • coefficient of variation Cv defined as the ratio between the standard deviation (σ) and average μ: Cv 5 σ/μ

• 95% confidence interval: two standard deviations on both sides of the average value Quoted examples are not rules, and cannot be used for computing and designing. Only results obtained with the used compound processed by a method similar to that used for real part production are convenient.

6.2.2.4 Standard Deviation Depends on Multiple Factors For laboratories trained in characterization of plastics, the distribution of the results depends, among other things, on the nature of the measured characteristic, the history of the samples, and the preparation of test specimens. Table 6.2 displays examples of statistical results of stress and strain measured under tensile, compression, and shear loads for 26 different samples. Coefficients of variation are in a broad range, from 0.5% up to 18.3%:

• 0.54% up to 3.4% for medium tensile strengths (TSs) and, 9% and 10.4% for high values of TS related to composites (samples E and F)

• • • • • •

9.3% and 11.6% for compression strength 3.9%
8.3% for shear strength 0.7%
7.1% for tensile modulus 3.3% and 6.2% for compression modulus 5.6%
12.5% for shear modulus 9.5%
18.3% for deformations.

Quoted examples are not rules, and cannot be used for computing and designing. Only results obtained with the used compound processed by a method similar to that used for real part production are convenient.

6.2.3 Be Cautious of the Real Sense of Common Terms Renewable, green, eco, bio grades, and others may have renewable content as low as 20% (or less) or as high as 100%. The data must be carefully verified because of the broad range of figures for a same polymer, the continuous evolution of commercialized grades, and the hypotheses and methods used for the calculation. Table 6.3 displays examples without claiming to be exhaustive and very different data can be found elsewhere. Pay close attention to carbon biobased content and renewable content. Biobased or renewable carbon content of a plastic is the amount of biobased carbon in the material or product as fraction weight or percent weight of the total organic carbon in the material or product. That does not include the weight contribution from oxygen and other elements leading to lower figures. For the same compound made out of 30% cellulose and 70% fossil polymer, the ASTM D6866 leads to only 20%
25% biocarbon content. Table 6.3 displays some renewable content claimed for some polymers. These data must be carefully verified because of the broad range of figures for a same polymer, the continuous evolution of commercialized grades, and the hypotheses

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Table 6.2 Statistical Distributions of the Results of Different Mechanical Tests. Average

Sample A Sample B Sample C Sample D Sample E Sample F

23.8 26.9 59.2 77.6 288 266

Sample G Sample H

155 150

Sample I Sample J Sample K Sample L

19 18 14 12

Sample M Sample N Sample O Sample P

0.274 0.295 14 13

Sample Q Sample R

16 15

Sample S Sample T Sample U

1.70 1.6 1.8

Sample V

0.10

Sample W Sample X

26.5 34.3

Sample Y Sample Z

409 311

Standard deviation

coefficient of variation Strength (MPa) Tensile strength 0.4 1.7 0.8 3 0.32 0.54 2.6 3.4 30 10.4 24 9 Compression strength 18 11.6 14 9.3 Shear strength 1.5 7.9 0.70 3.9 1 7.1 1 8.3 Modulus (GPa) Tensile modulus 0.017 6.2 0.021 7.1 0.1 0.7 0.7 5.4 Compression modulus Compression 1 6.2 0.5 3.3 Shear modulus 0.2 11.8 0.2 12.5 0.1 5.6 Poisson’s ratio 0.01 10 Deformation (%) Strain at yield 3.4 12.8 5.7 16.6 Elongation at break 39 9.5 57 18.3

and methods used for the calculation. Very different data can be found elsewhere. Some other common technical words may recover various real facts. For example, in the field of composting grades of a same generic name, they can:

• be composting or not according to the exact grade

• be composting by home means or industrial means

• certified up to a given thickness, for example 120 µm or up to 1300 µm

Often properties of polymers are those of isotropic materials, but do not forget that isotropic polymers can become anisotropic because of the used processing methods, for example extrusion, calendering, and others.

95% confidence interval

23 25.3 58.5 72.4 228 218

24.6 28.5 59.8 82.8 348 314

119 122

191 178

16 16.6 12 10

22 19.4 16 14

0.240 0.253 13.8 11.6

0.308 0.337 14.2 14.4

14 14

18 16

1.3 1.2 1.6

2.1 2 2

0.08

0.12

19.7 22.9

33.3 45.7

331 197

487 425

6.3 Environmental Indicators There are many environmental indicators (see also Chapter 3: Metrics of Sustainability in Plastics: Indicators, Standards, Software) whose only some examples are quoted. Without claiming to be exhaustive, let us quote:

• Energy requirement (MJ or GJ) expressed per unit, for example in MJ/kg of polymer, or expressed by functional unit for example MJ/ 1000 bottles or others, and may be categorized for nonrenewable energy use and renewable energy use.

• Net carbon footprint, CO2 and other greenhouse gases (GHGs), global warming potential (GWP) expressed in kg CO2 equivalent per kg

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Table 6.3 Examples of Natural Content of Renewable, Green, Eco-, and Bio-Grades.

213

Table 6.3 Examples of Natural Content of Renewable, Green, Eco-, and Bio-Grades.—Cont’d

Expected Renewable Content

Expected Renewable Content

PLA

up to 100%

Bio-PF

20%
50%

WPC PLA

up to 100%

Bio-PMMA

20%
30%

PA 1010

up to 100%

WPC PS 20 wood

20%

Bio-PE

80%
100%

Bio-PUR

8%
70%

PA 512

34%
100%

Bio-UP

8%
40%

PA 513

32%
100%

PA 514

31%
100%

PA 1212

up to 100%

PA 1012

40%
100%

PA 510

100%

TPU Bio

30%
90%

PEBA Bio

62%
97%

of plastic or by functional unit per instance per 1000 parts, etc.

PA 410

up to 70%

• The actual rate of renewable resource content

PA 612

up to 63%

of bioplastics.

CAB

Up to 60%

• Water footprint

Starch derivatives

.50%

PA 6
9 or 6
10 or 6
12

45%
63%

CA

40%
50%

COPE Bio

20%
60%

Starch/PCL

.60%

PP Bio

.50%

PA 11

.50%

WPC PE 60 bois

60%

WPC PP 60 bois

60%

PA Transparent

54%

PA 56

47%

Bio-EP

20%
90%

WPC PE 40 bois

40%

WPC PP 40 bois

40%

Recycled polymers

5% up to 100%

WPC PS 40 bois

40%

PTT—Sorona

22%
37%

PA 511

36%

PET

.30%

CAB, Cellulose esters; COPE, copolyester; EP, epicerol; PCL, polycaprolactone; PE, polyethylene; PF, phenolic resin; PET, polyethylene terephthalate; PLA, polylactic acid; PMMA, poly methylmethacrylate; PP, polypropylene; PS, polystyrene; PUR, polyurethane; TPU, thermoplastic polyurethane; UP, unsaturated polyester; WPC, wood plastic composite.

More detailed indicators may include, without claiming to be exhaustive:

• • • • • •

Particulate matter emission (g/kg) Ozone depletion Smog Acidification Eutrophication Biochemical (mg/kg)

oxygen

demand

to

water

• Chemical oxygen demand to water (mg/kg) • Eco-indicator 95—acidification (kg SO2 eq) • Eco-indicator 95—carcinogenicity (PAHeq— Polycyclic aromatic hydrocarbons eq.)

(Continued )

• • • • • • •

Human toxicity (kg 1,4 dichleq) Methane (g) Nitrate emissions to water (g) NOx emissions (g/kg) Phosphate emissions to water (g) SOx emissions (g/kg) Terrestrial ecotoxicity (kg 1,4 dichleq)

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

214

• Generation of wastes is broken down by type, for example: • Municipal waste in kg per product unit (weight, length of pipes, number of bottles, etc.) • Hazardous waste in kg per product unit (weight, length of pipes, number of bottles, etc.) Environment indicators are tools aiming skilled teams and must be used by well informed people. Use by people technically qualified, but unqualified from this point of view, may lead to misleading conclusions.

6.3.1 Use of Renewable Materials Instead of Fossil Resources A plastics production of more than 300 million tonnes and an annual growth of approximately 5%, represent the largest field of application for crude oil after the energy and transport sectors. Consequently, the plastics industry is highly dependent on crude oil. Price increases in crude oil and natural gas caused by strong demand and political conflicts, as well as the fear of crude oil being depleted, have a marked effect on the plastics market. Hence it is becoming increasingly important and pressing to utilize alternative raw materials. Obviously, the replacement of 1 kg of crude oil as raw material by a renewable source saves nearly 1 kg of crude oil. Renewable plastics may be divided into recycled material and virgin polymers based on renewable resources. Suitably recycled plastics can have properties that are good enough for many applications, with noticeable environmental and economic advantages. However, as some properties are affected by recycling, the designer must be vigilant concerning, for example, processability, ultimate mechanical performances such as tensile and impact strengths, and sensory properties. In addition, some use limitations are emitted by regulations, professional associations, laboratories, producers, and consumers. For example, underwriters laboratories (UL) accepts:

• No regrind for thermosets, thermoplastic elastomers, and recycled materials.

• Regrind up to a maximum of 25% by weight with the same grade of virgin thermoplastic at

the same molder facility without further testing.

• For regrind levels exceeding 25% in the same virgin thermoplastic, UL requires a special evaluation of relevant performance tests such as mechanical, flammability, and aging tests. Producers recommend maximum levels according to the type of polymer, the reinforcement, and, more generally, the formulation and the targeted applications. For example, levels of regrind for long fiber reinforced thermoplastics are very low because of the breakage of long glass fibers (GFs), which leads to a decrease of mechanical performances. More generally, levels depend on the history of the parts to be recycled, polymer sensitivity to hydrolysis and thermo-oxidation, the processing parameters. Table 6.3 displays some renewable content claimed for some polymers. These data must be carefully verified because of the broad range of figures for a same polymer, the continuous evolution of commercialized grades, and the hypotheses and methods used for the calculation. Very different data can be found elsewhere. Once again, please note some renewable contents are as low as 20% or less for grades sold as renewable, green, eco, and so forth.

6.3.2 Energy Requirements Making simple, embodied, energy includes:

• Feedstock energy: heat of combustion of the raw materials used to polymerize the plastic under consideration. For example, fossil styrene used to make polystyrene (PS).

• Process energy: energy used to process the plastic into the product under scrutiny. For example, pellets, tubes, molded parts, etc. Feedstock and energy may be:

• From fossil origin, the most common today. For example, crude oil, coal, natural gas, shale gas suitable as feedstock and primary energy, and uranium.

• From renewable source: hydropower, solar or wind energy, etc. Table 6.4 displays total embedded energy for 24 plastics families including 8 from natural resources

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Table 6.4 Statistical Analysis of Total Embedded Energy, MJ/kg Polymer. Mean

Standard Deviation

Minimum

Maximum

Samples

Bioplastics suitable for statistics

45

22

223

107

.60

Bio-PE

34

NA

18

50

2

TPS

35

13

19

55

15

PLA

47

13

17

70

24

PHA

49

33

223

107

18

PHB

57

20

45

80

3

Cellulose ester

83

19

65

106

5

Bio-UP

70

NA

70

70

1

PTT Sorona 37% renewable

82

NA

82

82

1

Mean

Standard Deviation

Minimum

Maximum

Samples

Fossil plastics suitable for statistics

89

20

52

145

.100

Fossil PVC

62

8

52

77

8

Fossil PP

76

8

53

86

12

Fossil PET

78

7

69

89

12

Fossil EVA

79

NA

75

83

2

Fossil PE

82

10

69

111

17

Fossil PCL

83

NA

83

83

1

Fossil PUR

86

7

78

96

5

Fossil UP

87

16

63

110

7

Fossil PS

90

7

82

105

15

Fossil PF

96

30

75

130

3

Fossil ABS

97

6

90

104

4

Fossil PVOH

102

NA

102

102

1

Fossil PMMA

104

NA

104

104

1

Fossil PC

111

8

103

120

5

Fossil EP

115

28

76

140

5

Fossil PA

131

11

116

145

7

ABS, Acrylonitrile
butadiene
styrene; EP, epicerol; EVA, ethylene-vinyl acetate; NA, not available for statistics; PA, polyamide; PC, polycarbonate; PCL, polycaprolactone; PE, polyethylene; PET, polyethylene terephthalate; PHB, polyhydroxybutyrate; PF, phenolic resin; PHA, polyhydroxyalkanoate; PLA, polylactic acid; PMMA, poly methylmethacrylate; PP, polypropylene; PS, polystyrene; PTT, polytrimethylene terephthalate; PUR, polyurethane; PVC, polyvinyl chloride; TPS, thermoplastic starch; UP, unsaturated polyester.

and 16 from fossil origin. These data must be carefully verified because of the broad range of figures for a same polymer family, the continuous evolution of commercialized grades, and the hypotheses and methods used for the calculation.

Very different data can be found elsewhere. Please note:

• All data are not suitable for a statistics analysis.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

216

• Except for cellulose ester, bio-unsaturated polyester (UP) and polytrimethylene terephthalate (PTT) with 37% renewable, mean values for renewable plastics are about half that of fossil plastics due to the low feedstock energy.

• The high standard deviations particularly for bioplastics.

• The special case of cellulose esters, bio-UP and PTT with 37% renewable with an embedded energy close to the average value of “all fossil polymers.”

• The broad range of fossil polymers with mean

calculation. Very different data can be found elsewhere. Please note:

• Net carbon footprint may be negative because of the absorption of CO2 by photosynthesis during plant growing.

• The high standard deviations, particularly for bioplastics.

• The special case of bio-UP and PTT close to the average value of “all fossil polymers.”

• The broad range of fossil polymers with mean values varying from 2.1 up to 7.7 kg CO2 equivalent per kg plastic

values varying from 62 up to 131 MJ/kg. Above data demonstrate that bio-polyethylene (PE) in comparison with fossil PE provides a reduction of consumed energy higher than 50%. An life cycle assessment (LCA) by Solvay demonstrates that bio-EP (epicerol) in comparison with fossil EP provides a 57% reduction of nonrenewable energy. Above data demonstrate that bio-UP in comparison with fossil UP provides a 20% reduction of consumed energy, but in all likelihood use of renewable raw material is partial.

6.3.3 Net Carbon Footprint, CO2 and Other Greenhouse Gases, Global Warming Potential GWP is an appraisal of GHG (e.g., CO2, methane, nitrous oxide, etc.) contribution to global warming. Global warming comes from an increase in the atmospheric concentration of GHG that changes the absorption of infrared radiation in the atmosphere leading to changes in climatic patterns and higher global average temperatures. GWP is measured in terms of CO2 equivalents and can be expressed in gram (or derived unit) equiv. CO2 per product unit (weight, length of pipes, number of bottles, etc.). Table 6.5 displays the net carbon footprint for 24 plastics families including 8 from natural resources and 16 from fossil origins. These data must be carefully verified because of the broad range of figures for a same polymer family, the continuous evolution of commercialized grades, and the hypotheses and methods used for the

Above data demonstrate that bio- polyethylene (PE) in comparison with fossil PE provides more than 100% reduction of the carbon footprint. A recent LCA by Solvay demonstrates that bioEP in comparison with fossil EP provides a 61% reduction of GWP. Surprisingly, the above data display that bio-UP in comparison with fossil UP provides an 8% increase of the carbon footprint. Data from Reverdia suggest a roughly 65% reduction in the carbon impact of bio-polyurethane (PUR) compared with fossil PUR.

6.3.4 Water Footprint The water footprint measures the amount of water, often expressed in m3, used to produce plastics. It can be measured for a specified weight (often kg) or for a defined number of products, for example 1000 bottles or 1 m2 of film or 100 m of pipe, and so forth. A water footprint assessment alone is insufficient to describe the overall potential environmental impacts of products. From the water point of view, emitted water pollution must be specified. Table 6.6 displays, without any warranty, some examples but, unfortunately, data are often unclear as for the quality of the used water and the end pollution of the emitted water. For example, processed water and cooling water are not differentiated. Water is expressed in m3 per kg of plastic.

6.3.5 Examples of Other Environmental Indicators For a limited number of plastics including high density polyethylene, polyacetal, polyvinyl

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217

Table 6.5 Analysis of Net Carbon Footprint, kg CO2 Equivalent per kg Plastic. Mean

Standard Deviation

Minimum

Maximum

Samples

Bioplastics suitable for statistics

0.9

2.0

2 3.9

4.6

.60

Bio-PE

2 1.4

2.4

2 3.9

2.2

8

PHB

0.6

3.1

2 3.0

2.6

3

PHA

0.8

2.3

2 3.1

4.6

17

Cellulose ester

0.9

1.7

2 0.3

3.8

5

TPS

1.4

0.7

0.9

3.6

14

PLA

1.4

1.4

2 2.0

3.8

24

Bio-UP

4.1

1

PTT Sorona 37% renewable

3.2

1

Mean

Standard Deviation

Minimum

Maximum

Samples

Fossil plastics suitable for statistics

3.8

1.9

0.7

9.0

.70

Fossil EVA

2.1

2.0

2.2

2

Fossil PVC

2.4

0.4

1.9

2.9

6

Fossil PE

2.4

1.1

1.0

4.8

17

Fossil PP

2.6

1.1

1.3

5.1

12

Fossil PET

3.0

1.2

0.7

5.3

10

Fossil PS

3.5

1.2

2.3

6.0

13

Fossil PUR

3.7

0.3

3.2

4

5

Fossil UP

3.8

1.1

2.3

5.2

6

Fossil PF

3.9

0.6

3.4

4.6

3

Fossil ABS

3.9

0.7

3.1

5.2

6

Fossil PC

5.8

1.3

4.1

7.6

5

Fossil EP

6.4

1.5

4.7

8.1

5

Fossil PA

7.7

1.4

4.5

9.0

8

ABS, Acrylonitrile
butadiene
styrene; EP, epicerol; EVA, ethylene-vinyl acetate; PA, polyamide; PC, polycarbonate.; PE, polyethylene; PET, polyethylene terephthalate; PF, phenolic resin; PHA, polyhydroxyalkanoate; PHB, polyhydroxybutyrate; PHB, polyhydroxybutyrate; PLA, polylactic acid; PP, polypropylene; PS, polystyrene; PTT, polytrimethylene terephthalate; PUR, polyurethane; PVC, polyvinyl chloride; TPS, thermoplastic starch; UP, unsaturated polyester.

chloride (PVC), poly methylmethacrylate, PA 66, styrene acrylonitrile, and acrylonitrile
butadiene
styrene, Table 6.7 gives a rough idea of the broad ranges observed for 7 LCAs. Many other environmental properties are not quoted in this example. Obviously, the use of average values would be unreal and misleading.

6.3.6 Variability and Weakness of Environmental Indicators Environmental indicators such as embedded energy depend on many parameters including those linked to raw materials, energy source, process, and so forth. The following information demonstrates the oversized ranges of values, which increases the

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Table 6.6 Expected Water Footprint of Bio- and Fossil Plastics. Mean

Standard Deviation

Minimum

Maximum

Samples

All bioplastics

200

115

100

300

4

PHA

200

100

300

2

PLA

200

100

300

2

Cellulose ester

27
325

14
88

11
243

43
429

5

Mean

Standard Deviation

Minimum

Maximum

Samples

All fossil plastics

176

105

15

425

28

Fossil PET

30

15

45

2

Fossil PVC

81

77

85

2

Fossil PUR

98

93

103

2

Fossil PC

142

Fossil UP

182

Fossil PE

185

Fossil PF

1 100

264

2

38

425

5

188

94

282

2

Fossil EVA

194

100

289

2

Fossil PP

199

189

209

2

Fossil EP

214

107

322

2

Fossil PS

215

108

323

2

Fossil ABS

263

250

277

2

Fossil PA

265

250

280

2

145

152

ABS, Acrylonitrile
butadiene
styrene; EP, epicerol; EVA, ethylene-vinyl acetate; PA, polyamide; PC, polycarbonate; PE, polyethylene; PET, polyethylene terephthalate; PF, phenolic resin; PHA, polyhydroxyalkanoate; PLA, polylactic acid; PP, polypropylene; PS, polystyrene; PUR, polyurethane; PVC, polyvinyl chloride; UP, unsaturated polyester.

risks of use of average values and requires choosing the parameters corresponding to the actual situation. For the total embedded energy, Table 6.8 displays:

Plastics-Resins-and-4-Polyurethane-PrecursorsRpt-Only/). Relative differences may be as high as B35%. Relative difference is computed as [(maximum 2 minimum)/2/mean].

• Coefficients of variation higher than 28% for

For the “total CO2 equivalent,” Table 6.9 displays even higher dissimilarity:

previously examined renewable plastics, thermoplastic starch (TPS) and polylactic acid (PLA).

• Total embedded energy comparison between US (American Chemistry Council—ACC) and European (PlasticsEurope) databases by Franklin Associates (cradle-to-gate life cycle inventory of nine plastic resins and four polyurethane precursors- https://plastics.americanchemistry.com/LifeCycle-Inventory-of-9-

• Coefficients of variation higher than 50% for previously examined renewable plastics, TPS, PLA, polyhydroxyalkanoate, and bioPE. Fossil plastics also lead to poor agreement.

• “Total CO 2 equivalent” comparison between US (ACC) and European (PlasticsEurope) databases by Franklin Associates (cradle-to-gate

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Table 6.7 Examples of Environmental Property Ranges for a Limited Panel of Plastics. Minimum

Maximum

Total energy

MJ

67

139

Fuel energy

MJ

32.3

108.4

Feedstock energy

MJ

20

47.8

• Elements

kg Sb eq

4.4E-08

3.20E-06

• Fossil fuel

MJ

72

126.9

Water use including cooling water

kg

74

2724

GWP

kg CO2 eq

1.8

6.4

ODP

g CFC-11 eq

7.23E-08

6.40E-04

AP

g SO2 eq

4.28

17.4

POCP

g Ethene eq

0.5

1.19

PO43 2

1.02

3.7

Abiotic Depletion Potential

Output Parameters

eq

EP

g

Dust/particulate matter

g PM10

1.37E 2 04

3.97

• Nonhazardous

kg

1.28E 2 03

1.05E 1 00

• Hazardous

kg

9.30E 2 04

4.50E 2 01

Waste Sent to Landfill

AP, Acidification potential; EP, epicerol; GWP, global warming potential; ODP, ozone depletion potential; POCP, photo-oxidant creation potential.

Table 6.8 Total Energy: Coefficient of Variation (%). TPS 37 PLA 28 Fossil PVC 13 Fossil PP 11 Fossil PET 9 Fossil PE 12 Fossil PS 8 Total embedded energy comparison between US and European databases American (MJ per 1 kg of PlasticsEurope Chemistry Council resin/precursor) (PlastEu) (ACC) Relative difference, +/- % HDPE 78.3 76.7 LDPE 83.6 78.1 LLDPE 78 72.7 PP 77 73.4 PET 70.4 69.4 GPPS 95.1 86.5 HIPS 96.1 87.4 PVC 59.2 56.7 ABS 105 95.3 Polyol—Rigid PUR 83.1 93.2 Polyol—Flexible PUR 95.7 93.2 MDI 59.8 91 TDI 51.8 108.2

1 3 4 2 1 5 5 2 5 6 1 21 35

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Table 6.9 CO2 eq: Coefficient of Variation (%). Bio-PE 171 PHA 288 TPS 50 PLA 100 Fossil PE 46 Fossil PP 42 Fossil PET 40 Fossil PS 34 Fossil PA 18 Total CO2 Equivalent Comparison of ACC Plastics LCI Database and PlasticsEurope Plastics LCI Database (kg CO2 equivalents per 1 kg of resin/precursor) kg CO2 equivalents per 1 kg of American Chemistry Relative Plastics Europe resin/precursor Council (ACC) difference, +/HDPE 1.897 1.93 1 LDPE 2.201 2.08 3 LLDPE 1.901 1.824 2 PP 1.86 1.964 3 PET 2.733 2.15 12 GPPS 3.242 3.432 3 HIPS 3.259 3.424 2 PVC 2.419 1.889 12 ABS 3.805 3.76 1 Polyol—Rigid PUR 3.718 3.547 2 Polyol—Flexible PUR 4.035 3.547 6 MDI 2.377 3.947 25 TDI 2.107 6.264 50

(A)

(B) Energy/weight Commodity Clear TP Engineering TP CFRP transverse CFRP parallel

Energy/TS

82 104 131 285 285

Index based on TS CFRP parallel Clear TP Engineering TP CFRP transverse Commodity

1 21 24 36 39

Energy/weight

Figure 6.3 (A) Examples of energy/TS versus energy/weight (B) ranking examples according to functional units. TS, Tensile strength.

life cycle inventory of nine plastic resins and four polyurethane precursors-https://plastics.americanchemistry.com/LifeCycle-Inventory-of-9-PlasticsResins-and-4-Polyurethane-Precursors-Rpt-Only/). Relative differences may be as high as B35%. Relative difference is computed as ([maximum 2 minimum)/2/mean]. Please note some renewable materials absorb more CO2 during growing of plants than the process emits during the manufacturing step.

6.3.7 Do Not Confuse Indicator per Weight and Indicator per Functional Unit Often literature quotes environmental indicators per weight, but for LCAs of parts, indicator per functional unit is of the prime importance. The following deals with the energy per weight on the one hand and the energy per arbitrary functional unit derived from TS on the other hand. Fig. 6.3A shows for commodity, clear thermoplastic (TP), engineering TP, and carbon fiber reinforced

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plastic (CFRP) (in Transverse and Parallel direction) the energy/TS (arbitrary functional unit) versus energy/weight. Results are widely spread with two points clearly outside the general range. Those points are linked to CFRP embedding high energy per weight and very high TS in fiber direction or very low TS in transverse direction. Of course any intermediate data is credible for intermediate directions. Fig. 6.3B displays two rankings for 5 plastics subfamilies from commodity up to hi-tech composite (CFRP). According to the chosen property, the commodity plastic is the best for the [energy consumption per weight] ranking and the worst for [energy per tensile strength (TS)]. Quite the opposite, CFRP in parallel direction is the worst for [energy per weight] but the best for [energy per TS]. The index based on TS is totally arbitrary and a few examples do not make a rule, so the only purpose here is to point out the importance of the functional unit.

6.4 Usual Indicators for Plastics Design Sustainability of a device involves the ability to assume the function during the forecast lifetime. Eco-design, sustainable design, or ECD targets the technical viability that involves a sound design using data from the use of standard tests. There are a number of standards dealing with plastics features and only a few are mentioned in the following (see some others in Chapter 7: Advanced Environmental and Engineering Properties to Support Eco-Design for Plastics):

• • • • • • •

Thermal behavior Relative temperature index (RTI) Low-temperature behavior Density Mechanical properties Water uptake Mold shrinkage

Of course there are many other properties required for more special cases and the reader must make their own study for his or her own project.

6.4.1 Thermal Behavior First we must remind some general features:

221

• Plastics are viscoelastic materials. • They can be semicrystalline or amorphous. • Properties are temperature-dependent with sometimes sudden variations: Glass transition temperature is an important parameter for property evolution.

• Thermal behavior isn’t an intrinsic property but depends on numerous parameters including among others, the shape and thickness of the part, the processing conditions, and the general history of the part. Of course, the following data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured with representative methods on the actual used compound must be considered.

6.4.1.1 Overview A temperature phenomena:

rise

causes

two

different

• Immediate physical effects: • Decay of the modulus and other mechanical and physical properties, physicochemical softening. • Dimensional stability: reversible thermal expansion and, eventually, irreversible shrinkage and warpage.

• Long-term effects: • Physical: more or less irreversible creep and relaxation.

• Chemical: irreversible degradation of the material, decrease of the mechanical properties, even after a return to the ambient temperature. Sometimes heat can complete curing of thermosets before the degradation step. The maximum service temperatures depend on the duration of service time and the possible simultaneous application of mechanical or other stresses. A fall in temperature has only physical effects:

• Increase in the modulus and rigidity. • Reduction of the impact resistance; the material can become brittle.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

• Eventually, crystallization for semicrystalline polymers. Low temperatures slow the thermal degradation and improve the lifetime from a chemical point of view.

6.4.1.2 Glass Transition Temperature For amorphous polymers or amorphous domains of semicrystalline polymers, the glass transition temperature (Tg) is a reversible transition from a hard and brittle state into a molten or rubber-like state. Designers must be aware of abrupt evolutions of some properties when temperature overcomes the Tg. The transition temperature value depends on the testing conditions, notably the cooling or heating rate, and the frequency of the measured parameter.

The Tg may be negative or positive in °C and is lower than the melting temperature of the crystalline domains. Table 6.10 displays 209 examples of Tg for various grades including among others carbon fiber (CF) reinforced grades, GF-reinforced grades, mineral and glass bead (GB) reinforced grades, conductive grades, friction grades, wood plastic composite (WPC):

• 57 materials have a negative Tg • 9 are approximately in the ambient temperature range

• 143 range from 40°C up to 425°C These results must be carefully read because measuring methods aren’t known.

Table 6.10 Glass Transition Temperature Examples. Subzero Temperatures

Over Zero Temperatures

Minimum

Maximum

Minimum

PE GF

2110

2110

PE wood WPC

2110

2110

PE 60% long GF

2110

2110

PE-HD

2110

2110

PE-HD antistatic, black

2110

2110

PE-LD

2110

2110

PE-UHMW

2110

2110

TPS shore D

280

240

COPE low shore D

278

210

PEBA 25
45 shore D

265

250

POM homo or copolymer

260

250

POM GF

260

250

POM long GF

260

250

POM GB

260

250

POM CF

260

250

POM conductive

260

250

POM far

260

250

POM low friction

260

250

POM MINERAL

260

250

COPE high shore D

260

50

Maximum

(Continued )

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Table 6.10 Glass Transition Temperature Examples.—Cont’d Subzero Temperatures

Over Zero Temperatures

Minimum

Maximum

Minimum

PEBA Bio

20

240

PVC plasticized

250

25

TPE based on PVC

250

25

TPU GF

248

220

TPU long GF

248

220

TPU Bio

248

220

TPU conductive

248

220

TPU shore D

248

6

PVDF

246

222

PEBA 50
72 shore D

240

240

PVDF CF

240

235

PVDF low friction

240

235

PVDF Mica

240

222

PVF

235

215

COPE Bio

235

22

PB

234

218

PP impact

230

220

PP recycle

230

210

PP Co

220

220

PP low-level GF

220

210

PP medium level GF

220

210

PP GB

220

210

PP Mineral

220

210

PP Talc

220

210

PP low-level CNT

220

210

PP medium CNT

220

210

PP cellulose fibers

220

210

PP long GF medium level

220

210

PP CaCO3

220

210

PP long GF high level

220

210

PP antistatic

220

210

PP CF

220

210

PP conductive

220

210

PP natural fibers

220

210

PP wood WPC

220

10

Maximum

(Continued )

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Table 6.10 Glass Transition Temperature Examples.—Cont’d Subzero Temperatures

Over Zero Temperatures

Minimum

Maximum

Minimum

Maximum

PVDC

215

215

PP Ho

210

210

SMMA

7

80

EVOH

15

72

PTFE

19

30

PTFE CF

19

30

PTFE low friction

19

30

PTFE GF

19

30

PMP

20

30

PMP GF

20

30

PMP mineral

20

30

PBT

40

60

PBT medium level GB

40

60

PBT medium level GF

40

60

PBT GF and mineral

40

60

PBT long GF

40

60

PBT long CF

40

60

PBT CF

40

60

PA 6

40

65

PA 6 GB

40

65

PA 6 medium level GF

40

65

PA 6 medium level long GF

40

65

6 GF recycled

40

65

PA 6 high level GF

40

65

PA 6 high level long GF

40

65

PA 6 FR

40

65

PA 6 mineral FR

40

65

PA 6 recycled

40

65

PVCC

45

45

PA 6
10

45

50

PA 6
10 CF

45

50

PLA

45

65

PLA GF

45

65

PLA natural reinforcement

45

65

PLA wood WPC

45

65 (Continued )

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Table 6.10 Glass Transition Temperature Examples.—Cont’d Subzero Temperatures

Over Zero Temperatures

Minimum

Minimum

Maximum

PA 6
12

45

70

PA 6
12 GF

45

70

PA 66

50

60

PA 66 CF

50

60

PA 66 GB

50

60

PA 66 medium level GF

50

60

PA 66 long CF

50

60

PA 66 medium level long GF

50

60

PA 66 mineral

50

60

PA 66 high level GF

50

60

PA 66 high level long GF

50

60

PA 66 conductive

50

60

PA 66 impact medium level GF

50

60

PTT Bio

55

55

PTT Bio GF

55

55

PVC GF

60

100

PVC unplasticized

60

100

PET

70

78

PET GF

70

78

PET amorphous

70

78

COC

70

180

PA 4
6

75

75

PA 4
6 GF

75

75

PA 4
6 mineral

75

75

CAB

80

120

CP

80

120

PS impact

83

95

PS 40% wood WPC

83

100

PS

83

102

ECTFE

85

85

PAA medium level CF

85

100

PAA medium level GF

85

100

PAA high level GF

85

100

PAA mineral

85

100

PPS

88

93

Maximum

(Continued )

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Table 6.10 Glass Transition Temperature Examples.—Cont’d Subzero Temperatures

Over Zero Temperatures

Minimum

Minimum

Maximum

PPS GF

88

93

PPS long GF medium level

88

93

PPS long GF high level

88

93

PPS CF

88

93

PPS CF 1 GF

88

93

PPS conductive

88

93

PPS far

88

93

PPS GF 1 mineral

88

93

PS GF

90

90

PMMA GF

90

110

PMMA impact

90

110

PMMA

90

135

PA transparent

93

155

ABS

95

115

ABS GF

95

115

ABS GB

95

115

ABS CF

95

115

ABS conductive

95

115

ABS FR

95

115

CA

95

130

PCT GF

100

105

SAN

100

115

SAN GF

100

115

PPE GF

100

150

PPE CF

100

150

PPE mineral

100

150

PPE

100

210

ASA

103

104

MABS

107

115

SMA

110

115

SMA GF

110

115

LCP

120

150

LCP CF

120

150

LCP GF

120

150

LCP mineral

120

150

Maximum

(Continued )

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Table 6.10 Glass Transition Temperature Examples.—Cont’d Subzero Temperatures

Over Zero Temperatures

Minimum

Minimum

Maximum

PPA

135

135

PPA GF

135

135

PPA mineral

135

135

PPA long GF

135

135

PPA CF

135

135

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

137

182

PAEK 30% GF

137

182

PET/PC

140

150

PEEK

143

157

PEEK GF

143

157

PEEK CF

143

157

Acrylique IMIDE

143

168

PMI or PMMI

143

168

PC CF

145

150

PC CNT

145

150

PC conductive

145

150

PC low friction

145

150

PC

145

200

PC GF

145

200

PEEK/PBI

150

155

PEEK/PBI GF

150

155

PEEK/PBI CF

150

155

Polyarylate

185

190

Polyarylate GF

185

190

PSU

187

190

PSU GF

187

190

PSU mineral

187

190

PES

210

230

PES GF

210

230

PES CF

210

230

PES low friction

210

230

PEI

215

217

PEI GF milled

215

217

PEI GF

215

217

PEI CF

215

217

Maximum

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.10 Glass Transition Temperature Examples.—Cont’d Subzero Temperatures

Over Zero Temperatures

Minimum

Minimum

Maximum

PEI conductive

215

217

PEI mineral

215

217

PPSU GF

220

250

PPSU

220

265

PAI

275

275

PAI GF

275

275

PAI CF

275

275

PAI low friction

275

275

PAI mineral

275

275

PI TP

315

315

PI TP CF

315

315

PI TP GF

315

315

PI TP low friction

315

315

PBI

400

425

Maximum

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; CF, carbon fiber; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EVOH, ethylene vinyl alcohol copolymers; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, Liquid crystal polymers; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; PEEK, polyether ether ketone; PES, polyethersulfone; PET, polyethylene terephthalate; PLA, polylactic acid; PMI, polymethacrylimide; PMMA, poly methylmethacrylate; PMP, polymethylpentene; POM, polyacetal; PP, polypropylene; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PSU, polysulfone; PTFE, polytetrafluoroethylene; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; PVDC, Polyvinylidene chloride; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; SMMA, Styrene methyl methacrylate; TP, thermoplastic; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; UHMW, ultrahigh molecular weight; WPC, wood plastic composite.

We can remark the broad range of Tg for many families coming from formulation versatility, succinct trade appellations, test method versatility, errors, and mix-up. For example, Tg of listed PVC grades evolve from 250°C up to 60°C according to the plasticization system. Tg is rarely used as a criterion of first rank for the selection of a plastic, but is very interesting for the low-temperature behavior (brittleness hazard) and the possible abrupt changes of many properties.

6.4.1.3 Thermal Behavior above Room Temperature: HDT, CUT, UL Temperature Thermal behavior above room temperature can be featured by some conventional thermal properties such as:

• • • • •

Heat deflection temperature (HDT) Continuous use temperature (CUT) UL temperature index Vicat softening temperature (VST) Accelerated aging

Heat Deflection Temperature or Deflection Temperature Under Load

The HDT (ISO 75) is the temperature at which a standard deflection occurs for defined test samples subjected to a given 3-point bending load and a linear increase in temperature. The outer fiber stresses usually selected are 0.45 MPa (HDT B) or 1.8 MPa (HDT A) and must be indicated with the results. Sometimes the outer fiber stress is 8 MPa (HDT C). Of course, for a same compound, HDT A(1.8 MPa) is lower than HDT B (0.45 MPa)

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Usually, a polymer cannot be used under this load at that temperature. The first part of Table 6.11 displays average HDT A and B for 8 subfamilies: expected neat grades and special grades including CF-reinforced grades, GF-reinforced grades, mineral and

229

GB-reinforced grades, conductive grades, friction grades, and WPC. Please note:

• General purpose grades can be formulated with plasticizers, fillers and reinforcements and are called “expected neat grades.”

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades. HDT A and B Examples for 261 Thermoplastic Grades HDT B 0.45 MPa (°C)

HDT A 1.8 MPa (°C)

Average HDT A and B for 8 Subfamilies

Average (°C)

Average (°C)

All thermoplastics

162

134

Neat TP

122

89

CF-reinforced TP

217

199

GF-reinforced TP

202

184

Mineral-reinforced TP

177

143

Conductive TP

135

114

Low-friction TP

165

130

WPC

90

78

Detailed Data for Thermoplastics

HDT B Minimum

Minimum

Maximum

PBI

427

435

PEEK/PBI CF

320

358

PEEK/PBI GF

310

310

290

323

PAI CF

282

282

PAI low friction

279

280

PAI GF

278

282

PAI

278

280

270

320

270

290

PEEK GF

PEEK CF

330

323

Maximum

HDT A

340

323

PA 4
6 GF PPA GF

285

300

266

294

PPA long GF

285

290

266

282

PPS long GF high level

280

290

266

282

PPS CF

280

297

260

277

PPS CF 1 GF

278

290

260

272

PPS long GF medium level

270

290

250

280

PPS GF

270

280

250

270

250

270

250

255

PPA CF

249

277

PI TP CF

245

319

PA 4
6 mineral

245

245

PAI mineral PA 66 long CF

270

275

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics PA 66 high-level long GF

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

260

285

243

263

240

319

PI TP GF PA 66 medium-level long GF

260

275

240

252

PI TP

260

343

235

319

235

300

PI TP low friction PAA high level GF

250

295

230

285

PA 66 CF

250

265

230

260

PPS conductive

230

275

225

268

PAA medium level CF

245

285

224

270

PCT GF

268

280

221

263

PAA medium level GF

240

280

220

270

PET GF

225

250

220

240

216

320

LCP CF PBT long CF

230

250

216

220

PA 66 high level GF

220

255

215

255

PK GF

220

222

215

216

PAEK 30% GF

270

360

213

350

PA 6 high-level long GF

230

265

212

240

PPSU GF

220

270

210

260

PA 4
10 GF Bio

240

243

210

215

PEI CF

215

230

206

223

PA 6 medium-level long GF

220

263

205

238

PES low friction

210

230

205

223

PLA/PBT GF

215

225

PPS Far

225

278

204

260

PES GF

210

224

204

220

PPSU

210

270

200

255

PA 66 medium level GF

215

255

200

240

PA 66 impact medium level GF

215

250

200

240

PPE/PA GF

220

254

200

235

PBT long GF

220

250

200

225

PES CF

210

230

200

225

ETFE GF

260

265

200

210

PET/PBT high level GF

220

250

200

210

PA 6 high level GF

215

220

200

210

PEI conductive

210

215

200

210

PEI GF

205

212

196

210

(Continued )

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231

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

PBT medium level GF

215

250

195

225

PES

205

220

195

204

PA 6 medium level GF

210

255

190

230

PA 6
12 GF

205

215

190

210

PEI mineral

200

215

190

210

PA 6 GF recycled

205

220

190

205

PTT Bio GF

200

226

190

205

PEI GF milled

205

210

190

200

PEI

195

210

190

200

185

190

PA 10
10 high level GF Bio LCP mineral

220

320

180

315

PP/PA GF

200

245

180

225

PPE/PA

191

195 174

180

PEEK/PBI PSU mineral

177

185

172

180

PBT CF

180

225

171

220

PPS GF 1 mineral

200

280

170

270

Polyarylate GF

180

185

170

171

PA 11 GF

175

192

165

177

LCP GF

210

370

160

355

PBT GF and mineral

205

220

160

205

PSU

170

210

160

205

PSU GF

170

190

160

185

160

170

PA 12 CF PSU/PBT GF

170

180

160

166

POM long GF

170

174

160

166

PA 12 GF

170

185

160

165

POM CF

162

168

158

163

PPA mineral

240

260

157

200

PA 4
6

250

280

150

190

150

162

PP long GF high level FEP GF

250

260

150

160

PA Far

170

255

149

240

PSU/ABS

150

170

149

150

PSU/PC

150

160

149

150

PSU modified

150

180

145

175

PLA GF

152

165

145

150

(Continued )

232

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

250

300

140

170

PEEK

250

295

140

165

PC CF

141

152

136

146

PC GF

140

220

135

205

PVDF CF

146

170

134

159

Acrylique IMIDE

140

170

132

160

PMP GF

140

177

130

166

PMI or PMMI

140

170

130

160

PPE GF

132

154

127

144

PC conductive

130

138

126

132

PC

130

195

125

180

POM GF

145

174

125

166

PP long GF medium level

140

165

125

160

PP medium level GF

140

165

125

152

PC CNT

135

160

125

145

PC low friction

130

150

125

140

PPE CF

127

190

121

173

POM far

140

168

121

160

PE 60% long GF

127

130

121

121

PC/SAN GF

130

135

120

126

ABS/PC GF

130

135

115

137

PVDF low friction

148

150

115

117

ABS/PC medium level long GF

125

130

113

113

Polyarylate

120

180

110

174

POM mineral

158

175

110

150

PE GF

125

130

110

121

ABS/PC_ low level long GF

120

128

107

108

LCP

180

310

105

275

PAA mineral

190

240

105

220

ASA/PBT GF

135

220

105

205

PC/PBT GF

125

220

105

185

PET/PC GF

130

205

105

170

POM GB

158

163

105

150

SMA GF

113

130

105

120

ABS GF

105

117

102

111

PA 6
10 CF

216

232

100

227

POM conductive

125

170

100

160

PP CF

132

166

100

150

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

233

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

PP natural fibers

110

156

100

134

PTFE GF

120

125

100

110

PK

200

210

100

105

ABS CF

102

110

98

99

SAN GF

100

115

95

110

PS GF

100

105

95

100

PA castable low friction

200

220

93

204

PA castable

180

220

93

204

ABS GB

102

103

93

99

PPE

100

190

90

170

ABS/PA 20 GF

120

160

90

150

PP low level GF

110

155

90

140

POM low friction

130

172

90

136

ABS/PC conductive

110

130

90

110

SMA

105

125

90

110

PPE mineral

100

120

90

110

TPU long GF

135

175

85

130

85

125

PPA ABS conductive

95

107

85

104

SAN

90

105

84

100

PPS

150

200

83

135

PA 66 mineral

150

245

80

205

PA 6 mineral FR

185

230

80

185

ABS/PC

90

140

80

132

PA 66 GB

190

220

80

121

ABS

90

125

80

120

PMMA GF

99

120

80

100

PVF

120

120

80

80

PVCC

94

120

79

106

PP cellulose fibers

110

142

78

134

PA 66 conductive

175

240

76

220

PA transparent

85

165

75

135

SMMA

76

101

75

100

ASA

80

101

75

96

PS 40% wood WPC

80

100

75

81

PA 4
10 Bio

160

165

75

80

ASA/PVC

80

85

75

77

(Continued )

234

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

ABS FR

90

120

74

110

MABS

92

94

73

90

ASA/PC

100

130

72

115

PMMA impact

75

100

70

95

PA 6 GB

180

185

70

90

TPU conductive

60

130

70

85

PA 6 FR

170

220

70

80

PVC GF

75

80

70

76

COC

68

150

66

148

ABS/PVC

72

94

66

75

TPU GF

120

175

65

130

PC/PBT

107

140

65

120

ABS/PA

90

100

65

75

PMMA antistatic

70

80

65

75

64

80

PVC wood WPC PBT medium level GB

170

210

63

100

ECTFE

90

116

63

77

PS

70

110

62

100

PS impact

70

100

62

85

PP wood WPC

61

98

PP low level CNT

60

120

PMMA

75

115

60

106

PA 66

160

240

60

105

PET

66

115

60

80

PET Amorphous

66

72

60

70

PP GB

98

110

56

100

POM homo- or copolymer

110

172

55

136

PA 6

150

240

55

105

PA 6
10

150

175

55

85

PLA/PP 30% GF

150

157

PA 6 recycled

130

170

55

70

PCTFE

120

125

PA 12 GB

100

155

55

65

PP CaCO3

90

110

55

65

EVOH

95

100

PVC unplasticized

57

80

54

71

PLA/PC

65

124

54

68

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

235

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

PVDC

80

90

54

65

PTT Bio

75

150

53

80

PA 6
12

135

180

51

90

PP conductive

82

166

50

150

PET/PC

110

135

50

120

PP antistat

80

149

50

120

PMP mineral

90

121

50

110

ETFE

88

105

50

100

PP Ho

75

120

50

100

PP mineral

65

135

50

100

PBT

115

185

50

85

PP talc

89

135

48

85

PP impact

75

104

46

70

PFA

70

75

CAB

54

108

45

95

PP/PA

60

200

45

80

PTFE

70

126

45

70

PA 12

100

140

45

65

PA 12 low friction

100

140

45

65

PA 12 conductive

95

135

45

65

PEBA 50
72 shore D

50

106

45

55

PA 10
10 Bio

120

125

45

50

CP

60

120

44

110

CA

50

100

44

90

COPE high shore D

50

156

44

55

43

62

PE wood WPC PP Co

75

108

43

60

PP recycled

75

100

43

55

TPU shore D

61

81

42

50

PVDF

68

135

40

113

PA 11

70

150

40

65

PE-X crosslinked

54

107

40

63

PE-HD

57

99

40

60

PMP

80

100

40

55

TPU Bio

60

80

40

50

PA 11 or 12 plasticized

50

100

40

45

(Continued )

236

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d Detailed Data for Thermoplastics

HDT B

HDT A

Minimum

Maximum

Minimum

Maximum

PE-HD antistatic, black

50

57

40

42

PE-UHMW

65

82

35

50

TPO shore D

50

130

30

72

FEP

70

77

30

48

PLA/PMMA

57

66

PLA/PE

54

55

PLA

51

65

PLA natural reinforcement

51

65

PE-LD

40

50

30

40

CPE

35

35

25

25

PEBA Bio

40

100

20

55

COPE Bio

20

150

20

55

PVC plasticized

20

69

20

53

COPE low shore D

20

85

20

48

PEBA 25
45 shore D

42

65

20

45

EMA

40

48

EVA

20

72

HDT A (1.8 MPa) Examples for 28 Grades of Thermosetting Resins HDT A Examples Minimum (°C)

Maximum (°C)

PI/GF molding

305

330

PI neat

235

320

EP/CF UD

260

291

EP/GF SMC

260

290

PF/GF SMC

200

310

PI/CF

230

260

EP glass fabric

230

250

EP/aramid fiber UD

230

250

PF/GF molding

150

310

MF filled

140

310

UP SMC

200

250

UP/GF mat

200

240

UP/GF BMC

200

230

EP filled, molding

120

300

UP filled, molding

100

250

MF modified

120

220

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

237

Table 6.11 Heat deflection temperature (HDT) A and B Examples for Thermoplastic and Thermoset Grades.— Cont’d HDT A (1.8 MPa) Examples for 28 Grades of Thermosetting Resins HDT A Examples Minimum (°C)

Maximum (°C)

PF organic filled

110

200

PUR SRRIM

70

230

UF cellulose

110

145

EP neat

45

200

UP cast

30

150

PUR RIM

20

90

PUR Sh D

20

65

PUR Sh A

Unsuitable test

Unsuitable test

Silicone HVR

Unsuitable test

Unsuitable test

PUR foam

Unsuitable test

Unsuitable test

Fluorosilicone

Unsuitable test

Unsuitable test

Silicone RTV

Unsuitable test

Unsuitable test

Silicone foam

Unsuitable test

Unsuitable test

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; CF, carbon fiber; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EP, epicerol; EVA, ethylene-vinyl acetate; EVOH, ethylene vinyl alcohol copolymers; FEP, fluorinated ethylene propylene; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; PEEK, polyether ether ketone; PES, polyethersulfone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PK, polyketone; PLA, polylactic acid; PMMA, poly methylmethacrylate; PMI, polymethacrylimide; PMP, polymethylpentene; POM, polyacetal; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PSU, polysulfone; PTFE, polytetrafluoroethylene; PTT, polytrimethylene terephthalate; PUR, polyurethane; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; PVDC, polyvinylidene chloride; RTV, room-temperature vulcanization; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; SMMA, styrene methyl methacrylate; TP, thermoplastic; TPU, thermoplastic polyurethane; UD, unidirectional; UHMW, ultrahigh molecular weight; UP, unsaturated polyester; WPC, wood plastic composite.

• The 8 subfamilies are not based on the same polymers. For the second part of Table 6.11 displaying ranges of HDT A and B we note that:

• Some soft material cannot be tested by these methods.

• The data range stretches from ambient temperature up to 435°C.

• For a same material, HDT A and HDT B are not correlated.

• For a given polymer, HDTs increase with the filler level and decrease with plasticizers.

• Chemical structure can dramatically change data. For example, HDT B of copolyester (COPE) is in the range of 20°C
150°C when other grades are not rigid enough to be tested.

• The broad range of HDT for many families coming from polymer structure diversity, formulation versatility, succinct trade appellations, errors, and mix-up. For example, HDTs B of listed PVC grades evolve from 20°C up to 120°C according to the plasticization and reinforcement. In addition, softer grades cannot be tested. The third part of Table 6.11 displays ranges of HDT A for 28 grades of thermosets. The number of studied samples is limited and other data may be found elsewhere. General Assessments Concerning Continuous Use Temperature

The CUT is not a standardized temperature, but an arbitrary temperature resulting from general experience and observation. It is the maximum temperature that an unstressed part can generally

238

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

withstand for a very long time without failure or unacceptable loss of function even if there is a significant reduction in the initial properties. This subjective value is not measurable and is deduced from aging test interpretations and information collected in the technical literature. Stabilized grades are proposed for each polymer families aiming higher use temperatures and/or longer service life. To give rough ideas, CUTs of thermoplastics are in the range of 45°C to 425°C, for exceptional families. Table 6.12 displays CUTs for unstressed applications.

• The first part of Table 6.12 displays average CUT for 8 thermoplastic subfamilies: expected neat grades, and special grades including CFreinforced grades, GF-reinforced grades, mineral and GB-reinforced grades, conductive grades, friction grades (bearings), and WPC. Please note: • general purpose grades can be formulated with plasticizers, fillers, and reinforcements and are called ‘expected neat grades.’ • The 8 subfamilies are not based on the same polymers. CF-reinforced compounds and friction grades have higher CUTs because of the choice of high-performing polymers and/ or because of special formulations.

• For the second part of Table 6.12 displaying ranges of CUTs we note that: • The data range stretches from 45°C up to 425°C • The broad range of CUTs for many families coming from: 2 formulation versatility, succinct trade appellations, errors, and mix-up. 2 Requirement levels depending on the targeted application. Packaging, automotive, building, aerospace, and electricity do not have the same requirements.

• The third part of Table 6.12 displays ranges of CUTs for thermosets. The number of studied samples is limited and other data may be found elsewhere. Examples of UL Relative Temperature Index

The RTI, derived from long-term oven-aging test programs, is the maximum temperature that causes

Table 6.12 Continuous Use Temperatures (CUTs) for Unstressed Samples. Thermoplastics: Average Data

Average CUT (°C)

All thermoplastics

124

Expected neat grades

117

CF-reinforced TP

152

GF-reinforced TP

128

Mineral-reinforced TP

125

Conductive TP

110

Low-friction TP

148

WPC

69

Thermoplastics: Detailed Data

Minimum (°C)

Maximum (°C)

PBI

260

425

PEEK/PBI

240

300

PFA

240

260

PEEK

180

260

PAI

200

220

FEP

200

205

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

180

260

PI TP

180

250

PI TP low friction

180

250

PAI low friction

180

220

PAI mineral

180

220

PPS

180

220

PPS conductive

180

220

PPS Far

180

220

PPSU

170

200

PEI

105

180

PEI conductive

170

180

PEI mineral

170

180

PES

160

180

PES low friction

160

180

PTFE

150

260

PTFE low friction

150

260

ECTFE

150

170

PVDF

150

150

PVDF low friction

150

150

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

Table 6.12 Continuous Use Temperatures (CUTs) for Unstressed Samples.—Cont’d

239

Table 6.12 Continuous Use Temperatures (CUTs) for Unstressed Samples.—Cont’d

Thermoplastics: Detailed Data

Minimum (°C)

Maximum (°C)

Thermoplastics: Detailed Data

Minimum (°C)

Maximum (°C)

PVDF mica

150

150

PMP

90

110

PPA

140

180

PMP mineral

90

110

PPA mineral

140

160

MPR

90

107

PSU mineral

140

160

COPE high shore D

85

135

PSU

140

160

COPE low shore D

85

135

ETFE

135

150

COPE Bio

85

135

LCP

130

240

ASA/PC

85

105

LCP mineral

130

240

TPE based on PVC

85

105

Acrylic IMIDE

120

150

SAN

85

95

PCTFE

120

150

PA 11

80

150

PMI or PMMI

120

150

PA 12

80

150

PSU/PC

120

140

PA 6

75

140

PA 4
6

110

150

PA 6 GB

75

140

PA 4
6 mineral

110

150

PA 6 FR

75

140

PSU modified

110

130

PA 6 mineral FR

75

140

PSU/ABS

110

130

PA 6
10

75

140

PVF

105

110

PA 6
12

75

140

PAA mineral

100

150

PA 66

75

140

PA Far

100

140

PA 66 GB

75

140

Polyarylate

100

140

PA 66 mineral

75

140

TPV shore D

100

135

PBT

80

155

PP Ho

100

130

80

140

PP low level CNT

100

130

PBT medium level GB

PP medium CNT

100

130

PA 66 conductive

80

130

PP conductive

100

130

PEBA 25
45 shore D

80

130

PP/PA

100

130

130

100

120

PEBA 50
72 shore D

80

PP/EPDM-V PB

95

105

PP impact

80

130

PC

90

140

PP Co

80

130

PC CNT

90

140

PP GB

80

130

PET/PC

90

130

PP mineral

80

130

PE-X crosslinked

90

130

PP talc

80

130

PC conductive

90

125

PP CaCO3

80

130

PC low friction

90

125

PP antistat

80

130

PE-UHMW

90

120

PA 12 GB

80

120

PK

90

120

PA CNT

80

120

COC

90

110

PA 4
10 Bio

80

120

(Continued )

(Continued )

240

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.12 Continuous Use Temperatures (CUTs) for Unstressed Samples.—Cont’d

Table 6.12 Continuous Use Temperatures (CUTs) for Unstressed Samples.—Cont’d

Thermoplastics: Detailed Data

Minimum (°C)

Maximum (°C)

Thermoplastics: Detailed Data

Minimum (°C)

Maximum (°C)

TPU conductive

80

120

ASA/PVC

70

85

TPU shore D

80

120

ABS

60

110

PA 12 conductive

80

110

ABS conductive

65

110

PA 12 low friction

80

110

PPE

65

110

PA 6 recycled

80

110

PPE mineral

65

110

PA castable

80

110

ABS GB

65

100

PA castable low friction

80

110

ABS FR

65

100

TPO shore D

60

120

POM homo- or copolymer

80

110

CAB

60

105

POM GB

80

110

CP

60

105

POM Far

80

110

CPE

60

80

PP recycled

80

110

ABS/PVC

60

70

POM conductive

80

105

PLA

50

100

POM low friction

80

105

PLA natural reinforcement

50

100

POM mineral

80

105

TPS shore D

50

100

PVCC

80

105

PMMA

50

90

PA 10
10 Bio

80

100

PMMA antistatic

50

90

PA Transparent

80

100

PMMA impact

50

90

PEBA Bio

80

100

PLA/copolyester

50

80

PE-HD

80

100

PS

50

80

PE-LD

80

100

PS impact

50

80

PP cellulose fibers

80

100

PVC plasticized

50

80

PP natural fibers

80

100

PVC unplasticized

50

80

SMA

80

100

PVC wood WPC

50

75

ASA

80

90

CA

45

95

PA 11 or 12 plasticized

80

90

EVA

45

70

PE-HD antistat black

80

90

PC/PBT

75

140

Thermosets: Detailed Data

Minimum (°C)

Maximum (°C)

Silicone resin

200

260

PET

75

155

Fluorosilicone

205

254

PET amorphous

75

140

Silicone HVR

160

300

ASA/PMMA

75

90

PI glass fabric

200

250

ABS/PA

70

110

PI/CF

180

260

ABS/PC

70

110

PI neat

180

250

ABS/PC conductive

70

110

PI/GF molding

180

250

TPU Bio

70

110

Silicone RTV

105

260

PVDC

70

100

EP/CF UD

130

230

(Continued )

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

Table 6.12 Continuous Use Temperatures (CUTs) for Unstressed Samples.—Cont’d Thermoplastics: Detailed Data

Minimum (°C)

Maximum (°C)

EP/GF SMC

130

230

EP glass fabric

150

190

EP/aramid fiber UD

150

190

Silicone foam

130

200

Cy neat

150

175

PF/GF molding

120

185

EP filled, molding

70

230

PF/GF SMC

120

170

PF organic filled

110

140

UP filled, molding

90

160

EP neat

70

170

MF filled

80

160

UP SMC

100

140

UP/GF BMC

100

140

UP/GF mat

100

140

MF modified

80

150

UP cast

90

140

PUR Sh A

70

130

PUR Sh D

80

110

PUR foam

50

110

PUR RIM

75

85

UF cellulose

70

80

241

Table 6.13 Examples of Relative Temperature Index (RTI): Effect of Thickness for a Same Grade. Effect of Thickness for a Defined Grade Temperature (°C)

Thickness (mm)

UL RTI, electrical

80

0.5

120

1.6

UL RTI, mechanical with impact

80

0.5

105

1.6

110

3

UL RTI, mechanical without impact

80

0.8

120

1.6

Effect of Thickness and Grade for a Defined Polymer Family Grade, thickness

A, Thickness 0.8 mm

B, Thickness 1.5 mm

UL RTI, electrical

130

240

UL RTI, mechanical with impact

130

220

UL RTI, mechanical without impact

130

240

UL, Underwriters Laboratories. ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; CF, carbon fiber; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EP, epicerol; EVA, ethylene-vinyl acetate; FEP, fluorinated ethylene propylene; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MPR, melt processable rubber; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; PES, polyethersulfone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PK, polyketone; PLA, polylactic acid; PMI, polymethacrylimide; PMMA, poly methylmethacrylate; PMP, polymethylpentene; POM, polyacetal; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PSU, polysulfone; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; PVDC, polyvinylidene chloride; RTV, room-temperature vulcanization; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; TP, thermoplastic; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; UHMW, ultrahigh molecular weight; UP, unsaturated polyester; WPC, wood plastic composite.

a 50% decay of the studied characteristics in the very long term. The UL RTI depends on (see Tables 6.13 and 6.14):

• The grade • The thickness of the tested samples • The studied characteristics gathered into 3 classes: electrical, mechanical with impact, and mechanical without impact. Data must be carefully examined, the RTI fluctuating, for example, from 130°C up to 240°C for different grades of a defined polymer family. Despite a relative consistency with CUTs, there are sometimes significant differences. In the end, only properties measured on the actual used compound must be considered.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.14 Examples of Relative Temperature Index (RTI). UL RTI (°C) Thermoplastic Examples

Electrical

Mechanical with Impact

Mechanical Without Impact

PEEK general purpose

260

180

240

PEI example A

170

170

170

PSU

160

140

160

FR 30 GF PET

155

155

155

PBT 30 GF

140

130

140

PA 66 30 GF

140

125

140

LCP GF FR

130

130

130

PP mineral

120

115

120

PC

120

105

120

PEI example B

115

115

115

PEI GF PTFE

105

105

105

POM

105

85

85

ABS FR

85

75

75

Acrylic/PVC FR

50

50

50

PVC 20 GF

50

50

50

PS FR

50

50

50

Polyimide

130
240

130

130

Silicone

170
200

Phenolic formaldehyde resin

150

150

150

PUR

110
140

EP

90
130

Thermoset Examples

ABS, Acrylonitrile
butadiene
styrene; EP, epicerol; FR, fire retardant; GF, glass fiber; LCP, Liquid crystal polymers; PBT, polybutylene terephthalate; PC, polycarbonate; PET, polyethylene terephthalate; POM, polyacetal; PS, polystyrene; PSU, polysulfone; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; UL, Underwriters laboratories.

Examples of Impact Strength Above Room Temperature

The VST is the temperature at which a standard indentation occurs for defined test samples subjected to a given linear temperature increase and a compression loading from a defined indenter of a specified weight. The load used is often 10 N (Vicat A) or 50 N (Vicat B) and must be indicated with the results. In either case, the polymer cannot be used under this compression load at this temperature. For a given thermoplastic family, VST is affected by reinforcements, fillers, and plasticizers. Table 6.15 displays some examples and other data may be found elsewhere.

Examples of Vicat Softening Temperature

Generally speaking, a temperature rise above room temperature has a plasticizing effect that is sometimes negligible. For example, between 20°C and 85°C, Izod impact strength (kJ/m2) of polyphenylene ether (PPE)/PS alloys more or less increases or is virtually unchanged: Temperature (°C)

20

45

65

85

PPE 1 PS

13

17

23

26

PPE 1 PS 30 GF

24

24

24

24

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• reduction in the impact resistance; the material

Table 6.15 Examples of Vicat Softening Temperature (VST). VST B (50 N)

243

VST A (10 N)

can become brittle. For example, commodity thermoplastics can have low service temperature as varied as 2110, 210, 0 or even 20°C.

• eventually, crystallization for semicrystalline

PEEK CF

320

TPI

260

PA 66 FR

250

PEEK

250

PEI 40 GF

221

PA 6

204

LCP 40 mineral

195

PBT 12 mineral

186

PBT FR

180

PBT

175

POM

158

PPE

135

140

PP 20 GF

132

165

PC/ABS

108

PC/ASA

103

111

SAN

102

106

CPVC

100

PP 20 talc

95

152

PS

91

95

PS

88

97

20°C. The minimum must be carefully considered because, perhaps, corresponding applications do not require impact strength and other mechanical loading.

Acrylic

86

98

• The wide range of minimum service tempera-

PP

85

150

PE-HD

80

129

PVC

75

polymers.

230

Apart from mechanical effects, low temperatures reduce degradations by aging and are sometimes used to store parts, which leads to longer lifetimes. Expected Minimum Service Temperatures

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CF, carbon fiber; FR, fire retardant; GF, glass fiber; LCP, liquid crystal polymers; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; POM, polyacetal; PPE, polyphenylene ether; PS, polystyrene; PVC, polyvinyl chloride; SAN, styrene acrylonitrile.

HDT and VST are not strictly linked but there is a certain relationship in that when HDT is low, VST is also low.

6.4.1.4 Low-Temperature Behavior A fall in temperature has only physical effects:

• increase in the modulus and rigidity. The modulus can be up to 100 and more times higher than that measured at room temperature

To provide a general rough idea of lowtemperature behaviors, Table 6.16 displays examples of minimum service temperatures for 207 grades. The minimum service temperature is an arbitrary temperature resulting from general experience and observation. It depends on general service conditions and mechanical loading notably dynamic constraints and impact. The first part of Table 6.16 displays a statistical analysis of thermoplastics minimum service temperatures. For the second part of Table 6.16 displaying ranges of minimum service temperature, we can remark:

• The data range stretching from 2269°C up to

ture for many families coming from: • formulation versatility, succinct trade appellations, errors, and mix-up. • Requirement levels depending on the targeted application. Packaging, automotive, building, aerospace, and electricity do not have the same requirements.

• Often, minimum service temperatures of reinforced and unfilled grades are similar, which implies that impact resistance isn’t considered or formulation is adapted, addition of plasticizers counterbalancing the harmful effect of fillers. The third part of Table 6.16 displays ranges of minimum service temperature for thermosetting resins with the same limitations as thermoplastics. Low-Temperature Tests

There are many methods to test low-temperature behavior, but no results can be used directly and therefore need careful interpretation. The possibility

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets. Thermoplastics: Statistical Analysis Average

260

Median

240

Minimum

2269

Maximum

20

Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets.—Cont’d Thermoplastics Minimum Service Temperature Ranges

Thermoplastics Minimum Service Temperature Ranges

Minimum (°C)

Maximum (°C)

PA 11 or 12 plasticized

2120

270

PA 12

2120

270

PA 11 GF

2120

250

PA 12 CF

2120

250

PA 12 GF

2120

250

PA 12 GB

2120

250

Minimum (°C)

Maximum (°C)

PPS

2269

220

PPS GF

2269

220

PPS long GF medium level

2269

220

PA 12 low friction

2120

250

ETFE

2100

2100

PPS long GF high level

2269

220

PES

2100

280

PPS CF

2269

220

PES GF

2100

280

PPS CF 1 GF

2269

220

PES CF

2100

280

PPS conductive

2269

220

PES low friction

2100

260

PPS Far

2269

220

EMA

2100

250

PPS GF 1 mineral

2269

220

ETFE GF

2100

250

PCTFE

2250

2150

PA 6
10

2100

250

PI TP

2250

260

PA 6
10 CF

2100

250

PI TP CF

2250

260

PA 6
12

2100

250

PI TP GF

2250

260

PAI GF

2100

250

PI TP low friction

2250

260

PAI CF

2100

250

PE-UHMW

2200

2100

PAI low friction

2100

250

PTFE

2200

280

PAI mineral

2100

250

PTFE CF

2200

280

PEEK/PBI

2100

250

PTFE low friction

2200

280

PEEK/PBI GF

2100

250

PTFE GF

2200

280

PEEK/PBI CF

2100

250

LCP

2200

250

Polyarylate

2100

250

LCP CF

2200

250

PSU

2100

250

LCP GF

2200

250

COPE high shore D

2100

240

LCP mineral

2200

250

COPE low shore D

2100

240

PAI

2196

260

PA 6
12 GF

2100

240

PBI

2160

2100

2100

240

PFA

2150

2150

FEP

2150

2100

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

2150

2100

PPSU

2100

240

FEP GF

2120

270

PPSU GF

2100

240

PA 11

PC

2100

225

(Continued )

(Continued )

6: ENVIRONMENTAL

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Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets.—Cont’d

245

Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets.—Cont’d

Thermoplastics Minimum Service Temperature Ranges Minimum (°C)

Maximum (°C)

PC GF

2100

225

PC CF

2100

PC CNT

Thermoplastics Minimum Service Temperature Ranges Minimum (°C)

Maximum (°C)

PE GF

270

250

225

PE 60% long GF

270

250

2100

225

PE-HD

270

250

PC conductive

2100

225

PE-HD antistatic, black

270

250

PC low friction

2100

225

PSU modified

270

250

Polyarylate GF

2100

225

PEEK

270

240

PA 12 conductive

280

250

PEEK GF

270

240

PA CNT

280

250

PEEK CF

270

240

PA 6

280

250

PAEK 30% GF

270

240

PA 6 GB

280

250

PSU GF

270

240

PA 6 medium level GF

280

250

PSU mineral

270

240

PA 6 medium level long GF

280

250

CPE

270

235

PVF 280

250

270

235

PA 6 high level GF

TPU GF

280

250

270

230

PA 6 high level long GF

TPU long GF

280

250

270

230

PA 66 impact medium level GF

TPU conductive

270

230

PA 6 GF recycled

280

240

TPU shore D

270

230

PA 6 FR

280

240

PP/EPDM-V

263

230

PA 6 mineral FR

280

240

PEBA 25
45 shore D

260

260

PA 6 recycled

280

240

PEBA Bio

260

240

PA 66

280

240

TPS shore D

260

240

PA 66 CF

280

240

TPE based on PVC

260

230

PA 66 GB

280

240

TPO shore D

260

230

PA 66 medium level GF

280

240

TPV shore D

260

230

PA 66 long CF

280

240

ABS/PA

260

220

PA 66 medium-level long GF

280

240

ABS/PA 20 GF

260

220

ABS/PC

260

220

PA 66 MINERAL

280

240

260

220

PA 66 high level GF

280

240

ABS/PC_ low-level long GF

PA 66 high-level long GF

280

240

ABS/PC_medium-level long GF

260

220

PA 66 conductive

280

240

ABS/PC conductive

260

220

ECTFE

276

276

ABS/PC GF

260

220

PE-LD

270

260

POM homo- or copolymer

250

240

(Continued )

POM GF

250

240

(Continued )

246

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets.—Cont’d

Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets.—Cont’d

Thermoplastics Minimum Service Temperature Ranges Minimum (°C)

Maximum (°C)

POM long GF

250

240

POM GB

250

POM CF

Thermoplastics Minimum Service Temperature Ranges Minimum (°C)

Maximum (°C)

ABS GF

240

220

240

ABS GB

240

220

250

240

ABS CF

240

220

POM conductive

250

240

ABS conductive

240

220

POM far

250

240

ABS FR

240

220

POM low friction

250

240

PET

240

220

POM mineral

250

240

PET GF

240

220

COPE Bio

250

230

PET amorphous

240

220

MPR

250

230

PET/PBT high level GF

240

220

PE-X crosslinked

250

230

PMP

240

220

PPE

250

230

PMP GF

240

220

PPE GF

250

230

PMP mineral

240

220

PPE CF

250

230

PP impact

240

220

PPE MINERAL

250

230

PS impact

240

220

PC/PBT

250

225

PVDF

240

220

PC/PBT GF

250

225

PVDF CF

240

220

TPU Bio

250

225

PVDF low friction

240

220

PA castable

240

240

PVDF mica

240

220

PEBA 50
72 shore D

240

240

PP Co

240

210

PTT Bio

240

240

PVC plasticized

240

25

PTT Bio GF

240

240

CA

230

225

PA castable low friction

240

230

PP low level GF

230

25

PBT

240

230

PP medium level GF

230

25

PBT medium level GB

240

230

PP mineral

230

25

PBT medium level GF

240

230

PP talc

230

25

PBT GF and mineral

240

230

PP low level CNT

230

25

PBT long GF

240

230

PP medium CNT

230

25

PBT long CF

240

230

230

25

PBT CF

240

230

PP long GF medium level

PET/PC

240

230

PP long GF high level

230

25

PK

240

230

PP antistatic

220

210

PK GF

240

230

PP CF

220

210

PET/PC GF

240

225

PP Ho

220

25

ABS

240

220

PP recycled

220

25

PP GB

220

25

(Continued )

(Continued )

6: ENVIRONMENTAL

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Table 6.16 Expected Minimum Service Temperatures for Thermoplastics and Thermosets.—Cont’d

247

ambient temperature, like the PS used for yoghurt packaging. It is necessary to distinguish between:

Thermoplastics Minimum Service Temperature Ranges

• Short-term tests: brittle point, low-temperature impact test, low-temperature rigidity, and elastic recovery for elastomers and TPEs.

Minimum (°C)

Maximum (°C)

PP cellulose fibers

220

25

PP CaCO3

220

25

PP conductive

220

25

PP natural fibers

220

25

PS GF

220

Standardized Impact Tests Processed at Low Temperatures Low-temperature impact tests:

20

PVDC

215

215

PVC GF

210

0

PVC unplasticized

210

0

cooled samples are subjected to a conventional impact test. Generally, the most often used temperatures are 220°C, 230°C, or 240°C. Table 6.17 displays examples of impact strength tested at low temperatures.

PVCC

0

0

ASA/PVC

0

8

Thermosets Minimum Service Temperature Ranges Minimum (°C)

Maximum (°C)

Polyimide

2250

260

Polycyanate

2210

Silicone

2110

PF

2100

PUR

260

214

EP

270

220

MF

250

230

UP

240

230

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CF, carbon fiber; CNT, carbon nanotubes; COPE, copolyester; EP, epicerol; FEP, fluorinated ethylene propylene; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MPR, melt processable rubber; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; PES, polyethersulfone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PK, polyketone; PMP, polymethylpentene; POM, polyacetal; PPE, polyphenylene ether; PS, polystyrene; PSU, polysulfone; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; PVDC, polyvinylidene chloride; TP, thermoplastic; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; UHMW, ultrahigh molecular weight; UP, unsaturated polyester.

to use a plastic at low temperature depends on the service conditions including loading and impacts. Some grades can be used at 2200°C or less if there are no impacts. Some other plastics can be brittle at

• Long-term tests: crystallization tests, which make it possible to detect a slow crystallization by the evolution of hardness with time.

Brittle Point

The very fuzzy definition of the brittle point is based on a more or less sudden reduction in the impact resistance or the flexibility. The indicated values must be carefully considered.

• Low-temperature brittleness or toughness: the samples are cooled to a temperature far lower than the supposed temperature of brittleness, and then gradually warmed up. At each selected step temperature, the test specimens are subjected to a specified impact. The temperature at which specimens deteriorate or fail is the brittle point. In some other tests, the lowest temperature to which specimens can be cooled without deterioration is regarded as the limiting temperature of “toughness” or “no brittleness.”

• Low-temperature flexibility of thin products: the product is rolled up on a specified mandrel at one or several temperatures. Dynamic Torsion Modulus

The oldest test is the Clash & Berg based on the evolution of the dynamic torsion modulus when the temperature decreases. Results can be:

• plotted versus the temperature • expressed as the value of the modulus for specified temperatures

• recorded as the temperatures for which the

modulus is 2, 5, 10, 100 . . . times higher than that measured at room temperature.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.17 Examples of Low-Temperature Impact Tests According to Various Methods. Izod Impact, Notched Temperature (°C)

240

230

218

23

Unit

J/cm

J/cm

J/cm

J/cm

PPE 1 PS

1.33

2.13

PA 6 33 GF conditioned

1.07

2.35

PA 6 33 GF dry

1.07

1.48

PPE 1 PS 30 GF

0.96

1.17

PA 6 dry

0.32

0.48

PA 6 conditioned

0.21

1.6

PPE 1 PA

1

ABS GP

0.8

PPE 1 PS 1 PA 30 GF

0.8

ABS GP

0.6

PS

0.6

2.2 0.85

2.4 1.06

1

3 1.5

Izod Impact, Notched (ISO) Temperature (°C)

240

Unit

kJ/m

PA 6 33 GF dry

8.5

230 2

kJ/m

220 2

kJ/m

23 2

kJ/m2 10

PC

12

65

PPE 1 PA

10

20

PPS low filler

7

PPE 1 PS

5

7

7 17

TPO

4

45

PP 20 mineral

2.1

6

Charpy Impact, Unnotched Temperature (°C)

230

Unit

J/cm

ABS GP

10

PC

NB

220 2

J/cm

23 2

J/cm2 18

NB

NB

NB

NB

8.31

8.24

PA 6/66 30 CF

5

4.5

PP 20 mineral

3

7

2.8

2.8

TPO PA 11 30 GF

8.39

PPS low filler

2.8

ABS GP

9

12.5

PP 30 long GF

5.5

5

LCP

5.3

26.7

Charpy Impact, Notched Temperature (°C)

230

220

23 (Continued )

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249

Table 6.17 Examples of Low-Temperature Impact Tests According to Various Methods.—Cont’d Unit

J/cm2

J/cm2

ABS GP

0.8

2.2

PC

1.2

5.5

TPO

0.5

PA 11 30 GF

1.2

0.6

J/cm2

5.8 2.06

PA 6/66 30 CF

0.4

0.7

PP 20 mineral

0.24

0.6

0.7

0.7

PPS low filler

0.7

ABS GP

0.7

PA 11 conditioned

1

PA 11 dry

1.1

0.8

PA 6 33 GF dry

1

1.5

PPE 1 PA

1

2

1.9 1

1

ABS, Acrylonitrile
butadiene
styrene; CF, carbon fiber; GF, glass fiber; LCP, liquid crystal polymers; PA, polyamide; PC, polycarbonate; PPE, polyphenylene ether; PS, polystyrene.

Table 6.18 displays on the one hand general ranges and some examples of low-temperature assessments and characteristics linked to minimum service temperatures, and on the other hand, brittleness temperatures. We can remark:

• Some examples of minimum service temperatures are out of the general range probably because of special applications and/or special formulations.

• Brittleness temperatures can be in or out the general range of minimum service temperatures according to the user’s requirements. Crystallization Test

The crystallization test consists of measuring the evolution of hardness at a specified temperature over several weeks. This method is of special interest for those polymers that can slowly crystallize at service temperatures. The combination of low-temperature periods and immersion in chemicals at temperatures superior to their melting point leading to chemical uptake can induce worsening of existing defects by volume increase of solidified chemicals during cooling.

6.4.2 Density Table 6.19 displays expected minimum and maximum values of density for thermoplastics and thermosets classified into:

• Expected neat grades: those compounds are claimed “neat” but some are probably more or less modified and may include secondary polymer and/or recycled materials.

• Special grades reinforced with fibers or CNT (carbon nanotubes), filled with minerals or GB, FR, conductive, “antistat,” WPC, “friction,” etc. Special grades with low density may be foamed. The first part of Table 6.19 reports a statistical analysis of thermoplastics density. The second part of Table 6.19 displays detailed data for thermoplastics. The third part of Table 6.19 displays detailed data for thermosets. Obviously, filled and reinforced grades have higher density than their unfilled counterparts. There are many sources of monomers, polymerization methods, formulae, processing methods, recycling routes, levels of recycled, and virgin

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.18 Examples of Low-Temperature Assessments and Characteristics. Minimum Service Temperature (°C) Plastic

General Range

Brittleness (°C)

Examples

Minimum

Maximum

PPS

2269

220

250

PPS GF

2269

220

250

PE-UHMW

2200

2100

2150; 2250

PTFE

2200

280

2250; 2268

ETFE

2200

250

2200; 2100

PFA

2150

2150

2200

FEP

2150

2100

2100

PA 11

2120

270

250

PA 12

2120

250

250

PA 6
12

2100

250

2100

PES

2100

250

250

COPE low shore D

2100

240

275

COPE high shore D

2100

240

250

PC

2100

225

260; 250

PA 6

280

250

230

PA 66

280

240

230

PA 66 medium level GF

280

240

220

PE-LD

270

260

PE-HD

270

250

250

275

PEEK GF

270

240

240

265

PEEK

270

240

250; 240

265

PEEK CF

270

220

220

265

PP/EPDM-V

263

230

260

TPE based on PVC

260

230

244

POM homo- or copolymer

250

240

250

PPE

250

230

250

PPE GF

250

230

250

MPR

250

230

249

POM conductive

250

220

220

PA castable

240

240

240

ABS

240

220

240

PET

240

220

240; 220

PVDF

240

220

253; 237

PVDF CF

240

220

0

2200

2130 280; 265 280; 276; , 2 70

269; 268

(Continued )

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251

Table 6.18 Examples of Low-Temperature Assessments and Characteristics.—Cont’d Minimum Service Temperature (°C) Plastic

General Range

Brittleness (°C)

Examples

Minimum

Maximum

PP Co

240

210

PVC plasticized

240

25

PP medium level GF

230

25

5

PP Ho

220

25

0; 5

PVC unplasticized

210

0

215; 26; 23; 15

PVCC

0

0

224

230; 4;5

220 247; 244; 225

PA 46

240

Acrylic

240; 234 , 2 70; 2100

EVA

ABS, Acrylonitrile
butadiene
styrene; CF, carbon fiber; COPE, copolyester; EVA, ethylene-vinyl acetate; FEP, fluorinated ethylene propylene; GF, glass fiber; MPR, melt processable rubber; PA, polyamide; PC, polycarbonate; PE, polyethylene; PET, polyethylene terephthalate; PFA, perfluoroalkoxy; POM, polyacetal; PPE, polyphenylene ether; PTFE, polytetrafluoroethylene; PES, polyethersulfone; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; UHMW, ultrahigh molecular weight.

Table 6.19 Density Examples. Density of Thermoplastics: Statistical Analysis Expected Neat Grades

Special Grades

Mean

1.22

1.41

Median

1.18

1.4

Standard deviation

0.26

0.30

Minimum

0.833

0.9

Maximum

2.2

4 Expected Neat Grades

Density of Thermoplastics: Details

Minimum

Maximum

PMP

0.833

0.84

PP impact

0.88

0.91

PP Ho

0.9

0.91

PB

0.9

0.94

PE-LD

0.917

0.94

PE-UHMW

0.92

0.955

PP low level CNT PP recycled

0.9

1

PP/EPDM-V

0.9

1

TPV shore D

0.9

1

EMA

0.93

0.97

PP medium CNT

Special Grades Minimum

Maximum

0.93

0.95

0.94

0.97

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

Special Grades Minimum

Maximum

0.9

1.01

0.95

0.97

0.96

1.05

PP CF

0.95

1.1

PP conductive

0.95

1.1

0.97

1.1

1

1.1

0.99

1.13

0.95

1.2

PMP mineral

1

1.15

PP cellulose fibers

1.02

1.13

PP antistatic PE-HD

0.94

0.98

PE-HD antistatic, black PP Co

0.9

1.04

COC

0.95

1.02

EVA

0.92

1.07

TPO shore D

0.9

1.1

PMP GF Starch/PE

1.01

1.01

PA 11 or 12 plasticized

1

1.03

PA 10
10 Bio

1.01

1.05

PLA/PE

1.03

1.03

PP low level GF PA 12

1.01

1.06

PS

1.02

1.05

Starch/PP

0.995

1.1

PEBA 50
72 shore D

1

1.1

PLA wood WPC PA 11

1.01

1.09

PP/PA

1.03

1.07

PP natural fibers ASA

1.05

1.07

PA 6
12

1.06

1.06

ABS/PA

1.06

1.07

PEBA 25
45 shore D

1

1.14

PEBA Bio

1

1.14

PPE

1.04

1.1

PP wood WPC ABS

1

1.15

SMMA

1.03

1.13

PA 6 recycled

1.06

1.1

SAN

1.06

1.1

PA 6
10

1.07

1.1

(Continued )

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Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

PA 4
10 Bio

1.08

1.09

MABS

1.08

1.1

TPS shore D

0.9

1.3

PA transparent

1

1.2

PS impact

1.03

1.17

PA 6

1.05

1.15

Special Grades Minimum

Maximum

0.97

1.25

PS 40% wood WPC

1.07

1.16

PE wood WPC

0.994

1.24

ABS CF

1.1

1.15

PP GB

1.1

1.15

PMMA antistatic

1.13

1.15

1.1

1.2

1.13

1.17

PA 12 friction

1.03

1.3

PP medium level GF

1.1

1.23

PP long GF medium level

1.1

1.23

PC CNT

1.12

1.21

1.04

1.3

PA 6 FR

1.16

1.2

ABS GF

1.17

1.19

PP talc PPE/PA

1.1

1.12

PA 66

1.04

1.2

SMA

1.05

1.2

Starch/PS

1.1

1.18

PA castable

1.13

1.16

ABS/PC

1.1

1.2

ASA/PMMA

1.1

1.2

EVOH

1.1

1.2

PA 12 CF PMMA impact

1.1

1.2

PPA

1.1

1.2

TPU Bio

1.1

1.2

PA CNT PE-X crosslinked

0.915

1.4

CPE

1.13

1.2

PSU/ABS

1.13

1.2

PA 12 conductive PC

1.15

1.2

PMMA

1.15

1.2

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

PA 4
6

1.17

1.19

PA far

1.15

1.22

1.15

1.23

PP CaCO3

1.14

1.25

ABS FR

1.15

1.25

PA castable friction

1.15

1.25

1.1

1.3

1.18

1.23

PP/PA GF

1.12

1.31

PP mineral

0.97

1.48

1.2

1.25

1.15

1.32

1.2

1.3

PPA CF

1.19

1.32

ABS GB

1.24

1.27

TPE based on PVC

Minimum

1.1

Maximum

Special Grades

1.28

ABS/PA 20 GF PLA/PMMA

1.17

1.21

Acrylique IMIDE

1.2

1.2

ASA/PVC

1.2

1.2

TPU shore D

1.2

1.2

COPE Bio

1.1

1.3

PE GF MPR

1.06

1.35

CP

1.17

1.24

PPE CF ASA/PC

1.12

1.3

PMI or PMMI

1.2

1.22

PET/PC

1.2

1.23

Starch/copolyester

1.13

1.32

CAB

1.15

1.3

PPE mineral PSU/PC

1.22

1.23

Polyarylate

1.2

1.26

ABS conductive PLA/PC

1.18

1.3

PK

1.24

1.24

ABS/PVC

1.13

1.36

COPE low shore D

1.1

1.4

ABS/PC conductive COPE high shore D

1.2

1.3

PC/PBT

1.2

1.3

PLA/Copolyester

1.24

1.27

(Continued )

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Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

Special Grades Minimum

Maximum

1.22

1.3

1.2

1.33

1.1

1.44

PPE GF

1.26

1.28

SMA GF

1.2

1.35

SAN GF

1.15

1.41

PPE/PA GF

1.2

1.37

PA 66 long CF

1.27

1.3

1.25

1.33

PC conductive

1.24

1.35

PP long GF high level

1.24

1.35

TPU conductive

1.28

1.31

PA 66 conductive

1.2

1.4

PA 66 impact medium level GF

1.2

1.4

PC/SAN GF

1.2

1.4

PVC wood WPC

1.2

1.4

PLA/PP 30% GF

1.1

1.5

PAA medium level CF

1.28

1.33

PLA natural reinforcement

1.28

1.33

ABS/PC GF

1.22

1.4

PA 11 GF

1.22

1.4

PA 4
10 GF Bio

1.3

1.35

PA 12 GB

1.22

1.44

PA 6 GF recycled

1.3

1.37

PA 6 medium level GF

1.2

1.5

PA 6 medium level long GF

1.25

1.45

PA 12 GF PSU

1.23

1.29

PA 66 CF PTT Bio

1.2

1.33

PA 6
10 CF PLA

1.21

1.33

PSU modified

1.23

1.31

CA

PEI

1.22

1.27

1.34

1.3

PC CF PAEK (PEK. PEKK. PEEK. PEEKK. PEKEKK)

PEEK

PBI

PPSU

POM homo- or copolymer

1.26

1.27

1.3

1.29

1.26

1.32

1.32

1.3

1.35

1.42

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

PA 6
12 GF

1.3

1.4

PC friction

1.3

1.4

1.3

1.4

PS GF

1.3

1.4

PMMA GF

1.3

1.42

ABS/PC low level long GF

1.36

1.36

PPS far

1.35

1.38

PA 6 GB

1.35

1.4

PA 66 GB

1.35

1.4

PA 66 medium level long GF

1.36

1.4

PEEK CF

1.33

1.44

PBT CF

1.34

1.44

PEI CF

1.31

1.48

PLA/PBT GF

1.2

1.6

ASA/PBT GF

1.3

1.5

PC GF

1.3

1.5

PC/PBT GF

1.3

1.5

PEEK/PBI CF

1.4

1.41

PI TP CF

1.4

1.43

PES CF

1.38

1.47

PAA medium level GF

1.4

1.45

PA 4
6 GF

1.41

1.44

POM Far

1.35

1.5

PAI friction

1.4

1.5

PBT long CF

1.4

1.5

PEI mineral

1.4

1.5

Polyarylate GF

1.4

1.5

PPS CF

1.4

1.5

PEEK/PBI

Minimum

1.3

Maximum

Special Grades

1.4

PEI conductive PES

1.3

1.4

PET

1.3

1.4

PET amorphous

1.3

1.4

PPS

1.3

1.4

PI TP

PBT

PAI

PVC unplasticized

1.33

1.3

1.4

1.35

1.43

1.5

1.42

1.5

(Continued )

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Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

POM CF

1.42

1.48

PET/PC GF

1.3

1.6

POM friction

1.4

1.54

PA 66 mineral

1.35

1.6

POM GF

1.35

1.6

PA 66 medium level GF

1.36

1.6

POM conductive

1.42

1.54

PAI CF

1.48

1.5

PI TP GF

1.43

1.56

PSU/PBT GF

1.47

1.52

TPU GF

1.3

1.7

LCP CF

1.4

1.6

PCT GF

1.4

1.6

PPSU GF

1.4

1.6

PSU GF

1.4

1.6

PTT Bio GF

1.4

1.6

PVC GF

1.43

1.57

PBT medium level GB

1.45

1.55

ABS/PC medium-level long GF

1.5

1.5

PE 60% long GF

1.5

1.51

PK GF

1.46

1.56

PA 10
10 high level GF Bio

1.5

1.52

PA 4
6 mineral

1.51

1.51

PEEK GF

1.49

1.54

PAEK 30% GF

1.49

1.54

1.45

1.6

PEI GF

1.48

1.6

PA 6 mineral FR

1.4

1.7

PI TP friction

1.4

1.7

PPS GF

1.4

1.7

TPU long GF

1.4

1.7

PA 66 high level GF

1.5

1.6

PBT medium level GF

1.5

1.6

PBT long GF

1.5

1.6

PVCC

PVC plasticized

Minimum

1.47

1.15

Maximum

Special Grades

1.55

1.9

PSU mineral PVF

1.37

1.71

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

PEEK/PBI GF

1.5

1.6

PEI GF milled

1.5

1.6

PET GF

1.5

1.6

PLA GF

1.5

1.6

PPA mineral

1.5

1.6

PAI mineral

1.5

1.61

POM GB

1.5

1.62

PPA GF

1.43

1.7

PAA mineral

1.45

1.7

PES friction

1.45

1.7

PPS CF 1 GF

1.45

1.7

POM mineral

1.47

1.7

PPS conductive

1.4

1.8

PA 6 high level GF

1.5

1.7

PES GF

1.5

1.7

PAI GF

1.6

1.61

PPS long GF medium level

1.52

1.7

PPA long GF

1.59

1.65

LCP GF

1.5

1.8

PA 6 high-level long GF

1.6

1.7

PA 66 high-level long GF

1.6

1.7

PBT GF and mineral

1.6

1.7

LCP mineral

1.5

1.9

POM long GF

1.7

1.72

PPS long GF high level

1.72

1.73

PAA high level GF

1.7

1.77

1.7

1.8

PVDF CF

1.7

1.8

PVDF friction

1.7

1.8

ETFE GF

1.7

2

PVDF mica

1.8

1.9

PPS GF and mineral

1.8

2

LCP

PVDC

Minimum

1.4

1.6

Maximum

Special Grades

1.8

1.75

ECTFE

1.6

1.9

ETFE

1.6

1.9

PET/PBT high level GF PVDF

1.7

1.8

(Continued )

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Table 6.19 Density Examples.—Cont’d Expected Neat Grades Density of Thermoplastics: Details

Minimum

Maximum

Special Grades Minimum

Maximum

2.05

2.22

FEP GF

2.2

2.2

PTFE GF

2.2

2.3

PTFE friction

3.5

4

PTFE CF FEP

2.1

2.2

PCTFE

2.1

2.2

PFA

2.1

2.2

PTFE

2.1

2.2

Density of Thermosets

Expected Neat Grades Minimum

Minimum

Maximum

PUR foam

0.02

0.16

Silicone foam

0.13

0.75

EP foamed

0.7

1.45

PUR SRRIM

1

1.7

PUR RIM

1.04

1.26

1.3

1.4

UP/GF SMC foamed

1.3

1.43

PF organic filled

1.3

1.5

PI/CF

1.43

1.56

UF cellulose

1.45

1.55

UP/GF mat

1.3

1.75

PF molding

1.3

1.8

EP/CF UD

1.5

1.67

UP glass fabric

1.5

1.85

EP filled, molding

1.1

2.3

MF modified

1.5

1.9

PF/GF SMC

1.6

1.8

PI/GF molding

1.5

1.9

UP filled, molding

1.3

2.1

Cy neat

1.15

Maximum

Special Grades

1.25

PUR Sh A

1.05

1.36

EP neat

1.1

1.4

Silicone RTV

1

1.5

UP cast

1.1

1.4

EP/Aramid fiber UD Fluorosilicone

1.3

1.4

PUR Sh D

1.1

1.6

Silicone HVR

1.1

1.7

PI neat

1.33

1.5

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.19 Density Examples.—Cont’d Density of Thermosets

Expected Neat Grades Minimum

Special Grades

Maximum

Minimum

Maximum

PF/GF molding

1.5

2

UP SMC 10/50 GF

1.6

1.9

MF filled

1.5

2.1

UP/GF SMC UD

1.7

1.9

UP/GF BMC

1.7

1.95

Silicone resin

1.8

1.9

EP glass fabric

1.8

1.95

UP glass roving

1.7

2.1

PI glass fabric

1.9

2

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; COC, cyclic olefin copolymers; CF, carbon fiber; CNT, carbon nanotubes; COPE, copolyester; EP, epicerol; EVA, ethylene-vinyl acetate; EVOH, ethylene vinyl alcohol copolymers; FEP, fluorinated ethylene propylene; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MPR, melt processable rubber; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PK, polyketone; PLA, polylactic acid; TP, thermoplastic; PMI, polymethacrylimide; PMMA, poly methylmethacrylate; PMP, polymethylpentene; POM, polyacetal; PPA, polyphthalamide; PES, polyethersulfone; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; PVDC, polyvinylidene chloride; SMMA, styrene methyl methacrylate; RTV, room-temperature vulcanization; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; UD, unidirectional; UHMW, ultrahigh molecular weight; UP, unsaturated polyester; WPC, wood plastic composite.

materials leading to a broad range of properties. These data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered.

6.4.3 Mechanical Properties 6.4.3.1 Hardness Fig. 6.4 displays an arbitrary hardness rating (without units) making it possible to quickly visualize the hardness of one subfamily compared to others.

6.4.3.2 Stress and Strain Under Unidirectional Loading: Tensile, Flexural, and Compression Properties Many standards exist defining various tests according to simplified loading conditions and specified tests pieces. Other standards must be used for specific products, films for example.

The following information only deals with the simplest cases of tensile and possibly flexural tests. The most common standards dealing with tensile properties of plastics, ASTM D638 and ISO 527-1, not strictly equivalent, are considered technically equivalent. Both standards specify the general principles for determining the tensile properties of plastics and plastic composites under defined conditions. Several different types of test specimen are defined to suit different types of material, which are detailed in subsequent parts of ISO 527 or other standards. The methods are used to investigate the tensile behavior of the test specimens and for determining the TS, tensile modulus and other aspects of the tensile stress/strain relationship including the option of determining Poisson’s ratio at room temperature under the conditions defined. According to these standards:

• Stresses are well-defined resulting of uniaxial loadings when in real life there is a complex combination of loadings.

• Test pieces have optimized shapes and are manufactured in the best conditions leading to the highest mechanical properties.

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Several typical points and values are defined, for example:

PEI PMMA PPS GF& MINERAL PEEK PET, PBT PAI ACRYLIC IMIDE POM GF POM PESU PS PPS PC SAN PA 6, 66 CA LCP PVC-U PPE ABS PSU PVDC PVCC PP TALC PCTFE PP PVDF ASA PA 11 or 12 ETFE Soft PVC

Elastic limit or proportional limit The elastic or proportional limit is the greatest stress at which the stress is proportional to strain. Note that some materials maintain this proportionality for large stresses and strains while others show proportionality for very low strains. For some materials, there isn’t proportionality. Yield point The yield point is the first point of the stress/strain curve for which one notes an increase in the strain without an increase in the stress. Parts must always operate well below this point during service. Note that some materials have not a yield point. Stress and strain at yield Stress and strain at yield are the values of the stress and strain corresponding to the yield point. Strain at yield may be slightly (one or some percent) or highly (up to more than 100%) inferior to elongation at break. Ultimate stress and strain Ultimate stress and strain, or stress and strain at break, are the values corresponding to the breaking of the samples.

PE-UHMW PE PTFE PFA FEP EVA 0

20

40

60

Figure 6.4 Arbitrary hardness rating, without unit.

• Test pieces with defects are rejected. • Test time range is of the order of one or a few minutes being not representative of high-speed loadings on the one hand, and creep or relaxation on the other hand.

• Environment is “clean” air. • Temperature is “room temperature,” often 20°C.

• Hygrometry must be defined for thermoplastics such as polyamides.

• Unless otherwise stated, properties of unidirectional composites are measured in the favorable direction.

Elastic modulus or Young’s modulus The elastic modulus is the slope of the tangent at the origin of the stress/strain curve. For some plastic materials, the elastic modulus can be misleading due to the material nonlinear elasticity leading to a flattening of the stress/strain curve. Initial modulus If the rectilinear region at the start of the stress-strain curve is too difficult to locate, the tangent to the initial portion of the curve must be constructed to obtain the initial modulus. For some plastic materials, the initial modulus can be misleading due to the material nonlinear elasticity leading to a flattening of the stress/strain curve. Secant modulus The secant modulus is the ratio of stress to corresponding strain at any point on the stress-strain curve. For example, the 1% secant modulus sometimes provided by

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

262

producers or compounders is the stress at 1% strain. For a define material, the secant modulus is lower than the initial modulus. We must keep in mind that literature data are not always clearly defined or sometimes are misleading, mixing for example Young modulus, secant modulus, and initial modulus or mixing yield strain and elongation at break. Table 6.20 displays yield strength and TS examples ranked in descending order for yield strength. The first part of Table 6.20 displays statistical results of 6 different runs carried out for the determination of TS of 6 compounds. Coefficients of variation evolve from 0.54 up to 10.4. The second part of Table 6.20 displays average yield strength for 8 subfamilies: expected neat grades, and special grades including CF-reinforced grades, GF-reinforced grades, mineral and GBreinforced grades, conductive grades, friction grades, and WPC. Please note that general purpose grades can be formulated with plasticizers, fillers and reinforcements and are called “expected neat grades.” For the third and fourth parts of Table 6.20 displaying ranges of stresses of thermoplastic and thermoset examples, respectively, we can remark:

• A significant lack of correlation between yield and TS.

• The broad range of strengths for many families coming from formulation versatility, succinct trade appellations, test method versatility, errors, and mix-up.

• High values of yield and TSs for fiber reinforced grades, in the decreasing order of carbon, glass, aramid, natural fibers. These data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered. Table 6.21 displays examples of strain at yield and elongation at break. The first part of Table 6.21 displays average yield strain for 8 thermoplastics subfamilies: expected neat grades, and special grades including

CF-reinforced grades, GF-reinforced grades, mineral and GB-reinforced grades, conductive grades, friction grades, and WPC. Note that general purpose grades can be formulated with plasticizers, fillers, and reinforcements and are called “expected neat grades.” The second part of Table 6.21 displays strain at yield and elongation at break of various thermoplastics subfamilies. Obviously, strain at yield is lower than elongation at break for a same compound with sometimes huge differences. For most experiments, elongations at break are in a broad range up to more than 200% and a mean value of more than 50% when strains at yield are limited to a mean value of about 5% and a maximum of 50% The third part of Table 6.21 displays a few examples for thermoset compounds and composites. These data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered. Table 6.22 displays examples of tensile or flexural modulus The first part of Table 6.22 displays standard deviations and coefficients of variation for 4 runs of tensile modulus tests The second part of Table 6.22 displays average tensile modulus for 8 thermoplastics subfamilies: expected neat grades, and special grades including CF-reinforced grades, GF-reinforced grades, mineral and GB-reinforced grades, conductive grades, friction grades, and WPC. Note that general purpose grades can be formulated with plasticizers, fillers, and reinforcements and are called “expected neat grades.” The third part of Table 6.22 displays tensile modulus examples for thermoplastics compounds and composites. The fourth part of Table 6.22 displays flexural modulus examples for thermoset compounds and composites. Please note:

• The vast range of modulus of thermoplastic and thermoset examples, 0.001 up to 32, that is to say a ratio of 32,000.

Table 6.20 Yield and Tensile Strength Examples (MPa). Thermoplastics: Examples of Statistical Analysis of 6 Tensile Strength Experiments Average TS of Each Run (MPa)

Standard Deviation of Each Run

Coefficient of Variation of Each Run (%)

23.8

0.4

1.7

26.9

0.8

3

59.2

0.32

0.54

77.6

2.6

3.4

288

30

10.4

266

24

9

Average Yield Strength of 8 Thermoplastic Subfamilies Yield Strength, Mean (MPa) Neat grades

52

Special grades

109

CF-reinforced grades

165

GF-reinforced grades

127

Mineral, GB-reinforced grades

77

Conductive grades

67

Friction grades

68

WPC

30

Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

PAA medium level CF

270

PPA CF

Neat Grades Minimum

Maximum

Special Grades Minimum

Maximum

315

270

315

263

270

152

270

PPA long GF

262

262

207

269

PA 6 high-level long GF

250

280

250

280

250

260

PA 66 long CF

Maximum

Tensile Strength (MPa)

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Maximum

Tensile Strength (MPa)

Special Grades Minimum

Maximum

PA 66 high-level long GF

230

PEEK/PBI CF

Neat Grades Minimum

Maximum

Special Grades Minimum

Maximum

323

230

323

230

240

185

230

PPA GF

221

221

179

221

PI TP CF

220

230

230

250

PAA high level GF

200

290

200

290

PAI CF

200

203

200

221

PEI conductive

190

210

200

210

PA 66 medium level long GF

185

200

160

200

TPU long GF

180

250

182

250

PBT long CF

180

220

180

220

PPS long GF medium level

167

168

165

176

PEEK CF

160

240

160

240

PPS CF

160

210

160

210

PA 10
10 high level GF Bio

160

200

160

200

PEEK/PBI GF

160

170

160

170

PI TP GF

160

170

160

220

PA 6 medium level long GF

157

210

157

210

PA 66 CF

150

310

150

310

PA 12 CF

150

273

140

273

PA 66 high level GF

150

240

150

255

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

PPS long GF high level

150

PEEK GF

Neat Grades

Maximum

180

165

180

150

180

150

180

PAEK 30% GF

150

180

150

180

PBT long GF

150

180

150

180

PET/PBT high level GF

150

180

150

180

PEI GF

150

160

150

160

ABS/PC medium level long GF

150

152

150

152

LCP CF

149

240

110

240

PES CF

148

185

117

185

PAI mineral

147

148

100

148

PPE/PA GF

140

185

120

185

140

160

Minimum

110

Maximum

Special Grades Minimum

PBI

Maximum

Tensile Strength (MPa)

160

PA 6
12 GF

130

140

140

170

PEI CF

137

255

131

222

PAI

130

150

130

195

PBT medium level GF

130

140

130

140

PBT CF

125

175

117

175

PAA medium level GF

125

170

125

185

PAI friction

125

170

84

170

ABS/PC_ low level long GF

125

125

125

125

PPS GF

120

195

120

195

POM long GF

120

123

123

123

PK GF

120

120

120

141

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

PA 6
10 CF

117

PES friction

Neat Grades

Maximum

126

117

234

115

150

115

150

LCP GF

110

220

110

220

PAI GF

110

210

110

221

110

188

Minimum

110

Maximum

Special Grades Minimum

LCP

Maximum

Tensile Strength (MPa)

188

LCP mineral

110

186

80

186

PA 4
10 GF Bio

110

170

110

170

PA far

110

121

70

121

PPS CF 1 GF

109

143

109

183

PPA mineral

107

107

103

117

PC CF

103

170

102

175

PAA mineral

100

185

100

185

PET GF

100

170

100

170

Polyarylate GF

100

145

145

150

PLA/PBT GF

100

125

120

125

PSU GF

100

125

100

130

PSU/PBT GF

100

120

100

120

PLA GF

100

110

100

114

PEI

100

110

90

100

PPE CF

96

99

83

103

PA 6 high level GF

95

210

95

210

PA 6 GF recycled

95

130

90

130

PP long GF high level

92

135

92

145

PE 60% long GF

91

115

91

115

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

PC GF

90

POM GF

Neat Grades

Maximum

160

90

160

90

147

90

160

PTT Bio GF

90

140

120

140

PCT GF

90

130

97

130

PC/PBT GF

90

130

90

140

PPE GF

90

130

80

130

SAN GF

90

130

70

130

PMMA GF

90

105

90

105

PEI mineral

90

100

90

100

90

90

Minimum

90

Maximum

Special Grades Minimum

PEEK/PBI

Maximum

Tensile Strength (MPa)

90

PA 4
6 GF

85

250

85

250

PEI GF milled

85

85

85

85

PP/PA GF

80

170

80

160

PA 11 GF

80

135

80

135

PA 12 GF

80

115

80

115

PET/PC GF

80

110

60

110

POM Far

80

96

50

96

ABS CF

78

106

78

106

PVDF CF

78

93

78

120

PPS far

77

100

65

100

PMI or PMMI

77

80

77

90

Acrylique IMIDE

77

79

77

79

PA 66 medium level GF

75

190

75

125

PES GF

75

169

75

150

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

PBT GF and mineral

75

PA 66 impact medium level GF ABS/PC GF PSU

72

Maximum

Tensile Strength (MPa)

PI TP

Maximum

147

70

147

75

120

73

120

75

80

75

125

70

160

63 70

70

Minimum

Maximum

Special Grades Minimum

83

POM CF

Neat Grades

80

160

140

70

140

PA 6 medium level GF

70

130

95

160

PPSU GF

70

120

75

140

70

85

69

72

PEEK

70

115

70

110

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

70

115

70

110

PPSU

70

94

70

94

PES

70

90

70

95

PS GF

70

85

PA CNT ETFE GF

70

83

60

83

PA castable friction

70

80

70

88

PLA/PP 30% GF

70

75

70

75

POLYARYLATE

69

70

25

70

PA 66 conductive

65

130

79

216

PPE mineral

65

75

50

75

PSU mineral

65

70

60

70

ASA/PBT GF

63

140

60

140

PPA

62

76

62

80

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

PPS GF and mineral

60

TPU GF

Neat Grades

Maximum

150

60

197

60

150

11

150

PPS conductive

60

140

60

169

PC/SAN GF

60

135

65

135

PA 66 GB

60

100

65

100

PVC GF

60

97

60

97

80

86

60

82

ABS GF

Minimum

50 60

Maximum

Special Grades Minimum

PA transparent

Maximum

Tensile Strength (MPa)

105

65

SAN

59

85

65

85

PK

59

60

55

63

PSU modified

57

66

56

66

PSU/PC

57

65

57

65

ABS/PC conductive

57

61

38

61

SMA GF

56

75

56

103

PA 6 mineral FR

55

120

55

120

PPE/PA

54

60

52

57

PE GF

52

63

50

63

PVDF friction

52

56

40

60

PA 4
6 mineral

50

106

50

106

50

95

50

75

30

50

PA 4
10 Bio

50

85

50

85

SMMA

50

85

25

70

PA 6 GB PC

50 50

75

POM mineral PA 6
10 PC CNT

55 50

50

80 75

70

45 50

77

65

90

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Special Grades Minimum

Maximum

POM conductive

49

TPU conductive

Neat Grades

Maximum

68

49

151

48

58

48

58

PVDF Mica

48

49

46

47

PP long GF medium level

46

125

46

125

POM GB

46

65

45

65

45

77

44

70

45

55

45

84

ABS/PA 20 GF PTT Bio

70 45

45

45 45

Maximum

84

77

70

PC conductive

Minimum

Special Grades Minimum

PA castable

Maximum

Tensile Strength (MPa)

70

70

PET

45

70

22

70

PPE

45

66

45

65

ABS/PC

45

65

41

65

PA 11

45

65

40

69

PA 10
10 Bio

45

55

45

65

PBT medium level GB ASA/PVC

45 45

55

50

45

50

PC friction

45

50

45

50

PI TP friction

44

66

44

145

POM friction

43

57

48

70

42

115

19

48

PSU/ABS

43

50

PP medium level GF

43 42

50

115

COC

42

71

32

71

MABS

41

50

41

48

PP CF PA 4
6

41 40

100

42 65

90

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Maximum

PA 66 mineral ASA/PC

40

Tensile Strength (MPa)

Special Grades Minimum

Maximum

40

100

65

PLA/PC

Neat Grades Minimum

Maximum

44

65

48

52

ASA/PMMA

40

65

44

65

PVCC

40

60

45

60

PA 6 recycled

40

60

40

60

PBT

40

60

40

55

PET/PC

40

60

40

57

PET amorphous

40

40

40

40

Special Grades Minimum

Maximum

40

100

PA 12 GB

39

52

39

52

PA 6 FR

38

90

38

80

PLA natural reinforcement

33

102

PP cellulose fibers

33

57

36

50

35

75

32

57

PC/PBT

37

53

ABS conductive

41 36

60

50

PA 6

35

90

40

95

PA 66

35

85

35

95

PP low level GF PMMA impact

36 35

50

65

PP natural fibers

35 35

65

57

PVC unplasticized

35

55

33

60

ASA

35

46

46

56

PVF

35

40

40

110

30

55

TPU shore D

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics PP Ho

Neat Grades Minimum

Maximum

35

40

Tensile Strength (MPa)

Special Grades Minimum

Maximum

Neat Grades Minimum

Maximum

20

40

Special Grades Minimum

Maximum

ABS GB

35

36

25

31

PMP GF

34

68

34

68

PLA wood WPC

34

36

34

35

35

42

PPS

33

90

30

90

CP

32

41

14

50

PA 6
12

31

65

31

65

POM homo- or copolymer

30

80

27

80

ECTFE

30

69

20

55

PA 12

30

65

30

65

PCTFE

30

50

30

41

ABS/PVC

30

46

41

50

PP low level CNT ABS/PA

30 30

45

45

30

45

PA 12 friction

30

45

30

40

FEP GF

30

40

30

40

27

48

ETFE

27

50

PP conductive PLA

21 27

26

50

42

60

41

83

PA 12 conductive

25

90

25

96

ABS FR

25

60

30

50

PVC wood WPC

25

49

10

40

PA 11 or 12 plasticized

24

30

25

35

PS 40% wood WPC

22

29

20

30

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Maximum

Tensile Strength (MPa)

Special Grades Minimum

Maximum

PP talc

21

PP wood WPC

21

Neat Grades Minimum

Maximum

Minimum

Maximum

35

21

35

32

20

30

10

55

EVOH

20

94

26

98

ABS

20

60

20

60

PVDF

20

56

24

50

PP/PA

20

50

23

56

PLA/PE

27

28

TPU Bio

25

39

PFA

21

30

Starch/copolyester

20

26

Starch/PE

20

53

Starch/PP

20

21

SMA

20

50

20

55

PLA/copolyester

20

44

20

22

PP antistatic

20

Special Grades

35

PVDC

20

30

20

35

PE-X crosslinked

20

26

11

32

PP GB

20

25

20

36

PE-HD antistatic, black

20

20

17

30

19

22

CA

19

51

13

67

COPE high shore D

19

50

22

50

PP CaCO3

19

22

PE-UHMW

17

49

17

49

CAB

17

43

18

52

PP Co

17

35

30

35

PP recycled

17

23

20

23

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Minimum

Maximum

PMP mineral PE-HD

16

Tensile Strength (MPa)

Special Grades Minimum

Maximum

17

21

32

Neat Grades Minimum

Maximum

18

40

FEP

19

27

PEBA 25
45 shore D

17

40

PEBA Bio

17

55

starch/PS

17

18

PTFE friction

16

18

PS

15

60

20

60

PTFE

15

43

15

43

PS impact

15

40

15

45

Special Grades Minimum

Maximum

17

22

14

16

PP mineral

15

35

13

35

PE wood WPC

15

34

15

23

PTFE CF

15

30

11

45

7

30

7

43

PMP

15

24

16

25

COPE Bio

12

34

12

34

PEBA 50
72 shore D

11

34

17

62

PP impact

11

28

23

35

PVC plasticized PE-LD

10 9

50

30

TPV shore D PTFE GF

7

10

30

12

28

20

CPE

6

12

6

23

TPO shore D

4

28

4

28

PB

4

18

22

36

EMA

3

37

11

39

COPE low shore D

3

36

3

36

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Yield Strength and Tensile Strength of Various Thermoplastic Compounds Yield Strength (MPa) Thermoplastics

Neat Grades Maximum

2

40

Special Grades Minimum

Neat Grades

Maximum

Special Grades

Minimum

Maximum

2

30

MPR

7

13

TPE based on PVC

6

19

TPS shore D

5

36

PP/EPDM-V

1.4

28

EVA

Minimum

Tensile Strength (MPa) Minimum

Maximum

Examples of Tensile Strength of Various Thermosetting Compounds Tensile Strength (MPa) Thermosetting Compounds

Neat Grades Minimum

Minimum

Maximum

EP/CF UD

1470

3040

PI/CF UD

1000

1200

UP/CF fabric

500

540

EP/GF fabric or roving

200

600

EP/CF SMC

280

350

PI/CF

200

233

EP/GF SMC

140

245

UP/GF SMC UD

92

285

PF/GF SMC

100

140

PI/GF molding

40

170

UP/GF SMC 35/50 GF

60

110

UP/GF SMC 10/30 GF

25

110

PF filled

25

100

MF modified

40

80

EP foamed

11

100

UP/GF SMC foamed

40

70

MF filled

20

90

PI neat

EP neat

30

20

Maximum

Special Grades

160

91

(Continued )

Table 6.20 Yield and Tensile Strength Examples (MPa).—Cont’d Examples of Tensile Strength of Various Thermosetting Compounds Tensile Strength (MPa) Thermosetting Compounds

Neat Grades Minimum

Minimum

Maximum

EP filled, molding

10

100

UP filled, molding

30

75

PI glass fabric

40

60

UP cast

4

90

PF molding

20

50

UF cellulose

30

40

PUR RIM

13

50

PUR cast

1

40

PUR structural foam

4

33

0.07

0.5

Silicone resin

25

Maximum

Special Grades

40

Silicone HVR

3

12

Silicone RTV

0.6

7

Fluorosilicone

2

4

PUR foam

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; CF, carbon fiber; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EP, epicerol; EVA, ethylene-vinyl acetate; EVOH, ethylene vinyl alcohol copolymers; FEP, fluorinated ethylene propylene; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MPR, melt processable rubber; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PE, polyethylene; PES, polyethersulfone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PK, polyketone; PLA, polylactic acid; PMI, polymethacrylimide; PMMA, poly methylmethacrylate; PMP, polymethylpentene; POM, polyacetal; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; PVDC, polyvinylidene chloride; RTV, room-temperature vulcanization; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; SMMA, styrene methyl methacrylate; TP, thermoplastic; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; TS, tensile strength; UD, unidirectional; UHMW, ultrahigh molecular weight; UP, unsaturated polyester; WPC, wood plastic composite.

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

277

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain). Thermoplastics Subfamilies

Strain at Yield, Mean (%)

Neat

9

Special

3.3

CF

1.5

GF

2.6

Mineral, GB

4.6

Conductive

4.4

Friction

6.8

WPC

4

Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

Maximum

TPO shore D

20

PA 11 or 12 plasticized

Special Grades

Minimum

Maximum

35

150

750

20

30

40

300

PEBA 25
45 shore D

20

25

50

700

PEBA 50
72 shore D

15

31

200

550

PEBA Bio

15

31

50

550

PE-UHMW

13

20

50

500

40

60

PA 12 friction

Minimum

12

Maximum

All Grades

20

PVF

10

30

90

110

PK

10

25

230

350

COPE high shore D

10

19

200

700

PA 6 recycled

10

15

50

150

PE-HD antistatic, black

10

10

11

100

PVC plasticized

8

10

30

500

PE-X crosslinked

8

10

10

440

PE-HD

7

100

50

700

PVDF

7

16

12

450

PP recycled

7

9

10

100

PTFE

7

8

200

400

PPSU

7

8

15

120

PEI

7

7

60

60

PI TP

7

7

8

110

PA 66

6

30

16

300

PP impact

6

13

200

700

PP Co

6

13

50

500

PA transparent

6

10

50

300

Polyarylate

6

9

20

100

PC

6

7

50

150

(Continued )

278

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

Maximum

PMMA antistatic

Special Grades

All Grades

Minimum

Maximum

Minimum

Maximum

6

7

10

18

POM homo- or copolymer

5

30

10

75

EVA

5

25

50

2000

PA 12

5

20

60

400

PA 11

5

20

50

400

PA 10
10 Bio

5

20

50

100

PA 4
10 Bio

5

16

16

100

10

70

11

600

20

71

POM friction PP Ho

5 5

14

8

PVDF friction

5

7

PPE/PA

5

7

12

100

FEP

5

6

250

340

PSU modified

5

6

90

100

PSU/PC

5

6

90

100

PSU

5

6

40

100

PTT Bio

5

6

15

20

EVOH

5

6

14

350

6

6

PVDF mica

5

5

PVCC

5

5

4

32

ETFE

4

23

100

460

PA 6

4

18

60

300

4

12

50

200

18

32

PA 6 GB PET/PC

4 4

10

7

PA 12 GB

4

7

PP/PA

4

6

95

400

PVC unplasticized

4

6

2

120

8

50

PP GB

4

5

PSU/ABS

4

4

4

25

Acrylique IMIDE

4

4

4

4

1

10

PP wood WPC

1

4

CAB

3.6

40

23

90

PA 6
12

3

20

100

340

PA 6 FR

3

20

20

100

PA 12 conductive

3

20

4

60

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

279

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics PE-LD

Neat Grades Minimum

Maximum

3

16

Special Grades Minimum

Maximum

All Grades Minimum

Maximum

200

900

PLA wood WPC

3

13

5

14

PP talc

3

10

8

60

PA 66 GB

3

9

5

12

PA 66 mineral

3

9

3

70

ABS/PVC

3

8

18

20

ABS/PC

3

8

3

125

PC/PBT

3

7

50

150

PPA

3

7

3

30

1

10

ETFE GF

3

7

ABS/PA

3

6

55

290

ASA/PVC

3

6

40

70

3

9

PAI friction

3

6

ASA/PC

3

5

60

100

PLA/Copolyester

3

5

12

300

ASA/PMMA

3

5

10

30

PA 4
6 mineral

3

5

4

20

PA 4
10 GF Bio

3

5

4

10

PBT

3

5

3

200

PEEK

3

5

3

150

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

3

5

3

150

PA 4
6 GF

3

5

3

10

PA 12 GF

3

5

3

8

MABS

3

4

12

20

ASA

3

4

8

40

CA

3

4

6

72

PEI mineral

3

4

6

6

ABS/PA 20 GF

3

4

3

7

3

6

PMI or PMMI

3

4

PP CaCO3

3

3.5

12

165

PPE/PA GF

3

3

3

8

PA 6 GF recycled

3

3

3

3

PPE GF

3

3

2

7

(Continued )

280

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

Maximum

Special Grades

All Grades

Minimum

Maximum

Minimum

Maximum

PP mineral

2

50

3

150

TPU GF

2

25

4

65

COPE Bio

2

19

200

310

COPE low shore D

2

10

300

900

2

400

PP antistatic

2

10

PMMA

2

10

2

10

PPE

2

9

9

60

PES

2

8

6

80

PPSU GF

2

8

2.5

6

ASA/PBT GF

2

8

2

9

PP conductive

2

7

1

9

PC conductive

2

6

4

20

PET/PC GF

2

6

3

6

PA 11 GF

2

6

2.5

8

PET GF

2

6

2

6

PAI GF

2

5

2

7

2

7

SAN

2

5

PI TP friction

2

5

2

6

PSU mineral

2

5

2

6

PVC GF

2

5

2

6

3

140

COC

2

4.5

PP/PA GF

2

4

3

5

PP low level GF

2

4

3

4

ABS FR

2

4

2

80

PA 6 medium level GF

2

4

2

5

PAEK 30% GF

2

4

2

4

PC GF

2

4

2

4

TPU conductive

2

3

4

5

ABS/PC conductive

2

3

3.4

11

3

300

PA 4
6

2

3

PLA natural reinforcement

2

3

3

10

PA 6
12 GF

2

3

3

5

ABS GF

2

3

3

3.5

PC/SAN GF

2

3

3

3

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

281

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

Maximum

PK GF ABS

2

Special Grades

All Grades

Minimum

Maximum

Minimum

Maximum

2

3

2.5

3

2

100

3

PBT medium level GB

2

3

2

4

PC/PBT GF

2

3

2

4

PP medium level GF

2

3

2

4

PA 10
10 high level GF Bio

2

3

2

3

PEEK GF

2

3

2

3

2

3

PBI

2

3

PBT medium level GF

2

3

2

3

PBT GF and mineral

2

3

2

3

PEI GF milled

2

3

2

3

PEI GF

2

3

2

3

PSU/PBT GF

2

3

2

3

SMA GF

2

3

2

3

PI TP GF

2

3

1.5

3

PP CF

2

3

1

400

POM conductive

2

3

1

5

PA 6 medium-level long GF

2

2.6

2

4

ABS conductive

2

2.5

2.4

4

PA 66 conductive

2

2.5

2

3.5

PA 66 medium-level long GF

2

2.4

1.9

2.4

PA 6 mineral FR

2

2

2

70

PAA medium level GF

2

2

2

5

ABS/PC GF

2

2

2

3

PAA mineral

2

2

2

3

PPA GF

2

2

1.8

2.5

PI TP CF

2

2

1.5

2

PPA long GF

2

2

1

3

ABS GB

1.8

1.9

3

11

ABS/PC_ low-level long GF

1.8

1.8

1.8

1.8

PSU GF

1.7

3

1.7

3

PA 66 high-level long GF

1.7

2

1.7

3

PET

1.5

30

2

600

PAI mineral

1.5

4

1.6

5

(Continued )

282

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

All Grades

Minimum

Maximum

Minimum

Maximum

PAI CF

1.5

4

1.5

6

PA 66 high level GF

1.5

3

2

3

PE GF

1.5

2.5

1.5

2.5

Polyarylate GF

1.5

2

2

2

PE 60% long GF

1.5

1.5

1.4

1.5

PA 6 high level GF

1.4

3.2

1.4

3.2

PA 6 high-level long GF

1.4

2

1.4

2

ABS/PC medium-level long GF

1.4

1.4

1.4

1.4

PE wood WPC

1.3

5

0.8

15

LCP mineral

1.2

4

1.2

5.5

POM long GF

1.2

1.2

1.2

1.2

10

300

ECTFE

1

Maximum

Special Grades

10

POM GF

1

7

1

12

POM GB

1

6

10

10

POM mineral

1

6

2

55

PA 66 impact medium level GF

1

6

2

10

PES GF

1

6

1.4

7

PA 66 medium level GF

1

6

1

8

1

40

PS

1

4

PC CF

1

3

2

3

PCT GF

1

3

2

3

PP long GF medium level

1

3

2

3

TPU long GF

1

3

2

3

PA far

1

3

1.6

8

LCP GF

1

3

1

6

PBT CF

1

3

1

4

PEEK CF

1

3

1

3

PPS GF and mineral

1

3

1

3

PEEK/PBI GF

1

2.7

1

2.7

POM far

1

2

2.4

10

PLA/PBT GF

1

2

2

5

PES CF

1

2

2

3

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

283

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

All Grades

Minimum

Maximum

Minimum

Maximum

PBT long GF

1

2

1.8

2

PES friction

1

2

1.6

2.3

PA 6
10 CF

1

2

1.5

2.5

PAA medium level CF

1

2

1.3

2

PEI CF

1

2

1.2

4

PLA GF

1

2

1

10

POM CF

1

2

1

4

PPS GF

1

2

1

4

PEEK/PBI CF

1

2

1

3.7

1

3

LCP

1

Maximum

Special Grades

2

PA 12 CF

1

2

1

3

PA 66 CF

1

2

1

3

PMP GF

1

2

1

3

PPA CF

1

2

1

3

PTT Bio GF

1

2

1

3

SAN GF

1

2

1

3

PPE CF

1

2

1

2.7

PP long GF high level

1

2

1

2.5

PA 66 long CF

1

2

1

2

1

2

PEEK/PBI

1

2

PEI conductive

1

2

1

2

PET/PBT high level GF

1

2

1

2

PAA high level GF

1

1.5

1.8

2

ABS CF

1

1.5

1.3

1.5

PPS Far

1

1.4

1.3

3

PPS long GF medium level

1

1.3

1

1.3

PPA Mineral

1

1

1

2

PPS long GF high level

1

1

1

2

PS GF

1

1

1

1.5

PMMA GF

1

1

1

1

2

65

PS impact

0.9

2

PBT long CF

0.8

1.8

0.8

2

PVDF CF

0.8

1

0.8

4

0.7

15

PPS

0.7

4

(Continued )

284

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

Maximum

Special Grades

All Grades

Minimum

Maximum

Minimum

Maximum

FEP GF

0.5

3

0.5

3

PPS conductive

0.5

3

0.5

3

PPS CF

0.5

2

0.5

3

PPS CF and GF

0.3

0.8

0.3

2

LCP CF

0.25

1

0.25

4

Starch/PE

480

680

CPE

400

800

TPV shore D

400

600

PP/EPDM-V

300

700

TPS shore D

300

650

PB

300

550

PFA

280

300

TPU shore D

250

550

PET amorphous

250

300

MPR

210

400

EMA

200

850

PVDC

160

250

TPU Bio

100

450

PA 6
10

100

300

PTFE friction

100

180

PCTFE

80

250

PTFE CF

70

350

PTFE GF

70

270

PP low level CNT

50

150

CP

30

100

TPE based on PVC

20

500

PA castable

20

50

PA castable friction

20

50

PMP

15

120

PP medium CNT

15

17

PPE mineral

10

40

PLA/PC

10

20

PLA/PE

10

20

PC friction

8

70

PAI

8

15

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

285

Table 6.21 Examples of Strain at Yield and Elongation at Break (Ultimate Strain).—Cont’d Range Examples of Strain at Yield and Elongation at Break of Thermoplastics Elongation at Break or Ultimate Strain (%)

Strain at Yield (%) Thermoplastics

Neat Grades Minimum

Maximum

Special Grades Minimum

All Grades

Maximum

Minimum

Maximum

PMP mineral

6

30

PLA/PMMA

6

15

PMMA impact

4

80

PP cellulose fibers

3

7

PP natural fibers

3

6

PLA

2.5

160

SMMA

2

54

SMA

2

30

PA CNT

2

4

Yield Strain Thermosetting Compounds

Neat Grades

Elongation at Break

Special Grades

All Grades Minimum

Maximum

Thermoset polyester GF BMC

B0

0.16

0.3

0.7

Thermoset polyester glass SMC

B0

1.6

0.4

1.8

0.7

140

Epoxy, cast, unreinforced Rigid PUR

5

7

110

140

Epoxy encapsulant, unreinforced

1

140

1

200

Epoxy cure resin

1

13

1

50

Epoxy adhesive

B0

10

B0

250

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EVA, ethylene-vinyl acetate; EVOH, ethylene vinyl alcohol copolymers; FEP, fluorinated ethylene propylene; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MPR, melt processable rubber; PA, polyamide; PBT, polybutylene terephthalate; PC, polycarbonate; PES, polyethersulfone; PET, polyethylene terephthalate; PFA, perfluoroalkoxy; PK, polyketone; PLA, polylactic acid; PMI, polymethacrylimide; PMMA, poly methylmethacrylate; PMP, polymethylpentene; POM, polyacetal; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; PVDC, polyvinylidene chloride; PVDF, polyvinylidene fluoride; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; SMMA, styrene methyl methacrylate; TP, thermoplastic; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; UHMW, ultrahigh molecular weight; WPC, wood plastic composite.

• The broad range of data for many families coming from formulation versatility, succinct trade appellations, test method versatility, errors, and mix-up.

• High values for fiber reinforced grades, in the decreasing order of carbon, glass, aramid, natural fiber

• Very low values for foams. These data are only examples providing a rough idea of the significant differences between

subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered. Table 6.23 displays examples of notched impact strength of thermoplastics, thermosets and compounds. Testing procedures should be more or less similar and units would be theoretically the same. However, it is risky to compare the different parts of the table.

286

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.22 Examples of Tensile Modulus. Statistical Analysis of Runs for the Measure of Tensile Modulus for 4 Thermoplastic Compounds Mean of a Run (GPa)

Standard Deviation of a Run

Coefficient of Variation for a Run (%)

0.274

0.017

6.2

0.295

0.021

7.1

14

0.1

0.7

13

0.7

5.4

Average Modulus for 8 Thermoplastic Subfamilies Thermoplastic

Tensile Modulus, Mean (GPa)

Neat

1.9

Special

9.1

CF

17.5

GF

9.8

Mineral, GB

6.1

Conductive

6.1

Friction

4.3

WPC

4.4

Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Maximum (GPa)

Special Grades Minimum (GPa)

Maximum (GPa)

PBT long CF

28

32

PAA medium level CF

22

25

PEEK/PBI CF

21

28

PI TP CF

20

29

PA 66 long CF

19

25

PA 66 high-level long GF

19

24

PA 6 high-level long GF

19

22

PAA high level GF

18

24

PAI CF

18

23

PPS long GF high level

18

21

PET/PBT high level GF

18

19

PPA long GF

17

19

PPS CF

16

36

PPS CF and GF

16

30

LCP CF

14

37

PPS conductive

14

24

PPS long GF medium level

13

17

PA 12 CF

12

19

POM long GF

12

14

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

287

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Minimum (GPa)

Maximum (GPa)

PBT long GF

12

13.6

ABS/PC medium-level long GF

12

13

PEI conductive

12

13

PA 66 CF

11

35

PEEK CF

11

26

PAI GF

11

15

PPA GF

11

14

PEI CF

10

26

PPS GF and mineral

10

22.6

PBT CF

10

21

PI TP GF

10

20

PA 6 high level GF

10

18

PE 60% long GF

10

14

PEEK/PBI GF

10

14

PLA GF

10

14

PA 10
10 high level GF Bio

9

16

PA 66 high level GF

9

16

PA 6 medium level long GF

9

12

PAA medium level GF

9

12

PEEK GF

9

12

PAEK 30% GF

9

12

PBT medium level GF

9

11.5

PA 66 medium level long GF

9

11

PES friction

9

11

LCP GF

8

32

PPA CF

8

25

POM CF

8

17

PBT GF and mineral

8

14

PP long GF high level

8

13.8

ABS/PC_ low-level long GF

8

9

PEI GF

8

9

PA 6
12 GF

7.9

9.5

LCP mineral

7.5

22

PK GF

7.3

10.3

LCP

9

Maximum (GPa)

Special Grades

21

(Continued )

288

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Minimum (GPa)

Maximum (GPa)

PES CF

7

22

TPU long GF

7

15

PAA mineral

7

13

PET GF

7

12

POM GF

7

11.3

PCT GF

7

11

PLA/PBT GF

7

11

PPE CF

7

10.6

PMMA GF

7

10.4

PPA mineral

7

9

PTT Bio GF

6.5

11

PA 6
10 CF

6

27

PPS GF

6

16

PC CF

6

14

PVDF CF

6

14

ABS CF

6

13

PAI mineral

6

12

PPE/PA GF

6

12

PSU GF

6

12

PA 4
10 GF Bio

6

10

PPS far

6

10

PPE GF

6

9

PS GF

6

9

PSU/PBT GF

6

9

Polyarylate GF

6

8

PEI GF milled

6

7

ETFE GF

5

18

PC GF

5

12

PA 6 medium level GF

5

11

SMA GF

5

10.6

PA 66 medium level GF

5

10

SAN GF

5

10

PA 6 GF recycled

5

9

PC/PBT GF

5

9

PEEK/PBI

5.1

Maximum (GPa)

Special Grades

5.6

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

289

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Minimum (GPa)

Maximum (GPa)

PC/SAN GF

5

9

PA 11 GF

5

8

ABS/PC GF

5

7

PAI friction

5

7

PEI mineral

5

7

PLA/PP 30% GF

5

7

PA 12 GF

4.6

6

PA 4
6 GF

4.5

10

ABS GF

4.5

6.1

ABS/PA 20 GF

4.5

5.5

ASA/PBT GF

4

10

PA 6 mineral FR

4

10

PA 66 mineral

4

10

PP medium level GF

4

9

PP long GF medium level

4

9

PPSU GF

4

9

PVC GF

4

9

PS 40% wood WPC

4

5.8

FEP GF

4

5

PLA wood WPC

4

5

PVDF mica

4

4.2

PSU mineral

3.8

7.7

POM mineral

3.7

8.5

PA far

3.6

9

PA 66 conductive

3.5

23

PES GF

3.5

11

PMP GF

3.5

6

3.3

10

PBI

PAI

5

4

Maximum (GPa)

Special Grades

6

5

PMI or PMMI

3.6

4.5

Acrylique IMIDE

3.6

4.3

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

3.5

4.2

PEEK

3.5

4

PP/PA GF

(Continued )

290

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Minimum (GPa)

Maximum (GPa)

PE GF

3.2

6.3

POM GB

3.2

4

PA CNT

3.2

3.5

PP CF

3

19

PI TP friction

3

12

PET/PC GF

3

8

PA 66 impact medium level GF

3

7

PBT medium level GB

3

4.1

PLA natural reinforcement

2.8

13.2

POM far

2.8

7

PP low level GF

2.8

5

PA castable friction

2.8

3.6

ABS GB

2.8

3.5

2.5

6

2.5

2.8

2.3

3.5

2.2

2.6

PP natural fibers

2.1

8

PP cellulose fibers

2.1

5.6

ABS conductive

2.1

3.5

PEI

3

Maximum (GPa)

Special Grades

4

PPS

2.8

4.2

SAN

2.8

4

PLA

2.6

3.8

PP wood WPC PMMA

2.5

5

PC conductive PSU/PC

2.4

2.5

EVOH

2.3

5.8

PPE mineral PVCC

2.3

3.2

PVC unplasticized

2.2

4

SMMA

2.2

3.6

PES

2.2

2.8

ABS/PVC

2.2

2.6

PVDF friction PPSU

2.2

2.5

PLA/PC

2.1

3.1

PPE/PA

2.1

2.9

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

291

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Maximum (GPa)

Special Grades Minimum (GPa)

Maximum (GPa)

2.1

2.7

TPU conductive

2.1

2.1

POM conductive

2

12

PVC wood WPC

2

8

PA 4
6 mineral

2

6

PA 66 GB

2

5

2

3

PP medium CNT

1.95

2.2

PP GB

1.9

3.3

1.8

4.5

1.8

3.1

PP low level CNT

1.73

2.1

PE wood WPC

1.7

5

PA 12 GB

1.7

3.6

PMP mineral

1.7

3.5

1.7

2.8

PC CNT PSU

2.1

2.7

PC

2.1

2.5

PSU modified

2.1

2.5

PSU/ABS

2.1

2.2

PI TP

2

3.6

PLA/PMMA

2

3.5

PS

2

3.5

PBT

2

3.2

ABS FR COC

2

3

PPE

2

2.8

PVF

2

2.7

ASA

2

2.6

Polyarylate

2

2.3

ASA/PMMA

2

2.2

ASA/PVC

2

2.2

PPA

1.9

2.7

PA 6 GB PET

1.8

3.5

SMA

1.8

3.5

POM friction ASA/PC

1.8

2.6

PET amorphous

1.8

2.2

ABS/PC ABS/PC conductive

1.7

3

(Continued )

292

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Maximum (GPa)

MABS

1.7

2.2

starch/PS

1.7

1.8

PTT Bio

1.6

2.5

PC/PBT

1.6

2.3

PET/PC

1.6

2.2

Special Grades Minimum (GPa)

Maximum (GPa)

1.5

4

1.5

2.3

1.4

19

PC friction

1.4

2

PMMA antistatic

1.4

1.7

1.1

3.7

1

4.2

1

3

1

1.7

PP Talc PMMA impact

1.5

3.5

PP CaCO3 PLA/PE

1.5

1.7

PP conductive PS impact

1.4

3

PA transparent

1.4

2.7

ECTFE

1.4

2

PK

1.4

1.6

PA castable

1.3

3

PA 10
10 Bio

1.3

2

ABS/PA

1.2

1.8

PA 6 FR PP Ho

1.1

1.8

Starch/PP

1.1

1.1

PP mineral POM homo- or copolymer

1

3.7

PA 4
6

1

3.3

ABS

1

3

PP antistatic PA 6
10

1

2.4

PCTFE

1

2.1

PTFE GF PA 6 recycled

1

1.5

PA 4
10 Bio

0.9

3.1

PP Co

0.9

1.8

PP recycled

0.9

1.5

PA 66

0.8

3.7

PA 6

0.8

3

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

293

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades

PA 6
12

Minimum (GPa)

Maximum (GPa)

0.7

2.6

PE-HD antistatic black CA

0.6

2.8

PLA/Copolyester

0.6

1.8

PVDF

0.5

2.6

PA 12 friction PA 11

0.5

1.9

PA 12

0.5

1.9

PMP

0.5

1.6

ETFE

0.5

1.4

PE-HD

0.5

1.4

PFA

0.5

0.8

CP

0.45

1.9

CAB

0.4

2

PTFE

0.4

1.4

PTFE CF PP impact

0.4

Special Grades Minimum (GPa)

Maximum (GPa)

0.7

0.8

0.5

2

0.4

1.4

0.35

6

0.3

13

1.3

PA 12 conductive PE-X crosslinked

0.35

3.5

PVDC

0.35

0.5

TPU GF PP/PA

0.3

2.3

PE-UHMW

0.3

1.3

FEP

0.3

0.7

PA 11 or 12 plasticized

0.3

0.6

COPE high shore D

0.2

1.2

Starch/PE

0.2

0.3

PEBA 50
72 shore D

0.16

0.8

PE-LD

0.13

0.5

TPO shore D

0.1

2.3

TPU Bio

0.1

0.7

TPU shore D

0.1

0.7

TPS shore D

0.1

0.3

TPV shore D

0.1

0.3

Starch/copolyester

0.08

0.1

COPE Bio

0.05

0.32

(Continued )

294

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.22 Examples of Tensile Modulus.—Cont’d Plastic

Tensile Modulus, Range Examples (GPa) Neat Grades Minimum (GPa)

Maximum (GPa)

PB

0.05

0.3

EMA

0.02

0.5

PEBA Bio

0.01

0.56

PP/EPDM-V

0.01

0.35

EVA

0.01

0.3

PEBA 25
45 shore D

0.01

0.15

COPE low shore D

0.006

0.17

MPR

0.003

0.005

CPE

0.002

0.007

Special Grades

PVC plasticized TPE based on PVC

0.001

Minimum (GPa)

Maximum (GPa)

0.001

2.2

1

Flexural Modulus Examples for Thermosetting Compounds and Composites (GPa) Thermosets

Neat Minimum (GPa)

Modified Maximum (GPa)

Minimum (GPa)

Maximum (GPa)

EP/CF UD

120

320

EP/aramid fiber UD

80

120

EP glass fabric

20

28

UP/CF fabric

20

25

EP/GF SMC

14

25

PI/CF

19

20

UP/GF roving or fabric

10

26

UP/GF SMC UD

14

22

MF filled

8

20

UP SMC 35/50 GF

10

16

PF/GF molding

9

13

UP SMC 10/30 GF

6

14

PI/GF molding

9

10

EP filled, molding

2

16

MF modified

6

11

PUR SRRIM

1.2

15

PF/GF SMC

6

10

UF cellulose

6

10

UP/GF BMC

5

11

UP/GF mat

5

11

UP/GF SMC foamed

4

12

PF organic filled

6

9

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

295

Table 6.22 Examples of Tensile Modulus.—Cont’d Flexural Modulus Examples for Thermosetting Compounds and Composites (GPa) Thermosets

Neat Minimum (GPa)

Modified Maximum (GPa)

Minimum (GPa)

Maximum (GPa)

3

11

EP foamed

0.4

9.5

PI glass fabric

3

5

PUR RIM

0.03

2

PUR structural foam

0.2

1.6

0.001

0.01

0.001

0.002

UP filled, molding PI neat

2

10

Cy neat

3

4

UP cast

2

4.5

EP neat

0.01

4

PUR Sh D

0.1

2.6

PUR Sh A

0.01

1.05

Silicone HVR

0.01

0.05

Silicone RTV

0.01

0.03

PUR foam Fluorosilicone

0.001

0.004

Silicone foam

ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, Cellulose esters; CF, carbon fiber; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EP, epicerol; EVA, ethylene-vinyl acetate; FR, fire retardant; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MPR, melt processable rubber; PA, polyamide; PC, polycarbonate; PE, polyethylene; PES, polyethersulfone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PK, polyketone; PLA, polylactic acid; PLA, polylactic acid; PMMA, poly methylmethacrylate; PMP, polymethylpentene; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; PVDC, polyvinylidene chloride; PVDF, polyvinylidene fluoride PMI, polymethacrylimide; RTV, roomtemperature vulcanization; SAN, styrene acrylonitrile; SMA, styrene maleic anhydride; SMMA, styrene methyl methacrylate EVOH, ethylene vinyl alcohol copolymers; TP, thermoplastic; TPS, thermoplastic starch; TPU, thermoplastic polyurethane; UD, unidirectional; UHMW, ultrahigh molecular weight; FEP, fluorinated ethylene propylene; UP, unsaturated polyester; WPC, wood plastic composite.

Table 6.23 Examples of Notched Izod Impact Strengths (J/m). Statistical Analysis of Runs for the Measure of Impact Strength of 4 Thermoplastic Compounds Mean of a Run (J/m)

Standard Deviation of the Mean Within a Lab

Coefficient of Variation for a Run (%)

24

1.2

5

30

1.3

4

77

4

5

106

4.4

4

142

8.2

6

326

41

13

551

46.9

9

577

7.3

1

(Continued )

296

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Statistical Analysis of Runs for the Measure of Impact Strength of 4 Thermoplastic Compounds Mean of a Run (J/m)

Standard Deviation of the Mean Within a Lab

Coefficient of Variation for a Run (%)

875

15.8

2

1037

51.3

5

Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Maximum

COPE low shore D

NB

NB

CPE

NB

NB

EVA

NB

NB

FEP

NB

NB

PB

NB

NB

PEBA 25
45 shore D

NB

NB

PEBA 50
72 shore D

NB

NB

PE-LD

NB

NB

PE-UHMW

NB

NB

PFA

NB

NB

PPA

950

NB

PEBA Bio

800

NB

ABS/PA

400

950

LCP

400

520

Special Grades Minimum

Maximum

PA 6 high-level long GF

380

530

PA 66 high-level long GF

375

670

PE 60% long GF

370

410

TPU long GF

363

670

POM long GF

335

335

PPS long GF medium level

310

342

PA 66 medium-level long GF

267

270

PA 12 GF

250

300

PA 6 medium-level long GF

240

270

ABS/PC_ low-level long GF

220

220

PPA long GF

214

347

EMA

365

NB

ASA/PVC

300

600

ETFE

270

NB

PA 11 or 12 plasticized

200

NB

TPU shore D

200

NB

COPE Bio

200

900

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

297

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Maximum

ASA/PC

200

700

PSU/ABS

200

374

Special Grades Minimum

Maximum

PA 66 long CF

200

240

PP 40% kenaf fiber

185

185

ABS/PC medium-level long GF

180

190

PPS long GF high level

160

370

FEP GF

160

200

PA 66 impact medium level GF

150

270

PPE mineral

150

210

PA 66 medium level GF

130

160

PTFE GF

120

150

PA 6 medium level GF

112

270

PA 6 high level GF

112

144

110

750

PA 4
6 GF

110

190

PAA high level GF

110

115

PET/PC GF

107

600

PA 11 GF

107

200

PA 6
12 GF

106

130

100

999

TPU GF

100

999

PI TP CF

100

850

PVF

PTFE

PVDF

PLA/PC

PC/PBT

180

160

130

117

110

181

200

400

854

850

PI TP GF PPE

110

400

COPE high shore D

100

999

ECTFE

100

999

PE-HD antistatic, black PP impact

100

999

ABS/PC

100

650

ASA

100

600

TPU Bio

100

600

PA 4
6

100

500

ASA/PMMA

100

400

(Continued )

298

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Maximum

ABS

100

350

PK

100

270

PPE/PA

100

250

Special Grades Minimum

Maximum

ABS/PA 20 GF

100

200

PA 6 mineral FR

100

200

PA 66 high level GF

100

150

PC friction

100

130

PTFE friction

100

108

95

130

PC GF

90

200

Polyarylate GF

90

200

PBT long GF

90

180

SMA GF

90

140

PC/SAN GF

90

100

PP 40% flax fibers

89

91

PA 6 GF recycled

85

100

PEI GF

85

100

PET GF

80

230

PP/PA GF

80

150

PK GF

80

140

PPE/PA GF

78

91

ETFE GF

75

485

ABS/PC GF

75

105

70

350

70

150

PAI

Starch/PS

100

100

150

100

PEEK GF PPSU

91

700

PC

80

950

PCTFE

80

250

PSU/PC

80

91

PI TP

80

90

PSU modified

80

90

PA 12

70

999

ABS/PVC

70

400

ABS FR Polyarylate PCT GF

70

290

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

299

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Minimum

Maximum

TPU conductive

70

124

PAA mineral

70

100

ASA/PBT GF

70

85

PEI conductive

70

75

PA 66 mineral

69

200

PPA GF

65

530

PA 66 CF

64

265

63

130

60

430

PLA/PP 30% GF

60

107

PE GF

60

85

ABS GF

60

70

PAA medium level CF

60

70

PMP GF

58

64

PVDF CF

58

59

PES GF

55

107

PPSU GF

55

100

PSU GF

55

96

PAA medium level GF

55

75

PVDF friction

55

60

ABS/PC conductive

54

961

53

85

53

60

Starch/PP

PLA/PE

66

64

Maximum

Special Grades

66

65

PAEK 30% GF PEEK

63

85

ABS conductive PS impact

60

350

PA transparent

60

150

PP Co

56

500

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

55

140

PES

53

999

TPO shore D

53

999

ABS CF PSU

53

70

ABS GB PA 66

50

999

POM homo- or copolymer

50

900

PET/PC

50

850

(Continued )

300

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Maximum

CAB

50

530

CA

50

400

Special Grades Minimum

Maximum

PP long GF high level

50

350

PS GF

50

350

LCP mineral

50

290

50

185

PC/PBT GF

50

150

PP low level GF

50

145

PPE GF

50

130

POM GF

50

110

50

100

PBT medium level GF

50

90

PAI friction

50

80

50

53

PA 6 FR

48

200

PC CF

48

100

PLA GF

48

59

PMMA GF

48

53

PPA mineral

48

53

PC CNT

48

50

PP long GF medium level

45

216

PP medium level GF

45

160

PBT GF and mineral

45

75

PP CF

43

320

42

53

PPS GF and mineral

40

140

PA 12 conductive

40

110

PVC GF

40

107

PVCC

50

290

PP natural fibers PA 6 recycled

MABS

50

50

160

100

PLA/PBT GF EVOH

PEI

50

50

90

60

PP cellulose fibers PA 6

PA 6
12

48

43

999

200

PES CF PA 11

40

999

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

301

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Minimum

Maximum

PA 12 GB

40

100

PAI GF

40

80

PPS conductive

40

80

PA 4
6 mineral

40

70

PEI GF milled

40

70

POM GB

40

70

PEI mineral

40

60

PEEK/PBI GF

40

50

PEEK/PBI CF

40

50

PAI CF

40

48

POM Far

39

302

POM CF

38

64

PA 6
10 CF

37

160

PA Far

37

146

PEEK CF

37

110

PA 66 conductive

37

100

PPA CF

37

70

PEI CF

37

69

LCP CF

35

320

PPS GF

35

100

PAI mineral

35

80

PBT medium level GB

35

51

PI TP friction

35

43

35

38

POM mineral

34

65

PPS CF 1 GF

32

101

PBT CF

32

69

PMMA antistatic

32

55

PP antistatic

30

290

PP talc

30

200

PPS CF

30

168

PP CaCO3

30

150

PLA/PMMA

PBT

PEEK/PBI

PA 6
10

PMMA impact

37

35

35

30

30

Maximum

Special Grades

117

55

38

999

130

(Continued )

302

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Minimum

Maximum

PVC wood WPC

30

107

PA castable friction

30

85

POM conductive

30

70

PP low level CNT

30

70

SAN GF

30

65

PSU mineral

30

55

PPS far

27

130

PA CNT

27

70

PPE CF

26

80

PMP mineral

26

43

25

78

20

100

20

90

PS 40% wood WPC

20

41

PP wood WPC

18

45

LCP GF

17

430

16

43

14

240

10

320

PMP

PBI

CP

27

27

25

Maximum

Special Grades

150

30

999

POM friction PE-HD

20

220

PP recycled

20

200

PVC unplasticized

20

110

PP Ho

20

107

PSU/PBT GF SMA

20

100

PC conductive PA castable

20

85

PP/PA

16

999

PVDC

16

66

SMMA

16

50

PE wood WPC PET

15

100

PTT Bio

15

40

PP mineral COC

13

350

PLA

13

267

PP conductive PE-X crosslinked

10

220

PET amorphous

10

100

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

303

Table 6.23 Examples of Notched Izod Impact Strengths (J/m).—Cont’d Thermoplastics: Examples of Impact Strength Expected Neat Grades Minimum

Maximum

PS

10

60

SAN

10

30

Acrylique IMIDE

10

25

PMI or PMMI

10

25

PMMA

10

25

PPS

5

80

Special Grades Minimum

Maximum

Thermosetting Resins and Composites: Examples of Impact Strength Thermosets

Neat Minimum

Modified Maximum

Minimum

Maximum

EP/GF SMC

1600

2160

UP/GF mat

1350

1450

PUR SRRIM

350

1600

EP/CF SMC

800

1080

UP/CF fabric

710

780

PI/GF fabric

650

700

UP/GF SMC

130

1190

UP/aramid fiber

470

500

PF/GF molding

14

900

MF filled

11

900

PI/GF molding

14

800

UP/GF BMC

100

700

EP/GF molding

20

300

PI/CF

100

110

PF organic filled

11

190

MF modified

11

25

UP filled, molding

11

16

EP syntactic foam

8

13

PUR RIM

49

648

UP cast

10

400

EP toughened

124

270

PI neat

80

90

NB non break ABS, Acrylonitrile
butadiene
styrene; ASA, acrylonitrile styrene acrylate; CAB, cellulose esters; CF, carbon fiber; CNT, carbon nanotubes; COC, cyclic olefin copolymers; COPE, copolyester; EP, epicerol; EVA, ethylene-vinyl acetate; EVOH, ethylene vinyl alcohol copolymers; GB, glass bead; GF, glass fiber; LCP, liquid crystal polymers; MABS, methylmethacrylate
acrylonitrile
butadiene
styrene; PA, polyamide; PC, polycarbonate; PE, polyethylene; PEEK, polyether ether ketone; PES, polyethersulfone SMA, styrene maleic anhydride; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PLA, polylactic acid, TP, thermoplastic; PMI, polymethacrylimide; PMMA, poly methylmethacrylate; PMP, polymethylpentene; PPA, polyphthalamide; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PTT, polytrimethylene terephthalate; PUR, polyurethane; PVC, polyvinyl chloride; PVDC, polyvinylidene chloride; SAN, styrene acrylonitrile; SMMA, styrene methyl methacrylate; TPU, thermoplastic polyurethane PVDF, polyvinylidene fluoride; UHMW, ultrahigh molecular weight; FEP, fluorinated ethylene propylene PK, polyketone; UP, unsaturated polyester; WPC, wood plastic composite.

304

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

6.4.3.3 Pay Attention to “Compression Modulus” That Can Hide “Bulk Modulus” Very often the compression modulus of polymers deals with the modulus of compression according to one direction of loading, the other directions being more or less free. More rarely, the bulk modulus in compression (in short, bulk modulus) describes the modulus of a sample subjected to an isostatic compression according to the three directions. Of course its value is significantly different. The bulk modulus (B) is defined as the ratio of an infinitesimal pressure increase to the resulting relative infinitesimal decrease of the volume at constant temperature. 

@P B52V 3 @V



where B is the bulk modulus, V is the volume, @P is the pressure variation, @V is the volume variation at constant temperature. Bulk and Young modulus are linked by the equation: B 5 E=3ð1 2 2vÞ where E is the Young’s modulus and ν is the Poisson’s ratio.

10

GPa

The first part of Table 6.23 displays standard deviations and coefficients of variation for impact strength averages of 10 runs within a laboratory. The second part of Table 6.23 displays impact strength examples for thermoplastics compounds and composites. Units are not reported, but are expected to be identical. The third part of Table 6.23 displays impact strength examples for thermoset compounds and composites. Units are not reported and are expected to be identical, but may be different from that used for thermoplastics. These data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered.

5

0 0

2

4

6

GPa

Figure 6.5 Example of range of bulk modulus versus Young’s modulus.

Fig. 6.5 displays the range of bulk modulus versus Young’s modulus for 31 thermoplastics and thermosets. These heterogeneous data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered.

6.4.4 Examples of Water Uptake Statistical analysis of water uptake after 24 h at room temperature for 65 compounds leads to: Mean

0.8%

Median

0.15%

SD

2.6

Min

0.005%

Max

10% and even 25%

Absorbed water may favor hydrolysis as far as temperature is higher and generally acts as a plasticizer of end products. The water absorption may be as high as 10% and even 25% for hydro-swelling grades. Open cell foams absorb very high levels of water. Table 6.24 displays examples of water absorption at room temperature for thermoplastic and thermoset compounds. These data are only examples providing a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered.

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

Table 6.24 Examples of Water Absorption, Room Temperature, 24 h (%). Minimum (%)

Table 6.24 Examples of Water Absorption, Room Temperature, 24 h (%).—Cont’d

Maximum (%)

Thermoplastics

305

Minimum (%)

Maximum (%)

PA 66, 6

1

3

PE, PMP

0.005

0.015

CA

1.9

7

ETFE

0.03

0.03

EVOH

6

10

FEP, PFA, PTFE

0.005

0.03

Thermosets

LCP

0.03

0.03

3

3.5

PP GF, mineral

0.01

0.03

RIM elastomer polyurethanes

LCP GF, CF, mineral

0.02

0.05

RIM structural foam polyurethanes

2

25

PCTFE

0.01

0.05

UP fireproofed

0.01

2.5

PVDF

0.03

0.06

UP

0.1

2.5

PPS

0.01

0.07

UP BMC

0.1

0.2

PPS GF, mineral

0.01

0.08

UP SMC

0.1

0.7

PEEK CF, GF

0.06

0.1

PF GF

0.05

0.2

PP

0.01

0.1

PF mineral

0.1

1

PS

0.01

0.1

PF organic filler

0.1

1.2

PPE

0.06

0.12

PF tribological

0.1

0.15

PPE GF, mineral

0.06

0.12

MF mineral

0.1

0.2

PBT, PET

0.1

0.2

0.8

0.1

0.2

MF cellulose/wood flour

0.1

PC PA 11 or 12

0.25

0.3

UF cellulose V0

0.1

0.8

PAI

0.1

0.3

EP molding

0.1

0.15

PBT 30% GF

0.05

0.3

EP mineral

0.1

0.5

PEI

0.2

0.3

EP silica

0.04

0.1

PEI GF, mineral

0.1

0.3

EP Al powder

0.1

3

PSU

0.3

0.3

EP SMC

1.4

1.6

PBI

0.4

0.4

EP syntactic foam

0.2

1

PC 20%
30% GF FR

0.1

0.4

PI

0.2

1.3

PI GF

0.2

0.9

PSU GF

0.3

0.4

PI graphite

0.1

0.6

PVC-U

0.04

0.4

PI tribological

0.2

1.3

PEEK

0.1

0.5

Silicone resin

0.1

0.15

POM

0.15

0.5

DCPD

0.1

0.2

POM GF, mineral

0.2

0.5

ABS

0.1

0.8

PMMA

0.1

0.8

Soft PVC

0.15

1

PESU

0.1

1.7

(Continued )

ABS, Acrylonitrile
butadiene
styrene; CF, carbon fiber; DCPD, dicyclopentadiene; EP, epicerol; EVOH, ethylene vinyl alcohol copolymers; FEP, fluorinated ethylene propylene; GF, glass fiber; LCP, liquid crystal polymers; PA, polyamide; PC, polycarbonate; PE, polyethylene; PEEK, polyether ether ketone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PMMA, poly methylmethacrylate; PMP, polymethylpentene; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PVC, polyvinyl chloride; PVDF, polyvinylidene fluoride; UP, unsaturated polyester.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

6.4.5 Examples of Mold Shrinkage Statistical analysis of mold shrinkage for 37 compounds shows a broad range of data:

Table 6.25 Thermoplastics: Examples of Mold Shrinkage (%).—Cont’d PEI

0.7

0.8

PEEK CF, GF

0.1

1.4

Minimum (%)

Maximum (%)

PA 66 mineral

0.6

1

Mean

0.6

1.6

PAI

0.6

1

Median

0.4

1

PPE

0.6

1

SD

0.6

1.4

PPS

0.6

1.4

Min

0.1

0.4

PEEK

1.1

1.1

Max

3

6

PA 11 or 12

0.7

1.5

PP TALC

0.9

1.4

POM GF

0.5

1.8

PET, PBT

0.2

3

POM mineral

1.5

2

PA 66

0.7

3

EVA

0.4

3.5

PP

1

3

POM

1.8

2.5

Soft PVC

0.2

5

PE, PMP

1.5

4

ETFE, FEP, PFA, PTFE

3

6

The mold shrinkage may be as high as 6% according to the grade, formulation, and molding process. Please note that the shrinkage can be anisotropic and other contexts can lead to higher or lower data. Table 6.25 displays examples of mold shrinkage for some thermoplastic compounds and thermosetting resins. These data are only examples providing Table 6.25 Thermoplastics: Examples of Mold Shrinkage (%). PPE GF

0.1

0.4

LCP CF, GF, mineral

0.1

0.5

PC GF FR

0.1

0.5

PC GF

0.1

0.5

PESU GF

0.1

0.5

PEI GF

0.2

0.4

LCP

0.1

0.6

PVC-U

0.1

0.6

PS

0.1

PA 66 GF

Thermosetting Resins and Composites: Examples of Mold Shrinkage Thermoset polyester glass SMC

2 0.100

0.5 %

RIM elastomer polyurethanes

0.8

1.4

PUR GF

0.3

0.7

RIM structural foam polyurethanes

0.7

0.9

0.7

0.5

0.5

UP fireproofed

0.05

2

PPS GF and mineral

0.3

0.7

UP antistatic

0.1

0.15

PMMA

0.2

0.8

UP textile fiber

0.01

0.2

PC

0.5

0.7

UP GF

0.01

0.1

PET, PBT GF

0.2

1

UP cellulose

0.01

0.4

PSU, PESU

0.6

0.7

UP BMC

0.01

0.2

ABS

0.4

0.9

UP SMC

2 0.1

0.15

CA

0.3

1

UP UD

2 0.3

2 0.03

PP GF

0.3

1

PF GF

0.1

0.6

(Continued )

(Continued )

6: ENVIRONMENTAL

AND

ENGINEERING DATA

TO

SUPPORT ECO-DESIGN FOR PLASTICS

Table 6.25 Thermoplastics: Examples of Mold Shrinkage (%).—Cont’d

307

Table 6.25 Thermoplastics: Examples of Mold Shrinkage (%).—Cont’d

PF mineral

0.2

1

PI

0.1

1

PF organic filler

0.3

1.2

PI GF

0.1

0.6

PF tribological

0.15

0.4

PI graphite

0.3

0.6

MF mineral

0.3

0.6

PI tribological

0.1

1

MF GF

0.1

0.6

Silicone resin

0.4

0.7

MF cellulose/wood flour

0.5

1.3

Silicone RTV

0.1

1

UF cellulose V0

0.9

1.1

DCPD

0.7

0.9

EP molding

0.1

0.8

PE-X

0.7

5

EP GF

0.1

0.8

EP mineral

0.05

0.8

EP silica

0.05

0.1

EP Al powder

0.1

0.5

EP SMC

0.1

0.1

EP syntactic foam

0.3

1 (Continued )

a rough idea of the significant differences between subfamilies, and other data can be found elsewhere. These theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered.

Further Reading Biron, M., 2014. Thermosets and Composites. Elsevier Ltd.

ABS, Acrylonitrile
butadiene
styrene; CF, carbon fiber; DCPD, dicyclopentadiene; EP, epicerol; EVA, ethylene-vinyl acetate; FEP, fluorinated ethylene propylene; FR, fire retardant; GF, glass fiber; LCP, liquid crystal polymers; PA, polyamide; PC, polycarbonate; PE, polyethylene; PEEK, polyether ether ketone; PET, polyethylene terephthalate; PF, phenolic resin; PFA, perfluoroalkoxy; PMMA, poly methylmethacrylate; PMP, polymethylpentene; POM, polyacetal; PPE, polyphenylene ether; PS, polystyrene; PTFE, polytetrafluoroethylene; PUR, polyurethane; PVC, polyvinyl chloride; RTV, room-temperature vulcanization; UD, unidirectional; UP, unsaturated polyester.

Biron, M., 2015. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2017. Industrial Applications of Renewable Plastics. Elsevier Ltd. Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Plastics Additives & Compounding, Elsevier Ltd. Plastics News.com, Crain Communications. Reinforced Plastics, Elsevier Ltd.

7 Advanced Environmental and Engineering Properties to Support Eco-Design for Plastics 7.1 Advanced Properties That can Help Eco-Design All the information and data provided here are basically unclear because of the use of numerous methods, assumptions, and models. In addition, only examples are quoted that do not make rules. The environmental impact may be significant in relative value, but very low in absolute value. However, keep in mind that the consumption level of plastics is on the order of hundreds of millions of tons per annum, that is to say 1011 kg is the unit often used for environmental indicators. Among the other points of importance are the actual or hypothetical energy sources from coal to solar cells, and the end-of-life assumptions. Once again, the following data, as displayed, are not suitable for computing of final environmental indicators. Each case must be studied by specialists of the environment in the expected actual conditions of fabrication, use, and disposal. As previously said, environment indicators are tools aimed at skilled teams and must be used by skilled people. Use by people technically qualified, but nonqualified from this environmental point of view may lead to misleading conclusions.

reduction of fossil feedstock is low, in relation with this low level of natural raw material. Table 7.1 displays process energy and feedstock energy for some fossil and renewable plastics. These data must be carefully verified because of the broad range of figures for the same polymer family, the continuous evolution of commercialized grades, and the hypotheses and methods used for the calculation. Different data can be found elsewhere. Please note:

• Many “green plastics” have a low naturalsourced content, for example, bio-PET (polyethylene terephthalate), cellulose esters, bio-UP (unsaturated polyester), and polytrimethylene terephthalate (PTT), etc., meaning that the feedstock energy is more or less above 0.

• The differences between production locations inside or outside continents (e.g., European Union and the United States).

• The high standard deviations particularly for the bioplastics.

• The broad range of fossil polymers mean values.

7.1.2 Gas Warming Potential 7.1.1 Fuel Energy and Feedstock Energy Energy requirements have been displayed (see Section 6.3.2) on the whole, which includes fuel energy necessary for all plastics polymerization and processing and the feedstock energy corresponding to the fossil raw materials used to polymerize the plastic under consideration. Feedstock energy tends toward 0 for natural-sourced plastics such as, for example, polylactic acid (PLA). For plastics claimed to be “green” or “natural-sourced,” etc., using a low level of natural raw material, the

As seen in Section 6.3.3, natural-sourced polymers have lower gas warming potential (GWP) impact than fossil ones, but there is an ambiguity for the carbon dioxide (CO2) absorbed during plant growing. In the different cases, it may or may not be deduced to compute a net GWP. The difference is significant. For example, the GWP of PLA may be:

• higher than 1.4 for emitted greenhouse gas; • higher than 0.6 for net GWP after the deduction of CO2 absorbed during plant growth.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00007-0 © 2020 Elsevier Ltd. All rights reserved.

309

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.1 Examples of Fuel Energy and Feedstock Energy. Fuel Energy

Feedstock Energy

Total Energy for European Union

Total Energy for United States

Fossil Plastics Mean

51

38

89

83

Median

43

41

84

83

Standard deviation

23

10

21

16

Minimum

30

19

57

59

Maximum

108

49

139

104

Samples

16

16

16

7

Natural-Sourced Plastics Fuel Energy

Feedstock Energy

Total Energy

Mean

42

4

46

Median

48

0

48

Standard deviation

27

5

24

Minimum

20

0

20

Maximum

100

13

115

Green PE

20

0

20

TPS

25 26

0 6

25 32

PHA

80 90

0

80 90

PLA

53

0

53

UP

59

13

72

Bio-PET partial renewable feedstock

69

9

78

Statistical Analysis

Examples

7.1.3 Rapid Overview of Examples of Advanced Indicators

data may be found elsewhere for resins and products.

Subchapter 7.1.3 deals with data examples of some advanced environmental indicators which show the broad diversity of published results.

7.1.3.2 Photo-Oxidant Creation Potential

7.1.3.1 Examples of Ozone Depletion Potential Table 7.2 displays the staggering range of ozone depletion potential (ODP) for 16 usual resins. The most polluting resin would be 100,000-times more polluting than the cleanest one. Results are expressed in g/kg as the usual unit for ODP. Data in T/kT and T/10 kT are more representative of consumption levels of industrial plastics. Different

Table 7.3 displays the range of photo-oxidant creation potential (POCP) for 16 usual resins. The most polluting resin would be 6-times more polluting than the cleanest one. Results are expressed in g/kg as the usual unit. Data in T/kT and T/10kT are more representative of global consumption levels of industrial plastics. Different data may be found elsewhere for resins and products.

7.1.3.3 Acidification Potential Table 7.4 displays the range of acidification potential (AP) for 16 usual resins. The most

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

Table 7.2 Ozone Depletion Potential Examples.

311

Table 7.4 Acidification Potential Examples.

CFC-11 equiv./ Resin Weight

g/kg or T/ kT

T/10 kT

SO2 equiv./Resin Weight

SAN

0.00000008

0.0000008

HDPE

4.28

42.8

ABS

0.00000026

0.0000026

PP

4.32

43.2

GPPS

0.00001630

0.000163

LLDPE

4.33

43.3

HIPS

0.00001720

0.000172

LDPE

4.36

43.6

PA66

0.00008300

0.00083

S-PVC

5.05

50.5

PA6

0.00012000

0.0012

GPPS

5.38

53.8

POM

0.00016000

0.0016

POM

5.4

54

PC

0.00019900

0.00199

HIPS

5.65

56.5

PMMA

0.00042000

0.0042

Amorphous PET

6.47

64.7

PP

0.00055000

0.0055

E-PVC

6.93

69.3

LLDPE

0.00057000

0.0057

PC

7.47

74.7

HDPE

0.00064000

0.0064

ABS

7.69

76.9

LDPE

0.00082000

0.0082

SAN

8.04

80.4

S-PVC

0.00220000

0.022

PA6

12

120

E-PVC

0.00240000

0.024

PA66

12.9

129

Amorphous PET

0.01800000

0.18

PMMA resin

17.4

174

Table 7.3 Photo-oxidant Creation Potential Examples. Ethene equiv./Resin Weight

g/kg or T/kT

T/ 10kT

PP

0.37

3.7

LLDPE

0.47

4.7

POM

0.5

5

E-PVC

0.54

5.4

S-PVC

0.56

5.6

PA6

0.6

6

HDPE

0.63

6.3

GPPS

0.85

8.5

HIPS

0.9

9

PMMA resin

0.94

9.4

PA66

1

10

ABS

1.09

10.9

SAN

1.19

11.9

LDPE

1.3

13

PC

1.61

16.1

Amorphous PET

2.313

23.13

g/kg or T/kT

T/ 10kT

polluting resin would be 4-times more polluting than the cleanest one. Data in T/kT and T/10kT are more representative of global consumption levels of industrial plastics. Different data may be found elsewhere for resins and products.

7.1.3.4 Eutrophication Potential Table 7.5 displays the range of eutrophication potential (EP) for 16 usual resins. The most polluting resin would be 9-times more polluting than the cleanest one. Data in T/kT and T/10kT are more representative of global consumption levels of industrial plastics. Different data may be found elsewhere for resins and products.

7.1.3.5 Dust/Particulate Matter (#10 µm3) Table 7.6 displays the huge range of dust/particulate matter (#10 µm3) (PM10) for 16 common resins. The most polluting resin would be 40,000-times more polluting than the cleanest one. Data in T/kT and T/10kT are more representative of global consumption levels of industrial plastics. Different data may be found elsewhere for resins and products.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

7.1.3.6 Ecotoxicity Potential

Table 7.5 Eutrophication Potential Examples. PO4 equiv./Resin Weight

g/kg or T/ kT

GPPS

0.48

4.8

HIPS

0.51

5.1

PC

0.92

9.2

S-PVC

0.94

9.4

SAN

1.02

10.2

ABS

1.03

10.3

LLDPE

1.15

11.5

PP

1.18

11.8

POM

1.2

12

HDPE

1.2

12

LDPE

1.25

12.5

E-PVC

1.25

12.5

Amorphous PET

1.49

14.9

PMMA resin

2.16

21.6

PA66

3.7

37

PA6

4.2

42

T/ 10kT

Table 7.6 Dust/Particulate Matter PM10. PM10 Weight/ Resin Weight

g/kg or T/kT

SAN

0.000137

0.00137

ABS

0.000235

0.00235

GPPS

0.15

1.5

HIPS

0.15

1.5

PC

0.267

2.67

POM

0.35

3.5

PMMA resin

0.46

4.6

PA66

0.8

8

PA6

1.2

12

S-PVC

3.84

38.4

HDPE

3.97

39.7

PP

3.97

39.7

LLDPE

4.01

40.1

LDPE

4.09

40.9

E-PVC

5.05

50.5

Amorphous PET

5.64

56.4

T/10kT

Ecotoxicity may be divided into:

• • • •

human toxicity terrestrial ecotoxicity marine aquatic ecotoxicity fresh water aquatic ecotoxicity

Table 7.7 displays some examples of ecotoxicity based on different units: 1.4 DB (dichlorobenzene) or As equiv. (arsenic). The most polluting resin would be 30-times more polluting than the cleanest one. Different data may be found elsewhere for resins and products. Many other indicators are used for special cases dealing with infrequent contexts due to the nature of compounds, inputs, outputs, use and disposal, land use, deforestation, source of electricity (nuclear pollutant, risk of nuclear accidents), nature conservation, biodiversity, etc.

7.1.4 Natural-Sourced Versus Fossil Polymers: A Mixed Bag of Benefits and Drawbacks All the information provided here are a limited number of examples tested in undefined conditions and are not rules. Different data may be quoted in scientific or technical literature. Table 7.8 displays an example of a natural fiber mat compared to glass fiber (GF). Results are expressed as the ratio of the considered property for the natural fiber mat to that of the used GF. Most impact categories of hemp are beneficial, but land occupation is detrimental. For an undefined end product based on epoxy, natural-sourced epoxy leads to:

• Beneficial impact categories: • Abiotic depletion • EP • ODP • Freshwater aquatic ecotoxicity • Questionable impact categories: • GWP • Cumulative energy demand (CED) • Human toxicity potential

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

313

Table 7.7 Examples of Ecotoxicity Based on Different Units. Human Toxicity Potential

Freshwater Aquatic Ecotoxicity

Marine Aquatic Ecotoxicity Potential

Terrestrial Ecotoxicity Potential

Toxicity expressed in kg 1.4 DB equiv. Petroleum-based epoxy

0.49

0.246

0.029

Human toxicity expressed in mg As equiv. PS

9 11

PP

0 1

PET

7 28

Table 7.8 Example of a Natural Fiber Mat Compared to Glass Fiber. Impact Category

Usual Units

Ratio Hemp/GF

Abiotic depletion

kg Sb equiv.

0.20

Acidification potential

kg SO2 equiv.

0.15

Eutrophication potential

kg PO4 equiv.

0.015

Global warming potential

kg CO2 equiv.

0.18

Ozone layer depletion potential

kg CFC11 equiv.

0.27

Human toxicity potential

kg 1.4 DB equiv.

0.014

Freshwater aquatic ecotoxicity potential

kg 1.4 DB equiv.

0.08

Marine aquatic ecotoxicity potential

kg 1.4 DB equiv.

0.09

Terrestrial ecotoxicity potential

kg 1.4 DB equiv.

0.04

Cumulative energy demand

MJ equiv.

0.17

m2a

22

Beneficial Impact Categories

Detrimental Impact Categories Land occupation (ecological footprint)

• Detrimental impact categories: • Terrestrial ecotoxicity potential For a rotor blade made out of a composite reinforced with natural fiber, carbon fiber (CF), or GF, evaluated according to the eco-indicator 95 method, scores in ascendant order are: • Flax fiber-reinforced epoxy

1.85 points

• Flax fiber-reinforced

1.58 points

epoxy (without pesticides)

• Carbon fiber-reinforced epoxy

2.40 points

• Glass fiber-reinforced epoxy

2.47 points

Comparing natural-sourced to fossil polyamides (PAs), “natural” PAs could lead to:

• Beneficial impact categories: • Renewable resources • ODP • GWP • Questionable impact categories: • CED • Detrimental impact categories: • EP • AP Relative to human toxicity measured in “mg As equiv.”, various PLAs are compared to various fossil commodity polymers:

• PLAs are beneficial versus polystyrene (PS) and PET

• PLAs are in the range of polypropylene (PP)

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

314

Concluding remarks:

Cont’d

• There is not a clear and total advantage for biobased polymers. Each case must be studied by a skilled and independent team.

of common grades. In addition, please remember that the properties measured on composites are not representative of the matrix properties.

• Biobased polymers can be more or less impacting than homologous fossil polymers depending on the actual context. For example, long transport of raw materials or the nature of the actual electricity mix may change the balance.

Of course, these theoretical data cannot be used for designing, computing, or to make economic predictions. Only properties measured on the actual used compound must be considered.

• Many results are expressed by weight, but in the real life, the most meaningful parameter is the functional unit.

• The end-of-life of the products have a heavy influence.

• Geopolitics and locally available resources must be taken into account, etc.

7.2 Advanced Engineering Properties Most properties of plastics are temperaturedependent including mechanical, physical, electrical, chemical, and aging characteristics among others. Many properties are also time-dependent such as creep, relaxation, fatigue, etc. For polymers used in thermoplastic or thermoset state, the thermoplastic state is more sensitive to heat. Glass transition temperature, heat deflection temperature, continuous use temperatures, and minimum service temperatures have been previously reported. This subchapter focuses on temperature and time effects on a limited number of short- and long-term mechanical properties. This fragmented information does not cover all other properties and cases. Of course, the data are only examples, providing a rough idea of the significant differences between subfamilies, but other data can be found elsewhere. For the same trade name and for identical conditions, published data related to a given property can be quite different. From a general point of view, the reader must keep in mind that advanced properties are most often studied on special grades optimized to achieve the best performance for the feature under consideration and are not representative (Continued )

7.2.1 Thermal Dependency of Mechanical Properties Formerly, from an engineering point of view, it must be remarked that thermal behavior is not an intrinsic property of a compound, but depends on numerous parameters including, among others, the shape of the part, the processing conditions, and the general history of the part. A temperature rise causes two different phenomena:

• Immediate physical effects, generally including decay of the modulus and other mechanical and physical properties (apart from strain, which increases), physicochemical softening, reversible thermal expansion, and, eventually, irreversible shrinkage and warpage. After a return to room temperature, the modulus and other mechanical properties recover their initial values.

• Long-term

effects including irreversible creep and relaxation for stressed parts, irreversible chemical aging, and related degradation of the material with decrease in mechanical properties, even after a return to room temperature.

Generally, a temperature drop causes opposite effects. Extremely low temperatures, notably cryogenic ones, can have some surprising effects.

7.2.1.1 Short-Term Effects of High and Low Temperatures In the following, property retentions are ratios: [Property at temperature t] divided by [property at 20°C] expressed in percent.

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

Decreases in performance when temperatures rise depend on:

• The considered property: Stress at yield or at break, modulus, elongation at break, etc. Generally, for the same compound there isn’t a correlation between stress, modulus, and elongation variations as can be seen in Fig. 7.1. Tensile strength decreases when elongation at break increases.

• The loading mode: Tensile, flexion, compression, shear, etc.

315

120 100 80 % 60 40 20 0 0

50

100 ºC

150

200

Figure 7.3 Examples of curves for modulus retention versus temperature.

• The used plastic and more precisely the recipe: See Fig. 7.2 showing examples of short-term tensile stress retentions for three grades of the same polymer.

• The test conditions: Short-term is a vague expression. For the same property, the evolution of shortterm retention versus temperature can obey diversified scenarios as shown in Fig. 7.3 relating to modulus. 250 200 150

EB

%

TS

100 50 0 0

20

40

60 ºC

80

100

Behavior Above Room Temperature

Table 7.9 for high-performance plastics and Table 7.10 for engineering and commodity plastics display mechanical property retentions approximately ranked in a descending order. In all likelihood, polybenzimidazole (PBI) offers the highest retentions with a 50% level and more at 300°C. At the opposite end, plasticized polyvinyl chloride (PVC) presents a 50% retention at temperatures as low as 60°C. Please note the broad range of values for each compound. Among thermosets, phenolics offer affordable opportunities; UP and epoxy families bring together grades offering medium and good heat retentions. Table 7.11 displays examples of elongation at break retentions. On the contrary to previous properties, elongation at break may significantly increase when the temperature rises.

120

Behavior Below Room Temperature

Figure 7.1 Examples of elongation at break and tensile strength retentions for the same compound. 120

Table 7.12 displays examples of mechanical property retentions at subzero temperatures. Cryogenic temperatures (http://lss.fnal.gov/archive/ test-tm/2000/fermilab-tm-2366-a.pdf) can lead to stratospheric moduli.

100 80

7.2.1.2 Long-term Heat Effect on Oxidizing Aging

% 60 40 20 0 0

50

100

150

200

250

300

350

ºC

Figure 7.2 Examples of tensile stress retentions for three grades of the same polymer.

Please see also Chapter 6, General Assessments Concerning Continuous Use Temperature and Relative Temperature Index. Long term resistance to heat aging results from conventional accelerated aging tests in air and predictions by modeling.

Table 7.9 Examples of Mechanical Property Retentions for High-performance Plastics. Temperature (°C)

20

50

100

150

180

Thermoplastics

200

225

250

300

350

400

80

65

45

25

Retentions (%)

PBI

Tensile strength (TS)

100

102

103

99

95

91

PAI GF

Flex Strength

100

97

87

72

63

58

51

PAI CF

Flex Strength

100

97

85

70

60

56

48

PAI CF

Flex Strength

100

PAI neat

Flex Strength

100

PAI neat

Strength

100

PPS

TS

100

PPS

TS

100

77 97

89

86

75

62

72

59

55

48

40

35

60

49

40

36 68

57

47

24 35

PES

TS

100

94

82

65

47

PEI CF

TS

100

90

72

55

47

PEI neat

TS

100

82

59

41

35

LCP mineral

TS

100

90

70

50

41

34

26

10 18

LCP mineral

TS

100

87

67

47

39

34

26

22

LCP mineral

TS

100

85

52

23

11

LCP GF

TS

100

90

85

78

53

38

27

15

PTFE

TS

100

76

47

34

32

31

29

28

PEEK CF

TS

100

90

66

42

28

23

21

20

PEEK CF

TS

100

PEEK neat

TS

100

PEEK neat

TS

100

ECTFE

TS

100

30 82

52

82

57

26

13

12

12

39

15

11

Thermosets PI

35

Retentions (%) Flexural modulus

100

100

100

97 99

92 97

90 96

85 95

80 94

PI

Modulus

100

55 90

PI

TS

100

50 85

PI

Flexural strength

100

44 70

Silicone

Elongation at break (EB)

100

Silicone

TS

100

Polycyanate

Mechanical property

100

93 98

79

62

75

56

48 40 75 85

74 84

73 83

72 82

60 85

Table 7.10 Examples of Mechanical Property Retentions for Engineering and Commodity Plastics. Temperature (°C) 20

40

50

60

80

Thermoplastics

100

120

150

175

Retention (%)

PES

TS

82

65

PSU

Strength

74

53

PC

TS

85

POM GF

TS

POM

Stress yield

100

87

80

74

63

52

38

POM antifriction

Stress yield

100

86

78

72

61

48

36

PA12 neat

TS

100

86

82

78

63

48

PA12 GF

TS

100

81

77

74

70

67

PA12 GB

TS

100

80

72

66

55

44

PA6 GF dry

TS

100

57

55

PA6 dry

TS

100

44

PBT GF

Stress yield

100

76

68

61

52

46

41

PBT neat

Stress yield

100

71

62

55

44

37

33

ETFE

TS

100

69

60

50

45

40

PVDF

Stress at yield

100

88

81

74

56

37

PVF

TS

100

83

75

65

45

30

ABS

Stress yield

100

HDPE

Stress yield

100

79

70

59

39

20

12

PMP

Stress yield

100

80

66

54

36

33

18

PMMA

TS

100

80

55

32

PVC

TS

100

81

56

31

PVC plasticized

TS

100

Temperature (°C)

81

20

49

44 27 36

33

10 35

25

18

24

12

42

69

12

50 40

50

60

80

Thermosets

100

120

150

60

43

27 B0 60

Retention (%)

UP, neat

Flexural modulus

100

50

UP GF

Flexural modulus

100

UP VE composite

Tensile modulus

100

100

100

100

98 104

81 105

53 103

PF

Tensile modulus

100

B100

B100

B100

B100

B100

B100

Temperature (°C)

20

40

50

60

80

Thermosets

100

120

150

Retention (%)

PF Long GF

Flexural modulus

100

92

PF

Compressive strength

100

PF

Flex modulus

PF

Flexural strength

100

MF

Flexural modulus

100

MF GF

Flexural modulus

100

EP

Modulus

100

EP

Flexural modulus

100

EP

Compression strength

100

EP

Flexural strength

100

54

EP

Flexural modulus

100

48

Furan, laminate

TS

100

100

100

100

99

94

86

84

Furan, laminate

Modulus

100

96

94

92

80

70

70

70

80 92 75 65 95

76

64

57

48

70 49 67

47% at 240°C

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

319

Table 7.11 Examples of Elongation at Break Retentions Versus Temperature. Temperature (°C) 20

50

80

Thermoplastic

100

150

180

200

193

198

200

Retention, %

LCP

EB

100

ETFE

EB

100

135

157

170

PVF

EB

100

140

175

200

PVC

EB

100

158

194

EB

100

Thermoset Silicone

79

62

48

Table 7.12 Examples of mechanical property retentions at subzero temperatures. Temperature (°C) 2 50

2 40

Thermoplastics

0

20

Retention (%)

ABS

Stress yield

140

100

PA6 GF dry

TS

149

100

PA6 dry

Modulus

104

100

PA6 dry

TS

152

100

PMP neat

Stress yield

POM GF

TS

POM GP

Stress yield

146

110

100

POM antifriction

Stress yield

154

115

100

PTFE

TS

118

100

PTFE

Modulus

132

100

PPE GF

Modulus

106

100

PPE neat

Modulus

108

100

LCP GF

EB

88

100

170

100

132

100

182

62

Thermosets 240

Temperature Furan laminate

TS

105

Furan laminate

Modulus

90

Temperature Polyimide

Modulus

Temperature

0

20 100

2269

2196

20

186 217

118 145

100

2173

2123

273

223

20

Epoxy

Tensile modulus

190 730

157 532

122 362

145 155

100

Epoxy

Poisson’s ratio

82 98

82 93

82 97

93 102

100

Epoxy

Maximum stress

180 366

151 403

119 339

110 150

100

320

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Conventional accelerated aging tests consist of exposing defined samples to controlled-temperature air in ovens protected from light, ozone, and chemicals, during one or more given times. The degradation is measured by the variation at room temperature of one or several physical or mechanical characteristics during the aging. The variations of impact resistance, hardness, tensile or flexural strength, and color are the most frequently studied. Electrical properties, fire behavior, weight, and other characteristics may also be tested according to the targeted application. Sometimes, properties are measured at the aging temperature, which is a more severe method. Accelerated aging is an arbitrary measurement that must be interpreted and must only be one of the elements used in making a judgment:

• All the properties do not degrade at the same rate.

• It is impossible to establish a direct relationship between the accelerated aging of a part and its real lifespan.

• For an unknown polymer, the results of accelerated aging must be compared with those obtained on a known polymer of a similar formula. Be careful of the accelerated aging conditions; more severe conditions can activate chemical reactions different from those observed at service conditions, which can lead to false predictions. For example, degradation at 150°C of commodity plastics is not of the same nature as the degradation at room temperature. For long lifetime prediction, testing in actual conditions is not useable and it is necessary to run accelerated testing in more severe conditions and

use mathematical models to predict the lifetime in actual conditions. It must be pointed out that kinetics may change during long-term tests in steady conditions. For example, aging kinetics can suddenly evolve with abrupt changes, thresholds, knees or sudden failures, crossing of glass transition, and so on. Generally speaking, it must be noted that a mathematical model is an equation giving a result in all cases. In real life, results can be completely different and the part may fail when the model predicts a longer life. The user must be aware of these risks. So, certain predictions can be disastrous, leading to completely false estimations. In optimistic cases, modeling can save time and money by reducing trials and property testing. The mathematical laws binding the effect of one property and a parameter such as time suppose that the property continuously evolves without abrupt changes. These laws cannot predict thresholds or knees or sudden failures and so on. These phenomena must be specifically modeled from specific studies analyzed with specific models. For broad ranges of temperatures, contrary to widespread expectations, an approach according to Arrhenius can lead to distorted lifetime predictions. The Arrhenius relation can yield a good fit for amorphous polymers, but for semicrystalline materials such as polybutyleneterephthalate (PBT) this approach needs to be deeply examined when the material is tested above and below its glass transition temperature (Tg). The temperature interpolation requires, at minimum, two tests above and two tests below Tg allowing two different Arrhenius equations with different slopes to be computed. For a PBT grade with a Tg of 50°C, Fig. 7.4 shows natural logarithm (LN) (tensile strength TS) versus 1000/T; it can remarked two different kinetics (bold lines) and the related trend lines (thin lines) intersecting approximately for 50°C.

4.8 4.6 4.4 4.2 LN(TS) 4 3.8 3.6 3.4 3.2 3

1000/T 1.5

4.5

(175°C)

Figure 7.4 Arrhenius plot for a PBT with a Tg of 50°C (1000/T 5 3).

(20°C)

7: ADVANCED ENVIRONMENTAL

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

AND

321

Table 7.13 Example of a PP Grade Degradation: Acceleration Factors for Gaps of Temperature of 10°C. Aging Temperature (°C) Service Temperature (°C)

70

60

2.9

70

80

90

100

110

120

130

140

150

2.8

80

2.7

90

2.7

100

2.5

110

2.3

120

2.3

130

2

140

Another widespread statement relates to the doubling of degradation for each increase of 10°C of the temperature. The values of factor F, see Table 7.13 for a given polypropylene grade, vary from around 1.5 to 2.9. The acceleration factor F for a temperature gap of 10°C is defined for each temperature. In theory, the level of degradation will be the same for a period D1 at T 1 10°C and for the duration D2 5 F D1 at temperature T. For example:

• 1 h at 150°C produces theoretically the same degradation as 1.5 h at 140°C.

• 1 h at 100°C produces theoretically the same degradation as 2.7 h at 90°C. For a series of compounds based on the same polymer, the parameters listed below influence the aging behavior significantly:

1.5

• Those data are not comparable and are quite arbitrary.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

• The lack of data for a defined temperature and/or time is not an indication of unsuitability, but is due to the unsuccessful research of data.

• A defined compound or family can be found in several lines because property, temperatures, and/or times are different and because compounds are different.

• Errors, lack of accuracy, and method uncertainty need to be verified in the data and the really used compound needs to be checked. Results should not be interpreted as an indication of the expected service life for any targeted application.

• Used additives, notably stabilizers and other antioxidants.

• Alloying with other (co)polymer(s), for example, acrylonitrile-butadiene-styrene (ABS).

• Sample thickness. • Checked property, namely elongation at break, impact, and yellowing are often sensitive.

• In real life, shape of the actual part, etc. Table 7.14 displays some examples of property retentions ranked by temperature and time in descending order. Results must be carefully examined:

7.2.2 Time Dependent Mechanical Properties Due to their structure, plastics have a viscoelastic behavior leading to time-dependent mechanical properties, particularly creep and stress relaxation. Generally speaking:

• Thermoplastics

are

more

sensitive

than

thermosets.

• Composites are less sensitive to the reinforcement direction than the matrix.

322

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.14 Examples of Property Retentions Versus Temperature and Time. Temperature (°C)

Time (h)

Plastic

Property

Retention

370

500

PBI

Compressive strength

B40

370

500

PBI

Weight

B45

315

500

PBI

Compressive strength

B90

315

500

PBI

Weight

B90

310

430

PEEK

TS

50

310

240

PEEK

EB

50

270

3000

LCP

TS

60

270

3000

LCP

Impact

30

260

20,000

PFA

EB

50

260

20,000

PTFE

EB

50

260

10,000

PAI

TS

67

260

4400

PAI

TS

83

260

1500

PAI

TS

104

260

500

PBI

Compressive strength

B100

260

500

PBI

Weight

B100

250

19,000

PEEK

TS

50

230

168

ETFE

TS

90

230

168

ETFE

EB

90

230

168

ETFE

Dielectric strength

90

220

20,000

LCP GF

Mechanical and electrical

50

220

20,000

PAI

Mechanical And electrical

50

220

20,000

PEEK

Mechanical and electrical

50

220

17,000

PES

TS

50

220

8760

PES

TS

50

210

3600

ETFE

TS

60

210

3600

ETFE

EB

50

210

3600

ETFE

Dielectric strength

25

205

20,000

FEP

EB

50

204

3000

LCP

TS

80

204

3000

LCP

Impact

60

Engineering Data

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

323

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

Engineering Data

200

43,800

PES

TS

50

200

20,000

LCP GF

Mechanical and electrical

50

200

200,00

PAI

Mechanical and electrical

50

200

8760

PEEK

EB

50

200

8760

PPS

TS

57

200

8760

PPS

EB

50

200

5760

ETFE

TS

50

200

2000

PA6 or 66 GF super heat stab

TS

95

200

2000

PA6 or 66 GF super heat stab

EB

50

200

1800

ETFE

EB

50

200

1700

PA6 or 66 GF heat stabilized

TS

50

181

8760

ECTFE

EB

50

180

157,000

PES

TS

50

180

96,000

PES

TS

50

180

21,900

ETFE

TS

50

180

20,000

PEEK

Mechanical and electrical

50

180

5760

ETFE

EB

50

180

1000

PBT GF

TS

50

180

960

PBT

TS

B80

180

960

PBT

TS

B30

180

100

PA6 or 66

TS

50

180

100

PBT

TS

B100

177

2000

PA6 or 66 GF

TS

82

175

17,500

ECTFE

EB

50

175

1200

COPE polyester ester

TS, EB

50

170

20,000

PEI

Mechanical and electrical

50

170

5000

PA6 and 66 GF

TS at 170°C

50 70 MPa

170

5000

PA6 and 66 GF

Modulus at 170°C

3.5 GPa

170

2000

PBT GF

TS

50

170

700

PA11 or 12

TS

50 (Continued )

324

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

Engineering Data

170

400

PA11 or 12

TS

50

170

200

PA11 or 12

TS

50

169

43,800

ECTFE

EB

50

165

87,600

ECTFE

EB

50

165

24,000

PVDF

Yield stress

85

165

24,000

PVDF

TS

100

160

43,800

ETFE

TS

50

160

20,000

PSU

Mechanical and electrical

50

160

17,500

ETFE

EB

50

160

10,500

PA11 or 12

TS

50

160

4500

PA11 or 12

TS

50

160

3000

PA6 or 66

TS

50

160

3000

PBT GF

TS

50

160

700

PA11 or 12

TS

50

160

250

PA6 or 66

TS

50

160

150

PA6 or 66

TS

50

160

4

PA6 or 66

TS

50

155

20,000

PET 30GF FR

Mechanical and electrical

50

155

240

PA11 or 12

EB

50

150

10,000

PBT GF

TS

50

150

5000

PA6 and 66 GF

TS at 150°C

70 80 MPa

150

5000

PA6 and 66 GF

Modulus at 150°C

4 GPa

150

5000

PA6 or 66

Modulus at 150°C

0.4 GPa

150

3000

LCP

TS

90

150

3000

LCP

Impact

70

150

1200

COPE polyester ester

TS, EB

50

150

960

PVF

TS

50

150

960

PVF

EB

25

150

960

PVF

Impact

10

149

2000

PA6 or 66 GF

TS

95

140

157,000

ETFE

TS

50

140

43,800

ETFE

EB

50 (Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

325

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

Engineering Data

140

30,000

PA11 or 12

TS

50

140

20,000

PSU

Mechanical and electrical

50

140

20,000

PBT GF

Mechanical and electrical

50

140

20,000

PA66 GF

Mechanical and electrical

50

140

20,000

PBT GF

TS

50

140

13,000

PA11 or 12

TS

50

140

4500

PA11 or 12

TS

50

140

2500

PA11 or 12

TS

50

140

2000

PA11 or 12

EB

50

140

1500

PA11 or 12

EB

50

140

1000

PA6 OR 66

TS

50

140

1000

PP, GF stabilized

TS

95 99

140

1000

PP, GF stabilized

Modulus

98 113

140

1000

PP, GF stabilized

EB

89 97

140

900

PA6 or 66

TS

50

140

840

COPE

TS, EB

50

140

800

PA11 or 12

EB

50

140

480

COPE

TS, EB

50

140

30

PA6 or 66

TS

50

130

20,000

PBT GF

Mechanical and electrical

50

130

20,000

PC

Mechanical and electrical

50

130

20,000

LCP GF FR

Mechanical and electrical

50

130

2400

PP, stabilized

Brittleness

Embrittlement

130

50

PP, unstabilized

Brittleness

Embrittlement

130

48

TPU

TS

50

130

24

TPU

TS

50

125

20,000

PA66 GF

Mechanical and electrical

50

125

20,000

PC

Mechanical and electrical

50

125

8760

PMP

TS

50

125

1000

TPO-V

EB

88 (Continued )

326

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

125

1000

TPO-V

TS

93

121

2000

PA6 or 66 GF

TS

105

120

50,000

PA11 or 12

TS

50

120

48,000

PA6 or 66 GF

TS

50

120

48,000

PA6 or 66 GF

TS

50

120

36,000

PA6 or 66 GF

TS

50

120

24,000

PA6 or 66 unreinforced

TS

50

120

21,000

PA11 or 12

TS

50

120

20,000

PP mineral

Mechanical and electrical

50

120

20,000

PC

Mechanical and electrical

50

120

16,800

PA6 or 66 unreinforced

TS

50

120

10,000

PA11 or 12

TS

50

120

4800

PA6 or 66 unreinforced

TS

50

120

4300

COPE polyester ether

TS, EB

50

120

3000

PA11 or 12

EB

50

120

500

TPO

TS

73

120

500

TPO

EB

65

120

400

PE, stabilized

EB

60 90

120

400

PE, unstabilized

EB

40

120

240

PE, stabilized

EB

80 100

120

240

PE, unstabilized

EB

60

120

216

TPU

TS

50

120

24

TPU

TS

50

115

20,000

PEI

Mechanical and electrical

50

115

20,000

PP mineral

Mechanical and electrical

50

110

20,000

PPE 1 PS, GF FR

Mechanical and electrical

50

110

20,000

PVC

Mechanical and electrical

50

110

20,000

PEBA

Mechanical and electrical

50

Engineering Data

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

327

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

110

2160

PEBA

EB

50

110

480

TPU

TS

50

110

48

TPU

TS

50

105

20,000

POM

Mechanical and electrical

50

105

20,000

PC

Mechanical and electrical

50

105

20,000

PPE 1 PS, GF FR

Mechanical and electrical

50

105

20,000

PEI GF PTFE

Mechanical and electrical

50

105

20,000

PPE 1 SEBS

Mechanical and electrical

50

105

20,000

PVCC

Mechanical and electrical

50

100

87,600

PMP

TS

50

100

70,000

PA11 or 12

TS

50

100

50,000

PA11 or 12

EB

50

100

48,000

PA11 or 12

EB

50

100

43,800

PMP

TS

50

100

43,800

SEBS

TS, EB

50

100

30,000

PA11 or 12

TS

50

100

20,000

PA11 or 12

EB

50

100

20,000

PA6 or 66

TS

50

100

20,000

SEBS

TS, EB

50

100

7200

PP, stabilized

Brittleness

100

3500

PA6 or 66

TS

50

100

2500

PA6 or 66

TS

50

100

1000

PP/NBR-V

EB

84

100

1000

PP/NBR-V

TS

147

100

960

PP, unstabilized

Brittleness

100

250

PA6 or 66

TS

50

100

200

PA11 or 12 unstabilized

EB

50

95

20,000

PPE 1 PS, GF FR

Mechanical and electrical

50

95

20,000

PEBA

Mechanical and electrical

50

Engineering Data

Embrittlement

Embrittlement

(Continued )

328

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

90

16,800

ABS 1 PC

Yellowing degree

90

16,800

ASA

Impact

90

16,800

ASA

Yellowing degree

90

16,800

ASA 1 PC

Impact

90

16,800

ASA 1 PC

Yellowing degree

90

9240

ABS 1 PC

Impact

0

90

8760

PB

Stress

40

90

6720

ABS

Impact

5

90

6720

ABS

Yellowing degree

70

90

6720

ABS 1 PC

Yellowing degree

20

90

6720

ASA

Yellowing degree

4

90

6720

ASA 1 PC

Yellowing degree

3

90

3500

ABS 1 PC

Impact

50

90

2500

ABS

Impact

10

85

48,000

TPU

EB

50

85

43,800

SEBS

TS, EB

50

85

43,000

TPE/PVC

TS

50

85

35,000

SEBS

TS, EB

50

85

26,000

TPU

TS

50

85

26,000

COPE polyester ether

TS, EB

50

85

21,600

TPE/PVC

EB

50

85

20,000

POM

Mechanical and electrical

50

85

20,000

ABS FR

Mechanical and electrical

50

85

20,000

PVC

Mechanical and electrical

50

85

20,000

COPE

Mechanical and electrical

50

85

12,000

TPU

EB

50

85

8000

SBS

TS, EB

50

Retention

Engineering Data 47

42 8 83 5

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

329

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

85

7200

TPU

TS

50

85

1300

TPE/PVC

EB

50

80

100,000

PA6 or 66

TS

50

80

30,000

PA6 or 66

TS

50

80

26,000

PEBA

EB

50

80

20,000

PPE 1 PS, GF FR

Mechanical and electrical

50

80

20,000

PC generic RTI

Mechanical and electrical

50

80

10,000

PA6 or 66

TS

50

80

4000

PA6 or 66

TS

50

80

1000

PS

TS

83

80

1000

PS

EB

70

75

20,000

ABS FR

Mechanical and electrical

50

70

438,000

PB

Stress

52

70

43,800

SBS

TS, EB

50

70

43,800

SEBS

TS, EB

50

70

19,000

PP, stabilized

Brittleness

70

8760

PB

Stress

63

70

8000

SBS

TS, EB

50

70

3600

PP, unstabilized

Brittleness

60

438,000

PB

Stress

62

60

8760

PB

Stress

73

55

43,800

SBS

TS, EB

50

55

26,300

SBS

TS, EB

50

50

20,000

Acrylic/PVC FR

Mechanical and electrical

50

50

20,000

PPE 1 PS, GF FR

Mechanical and electrical

50

50

20,000

PS FR

Mechanical and electrical

50

50

20,000

SMA

Mechanical and electrical

50

50

20,000

PVC

Mechanical and electrical

50

Engineering Data

Embrittlement

Embrittlement

(Continued )

330

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

50

20,000

PVC GF

Mechanical and electrical

50

50

20,000

COPE

Mechanical and electrical

50

50

9600

PP, unstabilized

Brittleness

50

8760

PB

Stress

80

40

43,800

SBS

TS, EB

50

20

450,000

PE100

Pipe standard

20

450,000

PVC

Pipe standard

370

334

PI

Mechanical property

50

370

100

PI

Mechanical property

50

370

B0

PI

Mechanical property

50

320

1000

PI

Mechanical property

50

320

800

PI

Mechanical property

50

320

1

PI

Mechanical property

50

265

10,000

PI

Mechanical property

50

265

1700

PI

Mechanical property

50

265

500

PI

Mechanical property

50

250

2208

Silicone

Mechanical property

50

240

21

EP heat resistant

TS

50

225

2500

PF BMC

Flex modulus

10 32

225

2500

Phenolic BMC

TS

21

225

2000

Phenolic BMC

TS

30

225

1500

PF BMC

Flex modulus

40 45

225

1000

PF BMC

Flex modulus

60 65

225

1000

Phenolic BMC

TS

50

225

500

PF BMC

Flex modulus

62 68

Engineering Data

Embrittlement

Thermosets

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

331

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

225

250

PF BMC

Flex modulus

75 80

220

417

EP heat resistant

TS

50

210

17,520

Silicone

Mechanical property

50

204

10,800

VE

Flex strength

0 25

204

7200

VE

Flex strength

0 50

204

3600

VE

Flex strength

0 75

200

72,000

PI

Mechanical property

50

200

10,000

PI

Mechanical property

50

200

10,000

PI

Mechanical property

50

200

2500

Phenolic BMC

TS

58

200

2000

Phenolic BMC

TS

62

200

1000

Phenolic BMC

TS

76

200

833

EP heat resistant

TS

50

200

240

Silicone

TS

57 78

200

240

Silicone

EB

22 70

200

240

Silicone

Tear strength

40 100

200

100

EP heat resistant

Flex strength

70

185

100,000

PI

Mechanical property

50

185

20,000

PI

Mechanical property

50

185

16,000

PI

Mechanical property

50

182

10,800

VE

Flex strength

0 60

182

7200

VE

Flex strength

0 80

182

3600

VE

Flex strength

30 95

175

8000

EP heat resistant

Flex strength

70

175

2500

Phenolic BMC

TS

71

175

2000

Phenolic BMC

TS

74

175

1000

Phenolic BMC

TS

76

160

50,000

EP heat resistant

Flex strength

70

160

10,800

VE

Flex strength

40 90

160

7200

VE

Flex strength

95 105

160

3600

VE

Flex strength

105 110

Engineering Data

(Continued )

332

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.14 Examples of Property Retentions Versus Temperature and Time.—Cont’d Temperature (°C)

Time (h)

Plastic

Property

Retention

150

43,800

Silicone

Mechanical property

50

150

2500

Phenolic BMC

TS

90

150

2000

Phenolic BMC

TS

92

150

1000

Phenolic BMC

TS

98

150

168

PUR

TS

40 50

150

168

PUR

EB

20 80

140

16

PUR foam

TS

.70

125

87,600

Silicone

Mechanical property

50

120

168

PUR

TS

70 90

120

168

PUR

EB

40 85

100

168

PUR

TS

70 95

100

168

PUR

EB

45 90

70

1800

PUR

TS

5 25

70

1800

PUR

EB

0 95

70

168

PUR

TS

70 95

70

168

PUR

EB

45 90

70

22

PUR

Compression set

7.2.2.1 Creep Creep is the time-dependent strain induced by a constant mechanical loading. The strain is a function of the stress level, the loading time, and the temperature. The results can be presented graphically in various ways by combining these three parameters or in quantified forms, creep modulus and creep strength, for example. The creep modulus for a specified stress, time, and temperature is the value of the stress divided by the strain measured after the selected time. The creep strength for a specified time and temperature is the value of the stress leading to failure after the time under consideration. Fig. 7.5A D shows some aspects of creep for polypropylene and polyethylene:

• (A) and (B) are the same strain results plotted against arithmetic or logarithmic scales for time.

Engineering Data

8% 69% permanent set

• (C) shows examples of creep strain according to the load level.

• (D) shows examples of creep strength at 100, 10,000, and more than 20,000 h. According to the temperature. It is not comparable with (A), (B), and (C). Creep modulus values are broadly inferior to their counterparts measured by dynamometry as can be seen in Table 7.15 displaying some examples of engineering modulus (EM; MPa), creep modulus at 1 and 1000 h (CM1 and CM1000, MPa), ratios (CM1/EM and CM1000/ EM, %). Data are ranked in descending order of CM1000/EM ratio. It should be noted that the creep modulus after 1000 h can be half of the engineering modulus for less than 42 days (1000 h), which is a short duration for usual applications.

7: ADVANCED ENVIRONMENTAL

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

(B)

5

333

5

Strain, %

Strain, %

(A)

AND

Time, h

0 0

5000

Time, h

0 1

10,000

100

10,000

(C) 5

Strain, %

PP, 15 MPa PP, 10 MPa

Time, h 10,000

0 0

5000

Stress, MPa

(D) 20

PE, 20°C PE, 50°C PE, 80°C

Time, h

0 1

100

10,000

Figure 7.5 (A) Creep strain versus time: example of polypropylene at 23°C under 10 MPa in tensile loading. (B) Creep strain versus time: example of polypropylene at 23°C under 10 MPa in tensile loading. (C) Creep strain versus time: example of polypropylene at 23°C under 10 and 15 MPa in tensile loading. (D) Creep strength versus time: example of polyethylene at 20°C, 50°C, and 80°C.

Results must be carefully examined:

• These data are not comparable and are quite

• Errors, lack of accuracy, and method uncertainty need to be verified in the data and the used compound needs to be checked.

arbitrary.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

• The lack of data for a defined time or a defined load is not an indication of unsuitability, but is due to the unsuccessful research of data.

• A defined family can be found in several lines because grades and/or loads are different and because compounds are different.

Results should not be directly interpreted as an indication of the expected service life for any targeted application. Tables 7.16 7.18 display more detailed data of creep modulus (MPa) versus time at room temperature and various higher temperatures for various loads. Results must be carefully examined:

• Reinforcement plasticization and impact modification are not always pointed out.

Table 7.15 Examples of Engineering Modulus (EM), Creep Modulus (CM), [CM/EM] Ratio Versus Time (1 and 1000 h). Expected Neat Grades EM (MPa)

PSU

2480

PS

3300

Modified Grades CM1 (MPa)

CM1000 (MPa)

[CM1/EM] (%)

2210 3300

2600

[CM1000/ EM] (%)

CM1 (MPa)

CM1000 (MPa)

[CM1/EM] (%)

[CM1000/ EM] (%)

PBT 30% GF

10,000

9800

8900

98

89

PPE 20 GF

6500

6100

5150

94

79

PEEK, reinforced

3500

LCP 30 GF

15,000

PEEK PTFE

3500

2500

71

PBT 30% GF

9700

6700

69

PPE 30 GF

9000

7100

6100

79

68

PBT 30% GF

10,000

9000

6600

90

66

PA6 30 GF

5300

PA66 40 mineral cond

3800

3500

2100

92

55

PA6 GF/mineral

5000

2800

1850

56

37

84.7

68.3

89 100

79

PC

2400

2200

1900

92

79

SAN

3700

3500

2800

94

76

PPE

2500

2300

1900

92

76

LCP

10,600

9000

6600

85

62

ABS

2500

2200

1500

88

60

ASA

2300

1850

1400

80

61

PMMA impact

1700

1400

1000

82

59

POM

2400

2000

1400

83

58

PPE

2100

1700

1200

81

57

PA12/ PEBA

370

PMMA

3100

2600

1600

84

52

POM

2760

2450

1350

89

49

PBT

2480

1800

1200

72

48

PBT

2480

POM

2850

2500

1300

88

45

PA66 cond

1600

1100

680

69

43

Mean

EM (MPa)

200

3040

12,600

10,900

87

84

3000

73

57

54

1200

48

85.1

60.9

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

• Type of loading is not known; often data result from tensile creep tests, but some others result from bending tests or others.

• Hygrometry of polyamides and other moisture sensitive polymers is unknown.

• These data are not comparable and are quite arbitrary; the nature of the loading and methods are unknown.

• The lack of data for a defined time or a defined load is not an indication of unsuitability, but is due to the unsuccessful research of data.

• A defined family can be found in several lines because grades and/or loads are different and because compounds are different.

• Errors, lack of accuracy, and method uncertainty need to be verified in the data and the used compound needs to be checked.

• Results should not be directly interpreted as an indication of the expected service life for any targeted application.

335

Table 7.16). For a given time, generally, creep modulus decreases when loading increases. Table 7.16 displays examples of 15 compounds named “ABS” without any additional indication. Total creep modulus range evolves from 910 MPa to 2520 MPa with an average value of 1624 MPa, that is to say, a deviation of 244% to 155%. For a defined load of 14 MPa, total creep modulus range evolves from 1127 MPa to 1988 MPa with an average value of 1600 MPa, that is to say, a deviation of 230% to 124%. Table 7.17 displays some examples of creep modulus (MPa) versus time at room temperature for various loads. Table 7.18 displays examples of creep modulus (MPa) versus time at various temperatures for various loads. Test temperatures are in descending order. Results must be carefully examined:

• These data are not comparable and are quite arbitrary.

• Type of loading is not known; often data result Compounds are diverse and creep moduli are broadly spread for given times and loads (see

from tensile creep tests, but some others result from bending tests or others.

Table 7.16 Examples of Creep Modulus for 15 Compounds Named ‘ABS’ Without Any Additional Indication. Time (h) Load (MPa)

1

10

100

100

Creep Modulus (MPa) ABS

7

2520

2380

2100

1540

ABS

10.5

1610

1568

1477

1316

ABS

10.5

1988

1946

1841

1680

ABS

10.5

2450

2310

2030

1470

ABS

14

1512

1372

1127

ABS

14

1610

1540

1400

ABS

14

1974

1841

1631

1344

ABS

14

1988

1876

1715

1477

ABS

17.5

1561

1456

1260

ABS

17.5

1946

1771

1512

ABS

21

1267

952

ABS

21

1477

1295

910

ABS

21

1778

1568

1190

ABS

21

1855

1638

1232

ABS

24.5

1631

1155

1092

336

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.17 Examples of Creep Modulus (MPa) Versus Time at Room Temperature for Various Loads. Time (h) Grade

1

Load (MPa)

10

100

1000

Creep Modulus (MPa)

Thermoplastics: Examples of Creep Modulus (MPa) Versus Time at Room Temperature PAI

Unknown

105

3400

2900

2500

LCP

Unknown

80

10,200

9900

9600

9200

PA66

High GF

70

10,710

9450

9240

PAI

Unknown

70

4400

3700

3200

PAEK

50

3400

3330

3225

3105

PES

50

2200

2010

1790

PEI

30% GF

49

8680

8680

8120

8120

PEI

20% GF

49

6650

6580

6160

5950

PEI

10% GF

49

4900

4900

4340

4200

PEI

49

3080

3010

2730

2660

PES

39

2360

2260

2160

PA66

CF

35

13,440

13,300

13,300

PA66

High GF

35

14,700

10,290

9695

PA66

CF

35

10,290

9310

9100

ETFE

30% GF

35

9660

9240

8820

PEI

30% GF

35

9240

8540

8470

POM homo

40% GF

35

9240

8200

8050

PEI

20% GF

35

6860

6860

6510

6300

PPE

GF

35

6601

6601

6482

5495

ETFE

30% GF

35

5670

5320

5145

PEI

10% GF

35

5180

4760

4480

PP

40% GF

35

5600

4550

3360

PA66

GF

35

5075

4200

3990

PP

20% GF

35

3710

3360

3220

2800

PEI

35

3360

3360

3010

2870

POM Co

35

2660

2380

1890

1540

1400

1050

9240

5180

PA66

Mineral

35

2450

1960

ABS

HR

35

1953

1659

PPS

Unknown

30

15,200

15,000

13,500

PPS

Unknown

30

9000

8900

8800

PAEK

30

3658

3658

3658

3409

PES

30

2550

2410

2280

PVC

30

2400

1950

PES

29

2420

2370

2600

2320 (Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

337

Table 7.17 Examples of Creep Modulus (MPa) Versus Time at Room Temperature for Various Loads.—Cont’d Time (h)

1

10

100

1000

Grade

Load (MPa)

PA6 RH

Medium GF

28

4270

3780

3360

PA6 Dry

Low GF

28

3220

2835

2135

ABS

HR

28

2156

1946

1610

PA6 RH

Rather low GF

28

1960

1645

1400

PA6 RH

Low GF

28

644

539

406

PVC

25

2900

2700

2400

2200

ABS

24.5

1631

1155

21

9800

9205

7770

5460

2450

2350

2200

PET

GF

Creep Modulus (MPa) 3010

1190

PSU

21

PA6 dry

21

3150

2856

2324

21

3220

2835

2240

21

2415

2275

2177

1827

21

2296

2135

1855

1519

ABS

21

1855

1638

1232

ABS

21

1778

1568

1190

ABS

21

1477

1295

910

21

1078

931

749

ECTFE

21

567

469

371

273

ABS

21

1267

952

FEP

21

119

107

SAN

20

3800

3000

2200

PES

20

2500

2400

2350

ASA

20

2200

1800

1400

PA6 dry

Low GF

PPE ABS

PA6 RH

HR

Low GF

PA66

CF

17.5

14,560

13,720

13,300

PA66

CF

17.5

12,460

10,010

9205

ETFE

30% GF

17.5

10,745

9660

8820 1092

ABS

17.5

1946

1771

1512

ABS

17.5

1561

1456

1260

FEP

17.5

161

147

130

PPE

GF

14

7910

7882

7875

7280

PET

GF

14

9590

9170

7700

6510

POM homo

30% GF

14

8050

5950

5530

POM homo

20% GF

14

5460

4410

3430

PA66

GF, PTFE

14

6510

4200

3920

PA6 dry PA6 dry PPE

Low GF

6090

14

3360

3094

2569

14

3255

2905

2415

14

2499

2450

2373

2058 (Continued )

338

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.17 Examples of Creep Modulus (MPa) Versus Time at Room Temperature for Various Loads.—Cont’d Time (h) Grade

Load (MPa)

ABS

HM

14

PE

20% GF

14

PE

20% GF

14

ABS

HR

PA6 RH

1

10

100

1000

Creep Modulus (MPa) 2380

2240

2100

2415

2170

1820

2590

2380

2170

14

2310

2240

2100

1680

Rather low GF

14

2660

2310

2030

1750

ABS

HR

14

2310

2261

2030

1708

ABS

FR

14

2100

2100

1890

1750

ABS

HI FR

14

2100

2100

1890

1680

14

2352

2177

1841

14

3360

2380

1820

1260

14

1988

1876

1715

1477

PA6 dry PA66

Mineral

ABS

2380

PVC

Impact

14

2050

2000

1700

1260

ABS

HI

14

1890

1820

1680

1330

ABS

FR

14

2030

2030

1680

1190

14

1974

1841

1631

1344

14

2100

1960

1610

1260

14

1610

1540

1400

14

1540

1470

1330

14

1512

1372

1127

14

1176

980

826

ECTFE

14

931

819

707

581

PA6 RH

14

427

385

336

308

ABS ABS

HI

ABS ABS

HI

ABS PA6 RH

Low GF

1050

PTFE

GF

14

385

329

294

PTFE

CF

14

350

292

266

14

252

217

189

6160

5250

4340

3500

3850

3290

2940

FEP POM homo

20% GF

10.5

PE

30% GF

10.5

ABS

10.5

2450

2310

2030

1470

POM homo

10.5

2730

2660

1960

1680

10.5

2100

2100

1890

1400

10.5

1988

1946

1841

1680

10.5

2100

2050

1750

1280

ABS

10.5

1610

1568

1477

1316

PA6 RH

10.5

868

714

595

483

FEP

10.5

210

130

65

ABS

HI

ABS PVC

Impact

PBT

50% GF

10

14,000

13,700

13,000

12,200

PBT

30% GF

10

9400

9100

8700

7900 (Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

339

Table 7.17 Examples of Creep Modulus (MPa) Versus Time at Room Temperature for Various Loads.—Cont’d Time (h)

1

10

100

1000

Grade

Load (MPa)

20% GF

10

5516

5390

5285

5110

PAEK

10

4000

3921

3846

3703

PES

10

2820

2810

2770

PVC

10

3100

3000

2800

PC

10

2415

2345

2240

2170

10

2500

2450

2200

1700

PS

10

2100

2100

1850

1350

PA12RH

10

840

679

546

434

PC

PBT

Neat

Creep Modulus (MPa)

HDPE

8.75

420

294

224

HDPE

8.75

385

252

182

154

8

571

444

320

140

7

6580

5810

4690

3780

PPE

7

2751

2744

2632

2338

PMMA

7

2870

2625

2394

PMMA

7

2800

2590

2380

PP POM homo

PA66

20% GF

Mineral

7

4025

3150

2520

1960

7

2800

2800

2450

1800

7

2380

2380

2310

2100

ABS

7

2520

2380

2100

1540

POM homo

7

2800

2520

2030

1750

PS ABS

HM

PVC

Impact

7

2300

2200

1900

1250

ABS

HI

7

2170

2100

1890

1400

ABS

HM HR

7

2450

2310

1820

1400

ABS

FR

7

2030

2030

1750

1260

ABS

FR

7

1820

1820

1540

1050

ABS

HI

7

1540

1470

1400

1260

PA6 RH

7

868

777

672

532

PP

7

882

658

581

448

FEP

7

392

329

273

HDPE

7

861

434

252

PTFE

7

196

140

105

77

PP

6

666

500

387

187

PA12 dry

5

1225

1120

1036

959

PMP

5

1130

850

575

370

329

273

224

175

666

571

470

228

PTFE PP

4.55 4

(Continued )

340

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.17 Examples of Creep Modulus (MPa) Versus Time at Room Temperature for Various Loads.—Cont’d Time (h) Grade

1

Load (MPa)

POM homo

20% GF

3.5

PE

30% GF

3.5

10

100

1000

Creep Modulus (MPa) 8540

7700

5600

4480

4865

4270

4165

POM Co

3.5

2660

2380

2170

1890

POM homo

3.5

2800

2590

2030

1750

3.5

1680

1540

1540

1330

ETFE

3.5

1400

1169

945

875

PP homo

3.5

1043

805

707

532

PP Co

3.5

735

560

518

374

FEP

3.5

469

420

371

FEP

3.5

336

315

287

PTFE

3.5

434

350

280

ABS

HI

Grade

Load (MPa)

220

Creep Modulus (MPa) 1h

10 h

100 h

1000 h

8600

8200

Thermosets: Examples of Creep Modulus (MPa) at Room Temperature PUR

Rigid

14

3200

UP

Unknown

15

10,000

UP/GF

Woven roving

15

21,000

UP/GF

Woven roving

15

14,100

13,500

13,300

UP/GF

Woven roving

15

11,800

11,000

10,600

UP/GF

Extrusion

28

12,000

9590

8200

UP/GF

Woven roving

30

17,000

16,500

UP/GF

Woven roving

45

14,000

13,000

UP/GF

Woven roving

45

9900

UP/GF

Woven roving

30

17,000

16,500

UP/GF

Woven roving

45

14,000

13,000

UP/GF

Woven roving

45

9900

PF

20,000

11,550

9300

9300

9100

9100

14

14,000

PF/GF

GF

14

17,000

PF mineral

Mineral filler

14

14,000

PF cellulose

Cellulose

14

14,000

EP/GF

Molding

25

14,700

14,070

EP

Neat

Unknown

2200

1980

EP/silica

Molding

Unknown

9200

7500

EP/nanoclay

Molding

Unknown

3800

370

13,350 7100

5900

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

341

Table 7.18 Examples of Creep Modulus (MPa) Versus Time at Various Temperatures for Various Loads. Time (h)

1

10

100

1000

Thermoplastics

Grade

Temperature (°C)

Load (MPa)

LCP

Unknown

180

8

4000

3500

3000

FEP

175

1.4

26

21

16

FEP

175

0.7

32

28

24

Creep Modulus (MPa) 2500

PAI

Unknown

150

70

3200

2500

1925

PES

30% GF

150

62

6000

5400

4900

4500

PPS

40% GF

150

49

2800

2600

2520

2450

PES

30% GF

150

37

6150

5500

5000

4600

PSU

150

21

995

700

500

PES

150

20

2100

2000

1900

PAEK

150

20

909

727

PES

150

10

2200

2100

PTFE

150

7

39

36

32

1111

2000

PPS

Unknown

120

30

6800

5450

5260

PA6

Medium GF

120

28

1890

1750

1470

1260

LCP

Unknown

120

20

6000

4500

3200

2200

PA6

120

7

490

420

385

315

PA6

120

4.9

560

490

455

ECTFE

120

3.5

84

56

35

PTFE

120

3.5

42

35

35

ECTFE

120

1.4

119

91

63

POM Co

110

7

504

434

385

315

POM Co

110

3.5

504

441

399

329

110

3.5

2275

1652

1302

PSU

100

21

1650

1450

1300

PAEK

100

20

2780

2564

2439

2272

POM Co

25% GF

LCP

Unknown

100

17

8400

7500

6400

5300

LCP

Unknown

100

17

8200

7400

6800

6200

ETFE

25% GF

100

14

2590

2030

1680

1540

POM homo

100

10.5

770

630

525

POM homo

100

7

840

700

560

FEP

100

5.25

78.4

61.6

53.9

POM homo

100

3.5

910

770

630

FEP

100

3.5

93.1

73.5

62.3

FEP

100

3.5

31.5

20.3

17.5

420 490

(Continued )

342

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.18 Examples of Creep Modulus (MPa) Versus Time at Various Temperatures for Various Loads.—Cont’d Time (h)

1

10

100

1000

Temperature (°C)

Load (MPa)

FEP

100

1.4

119

94.5

78.4

FEP

100

1.4

51.1

42

37.1

COC

90

20

500

180

40

COC

90

15

750

400

214

90

14

2310

1750

1330

90

8.6

1800

720

430

Thermoplastics

POM homo

Grade

20% GF

COC

Creep Modulus (MPa)

1120

ABS

HR

90

7

980

497

385

280

ABS

HR

90

7

770

357

224

161

ABS

HR

90

7

700

308

203

133

90

7

84

77

70

PTFE PA6

Low GF

90

5.6

623

574

532

ABS

HI

90

3.5

770

371

238

90

3.5

105

84

70

PTFE

168

PEI

30% GF

80

35

8050

8050

6230

6020

PEI

20% GF

80

35

6090

5810

4690

4480

PEI

10% GF

80

35

4200

3920

2940

2800

80

35

2660

2520

2240

2030

2870

2590

PEI POM Homo

20% GF

80

22

3745

PEI

30% GF

80

21

8610

8540

7000

6510

PEI

20% GF

80

21

6650

6510

5110

4900

PEI

10% GF

80

21

4480

4130

3430

3150

PEI

80

21

2800

2730

2520

2450

POM homo

80

17.5

2100

1610

1260

80

14

1974

1750

1463

POM homo

80

14

1120

910

700

POM homo

80

10.5

2310

2100

1680

1400

80

10.5

1120

980

770

525

PA12

80

9.8

252

245

210

189

POM homo

80

7

2660

2100

1540

1260

PA

POM homo

Transparent

20% GF

1078

PA

Transparent

80

7

1995

1792

1526

1162

POM homo

20% GF

80

7

1190

980

770

560

POM Co

25% GF

80

3.5

2870

2380

1820

1330

POM homo

20% GF

80

3.5

1260

1050

840

630 (Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

343

Table 7.18 Examples of Creep Modulus (MPa) Versus Time at Various Temperatures for Various Loads.—Cont’d Time (h) Thermoplastics

Grade

POM Co

1

Temperature (°C)

Load (MPa)

80

3.5

700

10

100

Creep Modulus (MPa) 616

539

476

2870

2660 525

POM Co

25% GF

80

3.5

3745

ABS

HR

70

10.5

1841

1421

945

70

10.5

714

581

490

PA6

1000

ABS

HR

70

7

1841

1631

1029

588

ABS

HR

70

7

1190

910

567

427

ABS

HI

70

7

910

658

399

273

ABS

HI

70

7

770

420

245

175

ABS

HR

70

3.5

1841

1750

1400

728

ABS

HI

70

3.5

770

441

252

182

ABS

HM FR

70

3.5

840

434

273

168

ABS

HI

70

3.5

700

413

252

168

ABS

HM

70

3.5

770

413

238

154

ABS

FR

70

3.5

644

364

210

140

ABS

HI FR

70

3.5

504

266

154

105

60

21

2250

2200

2050

60

21

651

518

420

PA6

60

21

231

196

168

ASA

60

15

1000

600

400

PSU PA6

Low GF

POM homo

20% GF

60

14

2940

2240

1750

1330

ABS

HR

60

14

1680

1120

840

644

60

14

1330

980

840

700 385

POM homo ABS

HI

60

14

1330

700

511

PA6

Low GF

60

14

714

616

560

PA6

60

14

329

280

224

ABS

60

10.5

1176

889

ABS

HI

60

10.5

980

770

546

378

ABS

HI

60

10.5

1260

490

315

231

POM homo

20% GF

60

7

3710

3220

2450

1960

POM h omo

60

7

1610

1330

1050

840

ABS

60

7

1197

952

532

ABS

HM HR

60

7

1330

910

630

PA6

Low GF

60

7

917

798

665

490

(Continued )

344

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.18 Examples of Creep Modulus (MPa) Versus Time at Various Temperatures for Various Loads.—Cont’d Time (h)

1

10

100

1000

Thermoplastics

Grade

Temperature (°C)

Load (MPa)

ABS

HI

60

7

1050

770

581

406

ABS

HM FR

60

7

1190

686

441

301

ABS

FR

60

7

910

567

357

245

ABS

HI

60

7

840

546

364

259

ABS

FR

60

7

1050

469

266

189

ABS

HI FR

60

7

700

413

259

175

ECTFE

60

7

469

322

252

PTFE

60

7

129

114

60

3.5

4760

4130

2870

2100

POM homo

60

3.5

1680

1400

1050

840

ABS

60

3.5

1127

924

539

ABS

60

3.5

1190

770

525

378

POM homo

20% GF

Creep Modulus (MPa)

ABS

HM

60

3.5

1120

630

392

287

ABS

HI

60

3.5

1260

525

350

252

ABS

FR

60

3.5

770

504

336

245

ABS

FR

60

3.5

1050

483

294

196

PP homo

60

3.5

360

294

276

234

PTFE

60

3.5

217

182

105

ABS

HR

50

14

1890

1750

1260

980

ABS

HI

50

14

1470

1330

840

616

50

14

1680

1330

1120

840

POM homo ABS

FR

50

14

1610

1120

658

413

ABS

HM

50

10.5

2030

1540

980

581

50

10.5

1750

1400

1120

910

POM homo ABS

FR

50

10.5

1540

1120

770

483

ABS

HI

50

10.5

1330

910

595

420

ABS

HI FR

50

10.5

1330

840

511

322

50

7

1750

1400

1190

980

50

7

1680

1330

980

770

50

7

1680

1190

840

602

POM homo ABS

HM HR

ABS ABS

HI

50

7

1330

1190

910

665

ABS

FR

50

7

1610

1120

700

462

50

3.5

1869

1617

1400

PMMA

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

345

Table 7.18 Examples of Creep Modulus (MPa) Versus Time at Various Temperatures for Various Loads.—Cont’d Time (h) Temperature (°C)

Load (MPa)

50

3.5

50

3.5

POM h omo

50

ABS

Thermoplastics

Grade

PMMA ABS

HM

1

10

100

1000

Creep Modulus (MPa) 1820

1540

1365

2030

1610

1050

630

3.5

1820

1470

1190

1050

50

3.5

1610

1190

840

581

ABS

HI

50

3.5

1330

1050

672

434

ABS

HI

50

3.5

1470

1050

700

525

ABS

FR

50

3.5

1260

840

560

392

PA6

Low GF

40

28

1435

1029

728

PE

20% GF

40

14

1960

1750

1610

PA6

Low GF

40

14

1505

1197

903

PTFE

40

7

168

140

112

PMMA

40

3.5

2212

1925

1680

PMMA

40

3.5

2170

1890

1645

PTFE

40

3.5

413

329

280

FEP

250

21

392

336

259

FEP

250

14

609

560

504

Thermosets

Grade

Temperature °C

Load, MPa

PI

100

10

2857

2500

2222

2000

PI

100

17

2615

2267

2000

1700

PI

300

17

1133

607

• Hygrometry of polyamides and other moisture sensitive polymers is unknown.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

• The lack of data for a defined time or a defined load is not an indication of unsuitability, but is due to the unsuccessful research of data.

Creep Modulus, MPa

Creep can lead to more or less fast breaking or failure according to the used load and temperature. Table 7.19 displays examples of time at rupture for various loads leading to creep strengths definitely lower than engineering strength at break. These data are not comparable because compounds, temperatures, loads, and time erratically and arbitrarily vary.

• A defined family can be found in several lines

• Type of loading is not known; often data result

because grades and/or loads are different and because compounds are different.

from tensile creep tests, but some others result from bending tests or others.

• Errors, lack of accuracy, and method uncer-

• Hygrometry of polyamides and other moisture

tainty need to be verified in the data and the used compound needs to be checked. Results should not be directly interpreted as an indication of the expected service life for any targeted application.

sensitive polymers is unknown.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

• The lack of data for a defined time or a defined load isn’t an indication of unsuitability,

346

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

7.2.2.2 Relaxation

Table 7.19 Creep Strength Examples. Temperature (°C)

Load (MPa)

Time at rupture (h)

Thermoplastics Examples PE

RT

8.75

800

PP GF

RT

35

8000

PP GF

RT

49

1000

PP GF

RT

60

1000

SAN

RT

42

152

PP GF

80

17

11,000

PP GF

80

23

1000

PP GF

80

28

1000

PP GF

80

32

1000

PP GF

80

38

100

PPE

100

14

5900

PPE

100

21

3700

Thermosets Examples EP

120

25

1000

EP

120

49

1

PF

120

20

1000

PF

120

35

1

UP

120

7

1000

UP

120

14

1

but is due to the unsuccessful research of data.

• A defined family can be found in several lines because grades and/or loads are different and because compounds are different.

• Errors, lack of accuracy, and method uncertainty need to be verified in the data and the used compound needs to be checked. Of course, results should not be directly interpreted as an indication of the expected service life for any targeted application. However, from this point of view, thermosets such as epoxies and phenolic resin (PF) seem to be of interest for creep at 120°C. Generally speaking, it can be noted that loads to creep rupture are much lower than engineering strengths.

Relaxation is the time-dependent stress resulting from a constant strain. For a defined part, the stress is a function of the strain level, the application time, and the temperature. The results of tests at a defined temperature can be presented as the curve of the stress versus the time or the curve of the stress retention versus the time. The stress retention for a defined time and temperature is the quotient of the actual measured stress by the original stress at time zero. The stress relaxation modulus, Er(t) is also used, is expressed by Er(t) 5 σ(t)/ε0, where σ(t) is the actual stress at time t; ε0 is the applied constant strain during the experiment. Fig. 7.6(A) shows a diagrammatic example of the retention percentage of stress with a fast drop at the beginning of the test followed by a gentle slope. Fig. 7.6(B) shows a diagrammatic example of the relaxation modulus at four temperatures for the same epoxy/carbon fiber unidirectional (EP/CF UD). Time scale is logarithmic and far lower than that seen in Fig. 7.6(A). The compounds used for building of Fig. 7.6A and B are totally different, preventing any comparison. Table 7.20 displays stress retention and relaxation modulus for various strains leading to actual stresses definitely lower than the original stress. It can be noted that the stress retention can be as low as 26% (or less) at room temperature for a specific engineering compound. Results must be carefully examined:

• These data are not comparable and are quite arbitrary. Test conditions are uncertain notably concerning loading scenario and test temperature for the original stress. Units are different.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

• The lack of data for a defined time or a defined strain is not an indication of unsuitability, but is due to the unsuccessful research of data.

• A defined family can be found in several lines because grades and/or loads are different and because compounds are different.

7: ADVANCED ENVIRONMENTAL

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

347

100%

Stress retention, %

(A)

AND

Time, h

0% 0

500

1000

(B)

Relaxation 10 modulus, GPa 9 8 7 6 5 4 3 2 1 0 0.001 0.01

relaxation modulus versus t 30°C 80°C 120° C 170° C

0.1

1

10

h

Figure 7.6 (A) Relaxation: diagrammatic example of stress retention versus time. (B) Relaxation: diagrammatic example of relaxation modulus versus time.

• Errors, lack of accuracy, and method uncertainty need to be verified in the data and the used compound needs to be checked. Results should not be directly interpreted as an indication of the expected service life for any targeted application.

7.2.2.3 Fatigue The cyclic mechanical leads to a speedier failure The Wohler curves or SN stress or strain (S) leading of cyclic loading. According to the actual stress can:

loading of a polymer than an instant loading. curves plot the level of to failure after N cycles plastic and formulation,

• Continuously decrease during fatigue test or • Decrease abruptly at the beginning of fatigue test and then gently decrease

• Decrease abruptly at the beginning and then stabilize. Fig. 7.7 shows four diagrammatic examples of the SN curves for four engineering plastics tested

between 100,000 and 10,000,000 cycles. The fast drop of strength at the beginning is not visible because it generally appears before 100,000 cycles. These experiments are not comparable because of differing procedures. Data cannot be used for design or economic purposes. Tests must be run with chosen compounds in actual use conditions. Two basic types of tests coexist, namely “at defined stress” or “at defined strain.” Thermoplastics being sensitive to creep, fatigue tests at defined strain are less severe than those at defined stress for comparable original stresses. Experimentation has shown that the frequency of loading may affect the number of cycles leading to failure at a given level of stress (see Fig. 7.8). Often tests are run at frequencies lower than 30 Hz. Generally speaking, higher frequencies lead to higher internal generation of heat and more rapid failure. The waveform (sine, square, triangle, sawtooth, etc.) is also of importance. In addition to the mode of loading, the loading level must be examined in detail taking into account minimum, maximum, and average stresses (or strains). The surrounding temperature and the geometry of the tested sample have an effect on heat dissipation. Thick samples and “high” surrounding

348

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.20 Relaxation of Some Specific Grades. Time 1h

10 h

30 h

100 h

1000 h

Thermoplastics: Stress Retention Examples Temperature (°C)

Strain

Stress Retention (%)

PVC

RT

0.03

86

80

76

PVC

RT

0.005

83

75

67

58

50

PE HD

RT

0.02

87

77

70

65

46

PP

RT

0.02

88

78

73

70

67

PS

RT

0.01

85

73

66

61

38

PS

RT

0.01

87

77

71

65

47

POM

RT

0.003

80

70

63

57

50

POM

RT

0.009

79

70

60

54

45

POM

RT

0.05

70

57

53

45

37

POM

RT

0.125

65

50

45

35

26

PBI

RT

0.01

80

75

71

67

58

PEEK

RT

0.01

88

84

82

79

74

PEI

RT

0.01

75

70

68

65

57

PPS

RT

0.01

80

77

77

76

75

PMMA

RT

0.05

80

PVC

40

0.03

74

68

64

PVC

50

0.03

68

62

58

PVC

60

0.03

53

37

31

PBI

150

0.01

46

45

43

41

38

PEEK

150

0.01

32

28

25

21

18

PEI

150

0.01

51

45

41

37

27

PPS

150

0.01

19

15

14

13

12

Thermosets: Relaxation Modulus (MPa) Examples Strain

Time 1h

10 h

MPa

MPa

EP/CF laminate

30°C

Unknown, low

8600

8400

EP/CF laminate

80°C

Unknown, low

6800

6650

EP/CF laminate

120°C

Unknown, low

5000

4200

EP/CF laminate

170°C

Unknown, low

500

350

25%

4.2

4.1

Silicone

temperatures lead to a temperature rise and have a harmful effect when low temperatures, notably subzero ones, lead to a modulus increase and

30 h

100 h

1000 h

brittleness. According to the type of solicitation, a higher thickness can lead to a higher deformation of the outer surface.

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

349

35 PI

30

PA

25

PMMA

20

PTFE

15 10 5 0 100,000

1,000,000

10,000,000

Figure 7.7 SN curves: diagrammatic examples based on PI, PA, PMMA, and PTFE. PTFE, polytetrafluoroethylene; PMMA, polymethylmethacrylate; PA, polyamide; PI, polyimides. 45

MPa 35

25 0

2000

4000

6000

Cycles

Figure 7.8 SN curves for the same polymer at three frequencies from 0.03 to 0.5 Hz.

It must be noted that an increase of the temperature of the material under dynamic loading leads to the usual consequences such as modulus reduction and aging. Table 7.21 displays the maximum stress leading to failure for the mentioned number of cycles. Tests procedures are not comparable, but stresses are definitely lower than the engineering strength at break. Most tests are run at room temperature and others are run at higher temperatures. Results must be carefully examined:

• The lack of data for a defined number of

• Those data are not comparable and are quite

tainty need to be verified in the data and the used compound need to be checked.

arbitrary. Test conditions are uncertain notably concerning the loading scenario (minimum, maximum, and average stresses or strains) and loading conditions (frequencies, waveform).

• Hygrometry of polyamides and other moisture sensitive polymers is unknown.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

cycles is not an indication of unsuitability, but is due to the unsuccessful research of data.

• A defined family can be found in several lines because grades and/or loads are different and because compounds are different.

• Properties of laminates and other composites are highly dependent of the form of the reinforcements, for example, sheet molding compound (SMC), fabrics, UD tapes, etc.

• Errors, lack of accuracy, and method uncer-

Results should not be directly interpreted as an indication of the expected service life for any targeted application.

7.3 Poisson’s Ratios Poisson’s ratio is the ratio of transverse contraction strain to longitudinal extension strain in the

350

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.21 Dynamic Fatigue Examples. Number of Cycles Temperature

1.E 1 03

1.E 1 04

1.E 1 05

1.E 1 06

1.E 1 07

1.E 1 08

Maximum Stress to Failure (MPa) Thermoplastics PEI CF

RT

PAI CF

150

110

77

RT

110

98

81

68

PASA GF

RT

105

85

65

55

PEI GF

RT

90

65

PAI GF

RT

96

70

53

41

PASA GF

RT

90

70

50

35

PEEK CF

RT

93

85

79

73

PPS 40GF

RT

95

85

75

70

65

LCP GF

RT

85

72

62

50

LCP mineral

RT

80

63

47

30

PAI

RT

80

55

41

35

PC 20GF

RT

75

55

40

35

PBT 30GF

RT

70

51

36

29

PEEK

RT

72

70

69

68

PEEK GF

RT

75

70

65

PA GF

RT

PPS GF and mineral

RT

POM 30GF

RT

PEI

RT

75

58

PVDF

RT

55

52

PPE 30GF

RT

PVDF

RT

PP talc

120

75

67

63

52

41

60

50

41

50

45

40

23

50

45

40

35

45

42

40

38

RT

42

32

28.5

PP talc

RT

38

22

17

POM

RT

35

27

21

PMMA

RT

44

PA46

RT

42

32

29

PA

RT

31

25

20

PE, HD

RT

31

24

17

PPE

RT

35

28

21

15

ETFE GF

RT

29

26

24.5

PC

RT

40

25

15

ABS

RT

33

25

17

48

38

35

15

10

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

351

Table 7.21 Dynamic Fatigue Examples.—Cont’d Number of Cycles Temperature

1.E 1 03

1.E 1 04

1.E 1 05

1.E 1 06

1.E 1 07

1.E 1 08

Maximum Stress to Failure (MPa) PVC

RT

33

23

17

12

PES

RT

42

15

12

PS

RT

14

10.5

ETFE

RT

14

13

12

PMMA

RT

25

POM

RT

PMMA

RT

31

PVDF

60

40

35

PVDF

100

24

22

PPS 40GF

120

75

65

55

49

38

PPS GF and mineral

120

55

49

41

37

33

PPS 40GF

150

51

45

35

27

25

PPS GF and mineral

150

41

35

30

25

20

32

Thermosets PI

RT

31

28

26

PI graphite

RT

24

22

20

PI unknown grade

RT

40

PI unknown grade

RT

35

PI unknown grade

100

32

PI unknown grade

100

28

PI unknown grade

200

25

PI unknown grade

200

18

PI unknown grade

260

20

PI unknown grade

260

12

EP GF laminate

RT

260

190

120

EP unknown grade

RT

188

170

152

145

EP unknown grade

RT

160

145

130

110 (Continued )

352

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.21 Dynamic Fatigue Examples.—Cont’d Number of Cycles Temperature

1.E 1 03

1.E 1 04

1.E 1 05

1.E 1 06

1.E 1 07

1.E 1 08

Maximum Stress to Failure (MPa) PF/GF laminate

RT

278

231

185

138

PF/GF

RT

276

225

175

124

73

UP/GF laminate

RT

106

93

81

68

55

UP/GF laminate

RT

83

77

70

64

57

UP/natural fiber

RT

31

27

23

19

Number of cycles: Maximum Stress (MPa) to Failure 1

5

30

50

100

PF/GF

200°C

320

307

283

265

258

PF/GF

200°C

254

245

249

214

219

direction of the stretching force. Tensile deformation is considered positive and compressive deformation is considered negative. The Poisson’s ratio (ν) is linked to E (tensile or flexural modulus of elasticity) and G (shear modulus or modulus of rigidity): E 2 2G E 5 21 v5 2G 2G v52

E 2 3K E 52 1 1=2 6K 6K

200 209

Only properties measured on the actual used compound must be considered. The Poisson’s ratio of a given compound can vary with temperature. For example, between 2100°C and 80°C:

• Poisson’s ratio evolves between 0.386 and 0.401 for a specific polycarbonate.

• Poisson’s ratio evolves between 0.352 and 0.359 for a specific PS.

• Poisson’s ratio evolves between 0.339 and 0.376 for a specific polymethylmethacrylate.

Table 7.22 displays some Poisson’s ratios of thermoplastics and a few inorganic materials for comparison. Tests are run at room temperature. Results must be carefully examined:

• Those data are not comparable and are quite

• Poisson’s ratio evolves between 0.364 and 0.385 for a specific PVC.

• Poisson’s ratio evolves between 0.35 and 0.39 for a specific polyphenylene sulfide (PPS) 40 GF.

arbitrary. Test conditions are uncertain.

• Reinforcement, plasticization, impact modification, etc., are not always pointed out.

• A defined family can be found in several lines because grades and compounds are different.

• Errors, lack of accuracy, and method uncertainty need to be verified in the data and the used compound needs to be checked. These theoretical data cannot be used for designing, computing, or to make economic predictions.

7.4 Electrical Properties Electrical properties can be affected by:

• the formulation of the considered polymer; • the test conditions including frequency of the electric current;

• the environment (humidity, temperature, chemicals uptake, etc.);

• aging conditions including dynamic loading.

7: ADVANCED ENVIRONMENTAL

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ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

353

Table 7.22 Examples of Poisson’s Ratios at Room Temperature. Thermoplastics 0.46 2 0.48

PTFE

0.46

PE UHMW

0.46

FEP

0.45

PE-HD

0.45

COPE

0.45

PE HD

0.45

PEEK 30GF

0.44

PEEK 30CF

0.43 0.45

ETFE

0.4

PP

0.4

PA66, extruded

0.4

PESU

0.4

PEEK, PEK

0.38 0.40

PBT 30 GF

0.39

PC

0.36 0.39

PVC

0.38

PET/PC

0.38

PC GF

0.38

PA/ABS

0.37 0.38

COC

0.34 0.41

PMMA

0.35 0.39

PA6 33GF

0.35 0.39

ABS

0.37

PSU

0.36

PC/ABS

0.36

PEI

0.35 0.40

PPS 40 GF

0.35

PP 40 GF

0.35

POM

0.35

PS crosslinked

0.34 0.35

PET 30 GF

0.34

PS impact

0.34

PVDF

Inorganic Materials

0.44

Lead

0.35

Aluminum

0.34 0.37

Copper

(Continued )

354

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.22 Examples of Poisson’s Ratios at Room Temperature.—Cont’d Thermoplastics 0.33 0.35

PS

0.33

PCTFE

0.32 0.34

PA66 mineral

0.31 0.38

PPE

0.27 0.28

PPE GF

0.25

TPU

0.1 0.12

Inorganic Materials

0.29 0.30

Steel

0.17

Fused quartz

Twintex PP/GF fabric Thermosets

0.3

PF

0.33 0.35

EP

0.34 0.35

PI

0.3 0.33

UP

0.3

UP GF and mineral SMC

All tables gather a limited number of examples tested in undefined conditions and are not rules. Different data may be quoted in scientific or technical literature.

7.4.1 Resistivity Examples Generally speaking, thermoplastics and thermosets are insulating materials, but some are conductive or antistatic. Resistivity can be affected by the formulation of special compounds. For a defined compound, initial resistivity may be modified by the environment (humidity, temperature, chemicals uptake, etc.) and aging including dynamic loading. Table 7.23 shows examples of resistivity at room temperature and normal hygrometry. Of course, other data may be quoted elsewhere.

7.4.2 Dielectric Strength Examples Table 7.24 shows examples of dielectric rigidity (kV/mm) at room temperature. Generally speaking, thermoplastics and thermosets dielectric strengths are in the range of a few tens of kV/mm, but figures are lower for conductive or antistatic grades. At the opposite end, some specific grades lead to higher data due to specific formulations. For a defined compound, the initial dielectric rigidity may be modified by the environment (humidity,

temperature, chemicals uptake, etc.) and aging. Of course, other data may be quoted elsewhere. Statistical analysis of examined data leads to: Mean

24 kV/mm

Median

20 kV/mm

SD

17

Minimum

0.4

Maximum

140

Samples

68

7.4.3 Examples of Dielectric Loss Factors Table 7.25 displays examples of dielectric loss factors (1024) at room temperature and normal hygrometry. Data can be affected by the formulation of special compounds. For a defined compound, initial figures may be modified by the state of cure (for thermosets), the frequency of the electric current, the environment (humidity, temperature, chemicals uptake, etc.) and aging including dynamic loading. Be cautious, frequencies are not defined and some data may be linked at high frequency measures that can lead to different figures. Of course, other data may be quoted elsewhere.

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

Table 7.23 Resistivity examples, Log (ohm cm). Mini

Maxi

355

Table 7.23 Resistivity examples, Log (ohm cm).— Cont’d

Examples of Thermoplastics

Mini

Maxi

PPS conductive

21

3

PSU, PESU

16

18

PEEK CF

5

5

PFA, FEP, PTFE

16

18

PA 66 mineral

11

11

Examples of Thermosets

PA 66 GF

11

13

EP aluminum powder

PK GF

13

13

UP antistatic

6

7

PVDF

12

14

PI graphite

2

13

Soft PVC

10

16

PF/GF molding

9

12

PA 11 or 12

14

14

MF modified

10

12

PA 6, 66, 6 10

14

14

PF organic filled

9

13

ASA

14

15

MF filled

10

13

PBI

14

15

Silicone foam

11.5

12.5

PCTFE

14

15

UF cellulose

10

14

LCP GF, mineral

15

15

UP filled, molding

10

15

PA 4 6

15

15

UP SMC

11

14

PMMA

14

16

Fluorosilicone

12.5

13.5

PC

15

16

UP/GF BMC

11

15

PC GF

15

16

PUR

12

15

POM

15

16

Silicone RTV

12

15

POM GF

15

16

UP cast

12

15

PPE

15

16

PI molding

12

16

PPE GF

15

16

PUR foam

14

15

PPS GF and mineral

15

16

PUR RIM

14

15

PVC-U

15

16

EP filled, molding

12

17

ABS

16

16

EP neat

12

17

Acrylic imide

16

16

PI/GF molding

14

15

LCP

16

16

PI neat

14

16

PA Ar GF

16

16

Silicone HVR

14

16

PBT, PET

16

16

Silicone resin

14.5

15.5

PBT GF

16

16

PEI

15

17

ETFE

15

17

PEEK

16

17

PESU GF

16

17

PP, PMP GF, Talc

16

17

PS

16

17

PE, PP, PMP

16

18 (Continued )

0.5

1

7.5 Flammability: Limiting Oxygen Index examples The (limiting) oxygen index (OI or LOI) is an indicator of the flammability of polymers, which is one of the parameters of fire resistance. Many other indicators coexist, but there is not a true correlation between them. The LOI is the minimum percentage of oxygen in an atmosphere of oxygen and nitrogen that

356

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.24 Examples of Dielectric Rigidity (kV/mm). Min

Max

CPE

12

13

CA

8

PC, structural foam

Table 7.24 Examples of Dielectric Rigidity (kV/mm).—Cont’d Min

Max

PEI

28

33

18

PBT, PET GF

25

36

14

15

PVDF

10

60

SMA

16

16

MABS

34

37

PESU

16

16

EMA

31

43

ABS

12

20

PA semi-aromatic

25

50

PMI

17

17

PVCC

20

60

SAN

12

24

LCP

37

47

PCT

16

21

POM

16

70

PMMA

15

22

LCP GF, mineral

37

50

PVDC

15

23

PBT, PET

45

60

POM GF

16

23

PMP

64

65

PS

12

28

Thermosets

PEEK

20

20

UP antistatic

1

2

Soft PVC

10

30

Silicone foam

1.5

2.5

PPE

16

25

EP aluminum powder

0.4

8

PA 6 10

16

26

PI graphite

9

10

PBI

21

22

UP SMC

10

15

PPE GF

22

22

UP/GF BMC

10

15

PPS GF, mineral

13

31

UF cellulose

12

16

PA 66, 6

10

35

PI molding

10

19

PP

20

28

EP filled, molding

10

20

PSU

20

30

Silicone RTV

10

20

PA GF

21

30

Fluorosilicone

13

19

EVA

25

27

PI neat

10

22

PTFE, PFA, FEP

13

40

PI/GF molding

10

22

PC

15

38

PF organic filled

8

25

PA 4 6

16

37

EP neat

16

20

PEI GF, mineral

20

33

MF filled

8

30

PAI

23

33

PF/GF molding

10

30

PC GF

20

38

Silicone resin

10

30

PVC-U

10

50

MF modified

20

25

PA 11 or 12

25

35

Silicone HVR

20

30

PE

16

45

UP cast

15

45

PUR

15

140

Thermoplastics

(Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

Table 7.25 Examples of Dielectric Loss Factors (1024). Mini

Table 7.25 Examples of Dielectric Loss Factors (10 2 4).—Cont’d Mini

Maxi

PMMA

200

2000

200

2000

Maxi

Thermoplastics

357

PE-UHMW

2

2

PA 11 or 12

PE, PP

3

5

Thermosets

PTFE, PFA, FEP

2

7

Silicone resin

10

20

PPE

4

9

PI neat

18

18

PP talc

7

11

Fluorosilicone

30

30

PEI mineral

10

15

Silicone HVR

2

98

PPE GF

10

15

PI graphite

45

10

PE-HD

3

20

Silicone RTV

2

198

PP GF

10

20

Silicone foam

10

190

PPS GF

13

20

PI molding

10

390

PEI

13

25

PI/GF molding

10

390

PS

1

28

EP neat

20

500

PEEK

30

30

PUR

100

500

LCP

40

40

EP filled, molding

80

820

POM GF

20

50

UP cast

20

980

PSU, PESU

10

50

UF cellulose

200

799

PEI GF

15

53

EP aluminum powder

1010

990

LCP GF

40

60

MF filled

100

2900

PBI

40

60

PF organic filled

100

2900

POM

10

70

PF/GF molding

300

2700

PC GF

9

75

MF modified

200

3800

ETFE

6

100

PC

7

100

PET, PBT GF

20

160

PBT, PET

10

200

PVC-U

60

200

PCTFE

10

250

ABS

20

350

PPS GF and mineral

70

580

PA 6, 66

100

600

PA Ar GF

700

700

CA

100

1000

PA 66 GF, mineral

200

1500

Soft PVC

400

1600

PVDF

200

1700 (Continued )

sustains the flame of an ignited polymer sample. Plastics with high LOIs burn with difficulty and low-LOI plastics, as per example 18, burn easily. Table 7.26 displays examples of LOIs:

• Inherent OIs are values for (expected) unmodified polymers.

• Noted maxima are the highest values found in the literature taken into consideration. Higher values may be possibly found elsewhere according to the considered literature and specific formulations for special applications. Maximum OIs correspond to fire retardant versions.

• Average LOI and median account for 30 with a broad range of between 16 and 98.

358

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.26 Examples of Oxygen Index. Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

Halogenated Molecule

FEP

95

96

PFA

95

96

PTFE

95

96

PTFE CF

95

96

PTFE GF

95

96

FEP GF

95

95

PCTFE

90

98

PVDC

60

60

PBI

58

ECTFE

58 52

60

PES CF

51

52

PAI GF

51

51

PVCC

50

65

PEI GF

50

50

PES friction

48

52

PEI GF milled

47

50

PEI mineral

47

48

PEI

47

50

PPS GF and mineral

45

53

PAI CF

45

52

PPS conductive

45

48

PAI

45

45

PI TP

44

53

PI TP GF

44

53

PAI friction

44

44

PAI mineral

44

44

PVDF Mica

44

44

PPS CF and GF

43

50

PPS GF

43

49

PPS long GF medium level

43

49

PPS long GF high level

43

49

PPS Far

43

49 (Continued )

7: ADVANCED ENVIRONMENTAL

AND

ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

359

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

PPS

43

47

PPSU

43

44

Halogenated Molecule

PVDF

42

67

PVDF friction

40

67

PVDF CF

40

65

PVC unplasticized

40

52

PPS CF

40

49

PES GF

40

48

PVC GF

40

45

PEEK CF

38

47

PPSU GF

38

42

LCP GF

37

49

LCP mineral

36

37

LCP

35

50

PEEK/PBI

35

45

PEEK/PBI GF

35

45

PSU/PBT GF

35

35

PVF

35

35

PES

34

39

PSU

32

40

PA 6 FR

31

32

ETFE

30

40

PSU

30

40

PSU GF

30

40

PSU mineral

30

40

PSU modified

30

38

ETFE GF

30

32

ABS/PVC

28

37

ABS FR

28

28

Polyarylate

26

36

PPA

26

35

PA 66 mineral

26

33

Polyarylate GF

26

28

PPA mineral

26

26 (Continued )

360

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

PA 4 6

25

27

PEEK GF

24

45

PAEK 30% GF

24

45

PEEK

24

35

PAEK (PEK, PEKK, PEEK, PEEKK, PEKEKK)

24

35

PPA GF

23

35

PET

23

30

PPA long GF

23

24

PC

22

41

PC GF

22

40

ABS/PC

22

34

ABS/PC medium level long GF

22

34

ABS/PC conductive

22

34

PA 11

22

33

PA 12

22

33

CPE

22

25

PAA high level GF

22

25

ABS/PC low level long GF

22

24

ABS/PC GF

22

23

PA 11 GF

22

22

PA 11 or 12 plasticized

22

22

PA 12 GF

22

22

TPE based on PVC

Halogenated Molecule

21

39

PA 66

21

36

PBT

21

35

PC/PBT

21

35

PC/PBT GF

21

35

PA 66 medium level GF

21

33

PA 66 medium level long GF

21

33 (Continued )

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361

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

PCT GF

21

30

PA 66 high level long GF

21

27

PA transparent

21

26

PAA medium level GF

21

25

PAA mineral

21

25

PET amorphous

21

25

PK GF

21

24

PA 6

21

23

PA 66 high level GF

21

23

PA 66 impact medium level GF

21

23

PET GF

21

23

PAA medium level CF

21

22

PBT medium level GB

21

22

PBT medium level GF

21

21

PBT GF and mineral

21

21

PBT long GF

21

21

PK

21

21

PVC plasticized

20

Halogenated Molecule

40

PA 6 GB

20

30

PA 6 medium level GF

20

30

PA 6 medium level long GF

20

30

PA 6 GF recycled

20

30

PA 6 high level GF

20

30

PA 6 high level long GF

20

30

PA 6 mineral FR

20

30

PA 66 GB

20

30

COPE high Shore D

20

28 (Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

PA 6 10

20

27

PA 6 12

20

23

PA 6 12 GF

20

23

PA 6 recycled

20

22

ABS/PA

20

21

ABS/PA 20GF

20

21

COPE low Shore D

20

21

COPE bio

20

21

EVA

19

39

ASA/PC

19

30

PET/PC

19

25

Acrylique imide

19

21

ASA/PBT GF

19

21

PBT long CF

19

21

PBT CF

19

21

PET/PC GF

19

21

PMI or PMMI

19

20

PTT bio

19

20

PTT bio GF

19

20

PPE

18

36

PPE GF

18

36

PPE/PA

18

36

ABS conductive

18

28

SAN GF

18

28

TPS Shore D

18

27

PPE mineral

18

22

ASA/PMMA

18

20

PMMA

18

20

PMMA GF

18

20

PMMA antistatic

18

20

PMMA impact

18

20

ABS

18

19

ABS GF

18

19

ABS GB

18

19

Halogenated Molecule

(Continued )

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ENGINEERING PROPERTIES TO SUPPORT ECO-DESIGN FOR PLASTICS

363

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

ABS CF

18

19

ASA

18

19

MABS

18

19

POM GF

18

19

POM long GF

18

19

POM GB

18

19

POM CF

18

19

POM far

18

19

POM friction

18

19

POM mineral

18

19

PPE CF

18

19

SAN

18

19

SMA

18

19

SMA GF

18

19

POM conductive

18

18

PP antistat

18

18

PP conductive

18

18

TPO Shore D

18

18

TPV Shore D

18

18

PS GF

17

38

PE-HD

17

30

PP mineral

17

30

PP talc

17

30

PS

17

30

PS impact

17

30

PP Co

17

27

PP Ho

17

27

PP/PA

17

20

PP/PA GF

17

20

Starch/co-polyester

17

20

Starch/PS

17

20

PE GF

17

19

PE 60% long GF

17

19

CA

17

18

Halogenated Molecule

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

CAB

17

18

COC

17

18

CP

17

18

PB

17

18

PE-HD antistatic black

17

18

PE-LD

17

18

PE-UHMW

17

18

PE-X crosslinked

17

18

PMP

17

18

PMP GF

17

18

PMP mineral

17

18

PP impact

17

18

PP recycled

17

18

PP low level GF

17

18

PP medium level GF

17

18

PP GB

17

18

PP low level CNT

17

18

PP medium CNT

17

18

PP cellulose fibers

17

18

PP long GF medium level

17

18

PP CaCO3

17

18

PP long GF high level

17

18

PP CF

17

18

PP natural fibers

17

18

PP/EPDM-V

17

18

Starch/PE

17

18

Starch/PP

17

18

TPU GF

17

18

TPU long GF

17

18

TPU bio

17

18

TPU conductive

17

18

Halogenated Molecule

(Continued )

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365

Table 7.26 Examples of Oxygen Index.—Cont’d Inherent Oxygen Index (%)

OI (%) Noted Maximum

Thermoplastics Nonhalogenated Molecule

Halogenated Molecule

Nonhalogenated Molecule

TPU Shore D

17

18

POM homo or copolymer

16

19

Halogenated Molecule

Thermosets General Purpose Grades Oxygen Index (%) PF BMC

OI (%) Noted Maximum 98

MF

35 40

95

UP

22

80

PI

30 44

53

EP

26 32

45

PF

22

50

HVR silicones

23 30

PE-X

17

7.6 Optical Properties: Examples of Transparent or Translucent Plastics

ABS copolymers can be transparent when compounds of SAN and polybutadiene are opaque.

• The actual crystallinity: transparency decreases when crystallinity increases.

The most usual optical properties of transparent plastics are:

• The compound recipe: the use of colorants, fil-

• Light absorption: the percentage of light

lers, reinforcements, nucleating agents, plasticizers, impact modifiers, and other additives.

absorbed by the polymer versus the incident light.

• Light transmission: the percentage of light transmitted through the polymer versus the incident light.

• Haze induced by light scattering within the polymer; a water haze can be caused by absorbed moisture.

• The possible treatments such as, for example, stretching, quenching, annealing, etc.

• The considered light wavelength. Table 7.27 displays some transparent or translucent plastics among others. Only specific grades are transparent or translucent.

• Gloss: capacity of the polymer surface to reflect light in given directions. Transparency and haze depend on, without claiming to be exhaustive:

• The used polymer and possible alloying. For the same designation, some grades can be transparent or translucent while others are not.

7.7 Gas Permeability For films, in several series of experiments concerning various thicknesses of various polymers, permeability coefficients have been calculated for a reference thickness of 40 µm. Units differ for the various gases, but are comparable for the different polymers tested with the same gas. The following

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Table 7.27 Examples of Transparent or Translucent Thermoplastics. Examples of Thermoplastics Acrylic

Polymethylmethacrylate (PMMA) Styrene methyl methacrylate PMMA and PC blend

Polycarbonate (PC)

PC Polycarbonate and polyester amorphous blends

Styrenic

Polystyrene (PS, HIPS, SB) Styrene acrylonitrile copolymer Transparent ABS and methacrylate ABS Styrene maleic anhydride Styrenic block copolymer elastomers (SBC, SBS, SEBS, SIS) Polyphenylene oxide/polystyrene blends (PPO 1 PS)

Chlorinated thermoplastic

Polyvinyl chloride

Olefinic

Clarified polypropylene Polymethylpentene Cyclic olefin (co)polymer Polyolefin elastomer/plastomer (POE/POP)

Polyester

Polyethylene terephthalate Polyethylene naphthalate Polyester copolymers (PETG) Thermoplastic ether ester copolymer elastomer

Cellulosic

Cellulose acetate, butyrate, propionate

Polyamide (PA)

Transparent PA Polyether block amide

Polyurethane

Thermoplastic polyurethane

Ionomer

Acrylate copolymer

Acrylonitrile

Acrylonitrile copolymer

Polyetherimide

Polyetherimide

Polysulfone

Polysulfone Polyethersulfone Polyphenylsulfone

Fluorinated thermoplastics

Fluorinated ethylene propylene Ethylene tetrafluoroethylene Polytetrafluoroethylene Polychlorotrifluoroethylene Perfluoroalkoxy

Thermoplastic polyimide

Polyimide, amorphous

Bio-sourced thermoplastic

Polylactic acid (Continued )

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367

Table 7.27 Examples of Transparent or Translucent Thermoplastics.—Cont’d Examples of Thermosets Polyurethanes (PU)

Neat PU

Unsaturated polyesters (UP)

Neat UP Glass fiber-reinforced UP

Urea formaldehyde (UF)

Neat UF

Epoxies (EP)

Transparent EP

Polyimides (PI)

Transparent PI

Silicones

Transparent silicones

data (without units) are two different examples only given to provide a general idea and cannot be used for designing any parts or goods.

• Water vapor: • Polyethylene (PE) has a low permeability, evaluated from 0.9 to 2.5 compared to the full range of 0.05 400 for all tested plastics. • PVDCs have permeabilities evaluated at 0.07 0.2.

• Air: • PE has a rather high permeability, evaluated at 750 2750 versus full range of 3 2750 for all tested plastics. • PVDCs have permeabilities evaluated at 3 6.

• Carbon dioxide: • PEs have permeabilities

evaluated at 7000 25,000 versus the full range of 30 59,000 for all tested plastics. • PVDCs have permeabilities evaluated at 40 440.

• Nitrogen: • PEs have

permeabilities evaluated at 500 1700 versus the full range of 1 3500 for all tested plastics. • PVDCs have permeabilities evaluated at 1 1.4.

• Oxygen: • PEs have

permeabilities evaluated at 1900 5000 versus the full range of ,1 to 11,000 for all tested plastics. • PVDCs have permeabilities evaluated at 1.1 7.

• Hydrogen: • PEs have

permeabilities evaluated at 6000 20,000 versus a full range of 400 up to 20,000 for all tested plastics. • PVDCs have permeabilities evaluated at 400 900.

These results show that it is essential to test the used compound with the gas used in actual applications.

7.8 Tribological Properties When a plastic is sliding on a counterpart: 2 There is always: • A resistance to the movement • An interface heating and, consequently: • A decrease of the modulus, tensile strength, and abrasion resistance • A change of the CoF • A thermal expansion of the polymer • A wearing of one or the two materials 2 There is possibly: • Fouling after a more or less long time that modifies the roughness, the coefficient of friction (CoF), and leads to the formation of abrasive particles. • Stick slip phenomenon, or stick-slip, is the jerky motion that can occur while two materials are sliding over each other. High differences between static and dynamic coefficients of friction favor stick-slip. Friction and wear can be characterized by the CoF, the wear factor and the pressure velocity (PV) limit.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

368

The CoF is the ratio of the friction force and the vertical force. It is always less than 1 if the polymer is not bonded. In practice, unlike metals, polymers have a low modulus and the vertical force alters the shape of their sliding face. The CoF depends on:

• The substrate material • The surface aspect and roughness of the plastics and the substrate

• The pressure of friction • The moving velocity; notably it must be distinguished between the static and dynamic CoFs

• The environmental conditions, for example,

2 Carbon or aramid fibers to decrease CoF and wear, and enhance mechanical properties. Glass fibers enhance mechanical properties and decrease the wear, but they are abrasive and attack the antagonist surface. According to the circumstances they can increase the CoF.

7.8.1 Coefficient of Friction Statistical analysis of static and dynamic CoFs for 89 samples of various general purpose and tribological compounds tested at room temperature leads to:

hygrometry and temperature

• The initial and final shapes of the sliding surface

• The possible use of lubricants • The duration The PV is the product of the pressure by the velocity. The used units affect the value. Each polymer has a PV limit and must be used only below it. For a defined test, the wear can be expressed by:

• The weight or volume loss • The height loss of the part. • The wear factor k 5 h/(P 3 V 3 t), where h is the wear expressed in height or weight or volume, P is the pressure, V is the velocity, and t is the test duration.

• The specific wear rate 5 V/P 3 d, where V is the volume loss, P is the pressure, and d is the sliding distance.

Tribological properties of a selected plastic family may be unsuitable for the aimed application, thus, needing the use of tribological additives. Of course, those products can modify the other properties. The most current are: 2 Specific fillers: molybdenum disulfure (MoS2), graphite, and, more rarely, boron nitride or silicon carbide. 2 Polymers: polytetrafluoroethylene, silicone masterbatches. 2 Oils: silicones, perfluoropolyether.

Mean

0.22

Median

0.20

SD

0.087

Minimum

0.05

Maximum

0.41

Samples

89

Results must be carefully examined:

• Used data are not truly comparable and are quite arbitrary. Test conditions are uncertain notably concerning the equipment and the test method. The substrate or counterpart is often unknown.

• Compounds may be general purpose or tribological grades.

• Hygrometry of polyamides and other moisture sensitive polymers is unknown.

• Errors, lack of accuracy, and method uncertainty need to be checked along with the used compound.

7.8.2 Limiting Pressure Velocity A plastic subjected to sliding heats up and can eventually reach a point of failure known as the PV limit (maximum of the pressure by the velocity product). The used units affect the value. Each polymer has a PV limit and must be used only below it. In addition, the PV limit is valid only within the P limit, on the one hand, and the V limit, on the other hand. The failure point is usually manifested by an abrupt increase in the wear rate.

7: ADVANCED ENVIRONMENTAL

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As long as the mechanical strength of the material is not exceeded, the temperature of the sliding surface is generally the most important factor. PV limit depends on many parameters such as:

• Hardness, surface finish, conductivity of the counterpart

• • • • •

CoF Ambient temperature Cooling Device design Lubrication if relevant

It is usually prudent to allow a generous safety margin in using PV limits because real operating conditions are often more rigorous than experimental conditions. Statistical analysis of PV limits for 52 samples of various general purpose and tribological compounds tested at room temperature leads to: Mean (MPa m/s)

1.05

Median (MPa m/s)

0.46

SD (MPa m/s)

2

Minimum (MPa m/s)

0.003

Maximum (MPa m/s)

13

Samples

52

References Technical guides, newsletters, and websites 3M, Akzo Plastics, Allied Signal, Allrim, Amcel, APC (AmericanPlasticsCouncil.org), Amoco, Arkema, Arco Chemical, Astar, Atochem, Atofina, Bakelite GmbH, BASF, Bayer, BF Goodrich, BIP, Bisco, BP Chemicals, Braskem, Bryte, Ceca, Celanese, Ciba, Covestro, Cray

369

Valley, Culver City Corp, Degussa, Devcon, Dow, DSM, Du Pont de Nemours, DuPont Dow, Dynamit Nobel, Eastman, Eleco, Emerson & Cumming, EMS, Enichem, Epotecny, Eval, Exatec, Exxon, Ferro, Ferruzzi, FiberCote, Framet Futura, General Electric Plastics, General Electric Silicones, Hexcel, Hoechst, Hu¨ls, ICI, Irathane, Isomeca, Kommerling, Kuraray, La Bake´lite, Loctite, Lohmann, Matweb, Mecelec, Menzolit, Mitsui Chem, Monsanto, Montedison, Naphtachimie, Natureworks, Neste, Nief Plastic, Nippon Gohsei, Nippon Mitsubishi, Nonacor, Norflys, Novamont, Orkem, Owens Corning, Perstop, Phillips Petroleum, PlasticsEurope, PPG, PRW, Raschig, Recticel, Repsol, Rhodia, Rhoˆne Poulenc, Rohm, Schulman, Scott Bader, Shell, Sika, Sintimid, SNIA Tecnopolimeri, SNPE, Solvay, spmp, Stratime, Symalit, Synres, Synthe´sia, T2L, Taber, Technochemie GmbH, Telenor, The European Alliance for SMC, Thieme, Toray, Tramico, Tubize Plastics, Tubulam, Ube, Union Carbide, Uniroyal, Vetrotex, Vyncolit, Wacker, Wilson Fiberfil, YLA.

Further Reading Biron, M., 2014. Thermosets and Composites. Elsevier Ltd. Biron, M., 2015. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2017. Industrial Applications of Renewable Plastics. Elsevier Ltd. Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Modern Plastics Encyclopaedia, McGraw-Hill Publications. Modern Plastics International, Canon Communications LLC, Los Angeles, CA, USA. Plastics Additives and Compounding, Elsevier Ltd. Plastics News.com, Crain Communications. Reinforced Plastics, Elsevier Ltd.

8 Economics Relating to Fossil and Renewable Plastics Economic feature is one of the pillars of sustainable products that must be efficient, competitive, cost effective, and beneficial for everybody. Polymeric raw materials are intrinsically expensive, but their use becomes appealing if one takes into account the processing costs, the new technical possibilities that they permit, and the total cost at the end of their lifetime. In comparison with traditional materials, plastics generally bring operating benefits during their useful lifetime. That must be taken into account in the end cost (the same for negative features in unfavorable cases if appropriate). Generally speaking, the structure of the cost of plastics parts must obey the general relevant rules and this aspect will not be covered, but some specific points will be clarified. Fig. 8.1 summarily analyses the various components of end costs. Of course, the following information is theoretical and cannot be used for design or financial studies. It is the responsibility of the reader to determine, on the one hand, the appropriate use of each product, processing method, machinery and ideas, and on the other hand, the compliance with processing rules, safety precautions, health hazards, existing national laws and regulations according to the actual context by countries of processing, commercialization, use, and application. Prices and costs for the problem of the reader must be studied according to the actual context and updated.

8.1 Raw Plastics Material Cost: Beware of Unusual “Raw” Materials and Waste Levels First and foremost, the designer must define the selected physical type of the selected material suitable for the selected processing method. The most usual type of plastics compounds is pellets used for injection and extrusion, but other

processing methods use powder, sheets, liquids or pastes, filaments, prepregs, etc. Of course, the cost increases with the sophistication of the selected physical form. There are two common pitfalls related to raw materials:

• Processing methods using sophisticated and expensive “raw” materials

• Processing methods producing high levels of waste and then consuming high levels of raw material

8.1.1 Usual Physical Types of Plastics Raw Materials The price per kg varies from about h1 to about h100 according to the nature of the polymer itself, the volume delivery, the formulation of the grades, and the inclusion of high-cost reinforcements including carbon fibers and so on. The highest prices relate to the polymers with the highest performances, which are also the least used. Fig. 8.2 illustrates this situation (logarithmic scale). Of course, these prices are approximate and cannot be used for economic forecast, competitiveness studies, and so on. Broadly speaking, prices per kg increase from commodities up to specialty plastics as:

• • • •

Commodities: h1(USD1.1) h3 (USD3.2) Engineering plastics: h2.3 (USD2.5) h7 (USD8) Specialty plastics: h4 (USD4.5) h100 (USD107) Fluoroplastics: h15 (USD17) h40 (USD43)

For comparison, the approximate prices per liter of conventional materials are roughly:

• h2 (USD2.2) h5 (USD5.5) for iron and steel • h11 (USD12) h27 (USD30) for special steels • h1 (USD1.1) for wood

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00008-2 © 2020 Elsevier Ltd. All rights reserved.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Polymer raw material

Additives

Reinforcements

Processing

Finishing assembling

Operation, maintenance

Use phase

End-of-life

Collection dismantling recycling

Figure 8.1 Cost structure of plastic parts.

8.1.2 Cost of Sophisticated Raw Materials Certain processes use more or less sophisticated raw materials needing a first transformation, for example:

• Thermoforming uses sheets or films costing about three- to eight-times the pellet prices.

• 3D printing uses plastics filaments costing USD15 to USD35 per kg, about 10- to 20times the pellet cost of common polymers.

• Certain composites use prepreg. For an epoxy/ glass fiber (GF) prepreg, the price may be about USD30 65/kg, that is to say more than 10-times the cost of common plastic pellets

• Fabrication by machining uses preforms manufactured by extrusion or molding. For the simplest cases, rods, bars, or sheets may be used with costs broadly variable with the shape and material. Price may be 5- to 20-times that of pellets and even much higher. For more complex cases, it is necessary to use a simplified mold or die.

These prices are examples and different data may be found elsewhere.

8.1.3 Examples of Additive Costs Apart from reinforcements, additives are numerous and some are more expensive than raw polymer. Fig. 8.3 displays the main additive categories used in thermoplastics. For thermosets, hardeners and so on must be added to cure resins. Average prices for overall additives are roughly estimated from h1.6/kg (USD2/kg) to h2/kg (USD2.2/kg) with a broad range of individual prices from less than h1/kg (USD1.1/kg) for cheap fillers up to tens of h/kg (or USD/kg) for specialty additives. To solve the same problem, it is sometimes possible to choose between different economic routes. For example:

• compatibility between fillers and polymers can

be obtained with silanes ranging from h10/kg (USD11/kg) to h20/kg (USD22/kg) or with functionalized polymers ranging from h3/kg (USD3.3/kg) to h5/kg (USD5.5/kg)

• UV protection can be obtained with cheap carbon blacks (but color is gray to black) or with expensive photostabilizers The final choice depends on the specifications and end-user requirements.

8.1.4 Examples of Reinforcement Costs For the global advanced composites market, the average cost of high-performance fiber reinforcements (carbon, aramid, high-modulus polyethylene (PE), boron, R/S/T-glass, and some E-glass) is estimated from h5 (USD5.5) to h70 (USD80). This moderate price is due to the decrease in carbon fiber price. Some grades could fall to less than h20 (USD22)/kg in the short or medium term. The price of fibrous reinforcements (Fig. 8.4) depends on the nature of the fibers and the form of the reinforcement, (and the delivery volume), namely continuous or chopped fibers, mats, rovings, 2D or 3D fabrics, or unidirectional. The prices of fibers cover a large range, which partly explains the low consumption of fibers other

8: ECONOMICS RELATING

TO

FOSSIL

AND

RENEWABLE PLASTICS

373

PEEK PAI Fluoroplastics LCP PEI PPS EP, specialty electronics UP, Specialty VE PPE P Arylate PC SMA CA PUR PET/PBT SAN POM PA ABS MMA EP, GP MF UP, GP PS PF PVC Bottle PET PE PP UF 1

10

100

Figure 8.2 Plastics raw material costs per kilogram (h/kg).

than those of E-glass. For example, without any warranty: Carbon fiber sleeves

h70 (USD80) h270 (USD300)

Carbon and aramid fiber sleeves

h70 (USD80) h90 (USD100)

Aramid fiber sleeves

h60 (USD70) h73 (USD80)

Basalt fiber

h25 (USD30)

Glass fiber chopped strand mat

h0.9 (USD1)

Fiber glass woven rovings

h0.7 (USD0.9) h7 (USD8)

The prices of sandwich composite cores (Fig. 8.5) range from 1 (reference) for balsa to 5 for the aramid honeycombs.

8.1.5 Beware of the Actual Consumption of Plastic Compared to the Weight of the Part Certain part design, selection of processing method, and machine may be inherently productive of high levels of waste even if there is no processing trouble. For instance, there some striking examples, without claiming to be exhaustive:

• Tiny injected parts can cause high levels of sprues and runners. For example, “The Fallacies

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Additives

Property enhancers

Sensorial properties

Mechanical performances

Processing improvers

Rheology modifiers

Lubricants

Release agents

Long-term behavior

Heat aging

Weathering

Others

Cost cutters

Fillers

Regrind recycled

Foaming agents Specific characteristics

FR

Conductive

Tribologic

Miscellaneous

Figure 8.3 Examples of additives for thermoplastics.

70% versus the worst one, and in addition, the cycle time is divided by 2.3.

E-glass fiber

• Cutting of circular parts from sheets or cutting

R-glass fiber Aramid fiber Carbon fiber

Figure 8.4 Relative reinforcements.

costs

of

various

fiber

of Injection Molding as compared to MicroMolding” by Scott Herbert, Rapidwerks Inc. (www.rapidwerks.com/media/; TheFallacies OfInjectionMolding.pdf) studies two options for the molding of a part weighing 0.017 g. In each case sprue/runner weight is 0.165 or 0.044, that is to say 3- to 10-times the part weight. The best solution leads to a saving of more than

blanks for thermoforming; without any error or other trouble, the use of a circular shape cut in a square of the same diameter, 10 cm for example, leads to an inherent cut-off estimated to be about 20%. If the sheet width is not a multiple of the circle diameter, the unused edge must be added to the waste.

8.2 Processing Costs As already seen in Chapter 2, Plastics Overview: Outline of the Current Situation of Plastics, satisfactory combination of part, polymer, and process, is essential:

• each process does not allow for the fabrication of all types of parts

8: ECONOMICS RELATING

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375

Balsa Aluminum honeycomb PVC foam Aramid honeycomb

Figure 8.5 Relative costs of various cores for sandwich composites.

• polymers are not all suitable for processing by all methods

• machinery is often dedicated to a family of plastics, thermoplastics, thermosets, or composites. For the choice of process, the main points to be considered include, but are not limited to:

• • • • •

Thermoforming Welding Machining Boiler making and fabrication 3D printing

Processes for thermosets include, among others:

• the polymer family: thermoplastics, thermosets, or composites

• the shape: parts of all shapes, limited or large sizes, unlimited length, microparts, etc.

• the required aspect • the quantity to be produced by year, by run, etc.

• the available or potential machinery and tools Processes for thermoplastics include among others:

• • • •

Injection molding Injection and extrusion blow molding Rotomolding Compression molding (not much used for thermoplastics)

• Compression transfer molding (not much used for thermoplastics)

• Slush molding used with thermoplastics in powder form for the fabrication of automotive parts

• • • • •

Extrusion and connected processes Calendering Casting, pouring Dipping Low-pressure injection molding, reaction injection molding (RIM), and reinforced RIM (RRIM) for liquid polyamide (PA)

• • • • • •

Compression molding Compression transfer Injection molding Casting Low-pressure injection molding, RIM, RRIM Boiler making is reduced because of the 3D network that forbids thermoforming and welding

• Machining • 3D printing Please note that machines having the same name as those dedicated to thermoplastics are technically different, thermosetting resins having to be cured. Processes for composites differ according to the nature of the matrix, thermoplastic, or thermoset polymer and included among others are:

• Atmospheric molding processes: hand lay-up, spray lay-up

• Liquid molding: RRIM, resin transfer molding (RTM), impregnation, infusion, etc.

• Solid state molding: compression and injection, sheet molding compound, bulk molding compound, ZMC, etc.

• Prepreg systems • Bag molding • Filament winding

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Centrifugal molding

processing equipment, and other realities on the ground are closely linked, meaning that general rules are often exceeded. The theoretical information provided here should not be construed as a rule and the practical window is drastically broader.

Continuous sheet manufacture Pultrusion Sandwich composites 3D printing, etc. Machining: Machining destroys the gelcoat if it exists. To avoid the risks of a later attack, it is necessary to remake a new gelcoat locally. Machining cannot be done in all directions.

• Assemblage: Welding does not apply to thermosets. For thermoplastics, the presence of fibers disturbs welding, which is not often used. Of course, this broad diversity leads to diverse costs and the following information is theoretical and general, aiming to help the reader to get a rough idea of the problem. They are not intended to be used directly for design or economic studies.

8.2.1 Capability Proposals for Some Processing Methods Material type, physical form of raw materials, part features, series size, potentially available

8.2.1.1 Proposals for Thermoplastics Table 8.1 proposes examples of outputs and linked processing cost elements for a broad range of run sizes. Of course, there are many exceptions and different data may be found in the literature. Equipment capital cost, tooling cost, and labor cost are expected to be representative of the share of the considered item versus the total cost.

8.2.1.2 Proposals for Composites Table 8.2 proposes examples of outputs and linked processing cost elements for a broad range of run sizes. Of course, there are many exceptions and different data may be found in the literature. Equipment capital cost, tooling cost, and labor cost are expected to be representative of the share of the considered item versus the total cost. Table 8.3 proposes examples of usable processing methods for a broad range of composite part

Table 8.1 Examples of Outputs and Linked Processing Cost Elements.a

Process

Standard Output

Linked Processing Cost

Equipment Capital Cost

Tooling Cost

Labor Cost

Injection

1,000,000

1

High

High

Low

1000

14

High

High

Low

1,000,000

1.5

Med high

Med high

Low

1000

12

Med

Med

Low

Rotomolding, sophisticated machinery

1,000,000

2.5

Low med

Low med

Low

100

16

Low

Low

Rather low

Thermoforming

10,000

5

Low

Low

Med

10

16

Low

Low

Med

1000

6

Low

Low

Rather low

10

15

Low

Low

Low

1000

12

Med

Low

Med high

1

14

Med

Low

High

Blow molding

Rotomolding, basic machinery Fabrication by machining, cutting, welding, gluing, etc. a

Relative to the processing cost of a standard part injected at 1 million units.

Table 8.2 Examples of Outputs and Linked Processing Cost Elements. Equipment Capital Cost

Labor Cost

30 min to some days

Low

High

1 1000

30 min to some days

Low

High

Resin injection

200 10,000

30 min to some h

Medium

Medium

Cold compression molding

500 20,000

5 30 min

Medium to high

Medium

Hot compression molding mats and preforms

Mass production

1 10 min

High

Medium

Hot compression molding prepregs

Mass production

2 5 min

High

Low

Method

Output (Units)

Cycle Time

Hand lay-up

1 1000

Spray lay-up

RRIM

1000 250,000

High pressure injection

.10,000

High

Low

Medium

Autoclave

,5000

Medium-high

Medium

Stamping

Medium output

Medium

Low

Filament winding

,10,000

According to part

High

High

10 min to some h

High

Low

Centrifugal molding Pultrusion

Continuous

Continuous

High

Low

Continuous impregnation

Continuous

Continuous

High

Low

RRIM, Reinforced reaction injection molding.

Table 8.3 Examples of the Process Choice Versus the Part Characteristics.a Composites Part Size (Maximum Area in m2 )

Thickness (mm)

Virtually unlimited, ,300

Examples of Parts

Smooth Surface

Method

Unlimited 2 10

Ship

1

Hand lay-up

Virtually unlimited

Unlimited 2 10

Ship

1

Spray lay-up

Up to 15

1 10

Car body element

2

Resin injection

Up to 15

3 10

Car body element

2

Cold compression molding

Up to 5

1 6

Car body element

2

Hot compression molding mats and preforms

Up to 5

2 10

Car body element

2

Hot compression molding prepregs

Up to 10

Housing

1

RRIM

Limited

Electric and electronic parts

2

High pressure injection

Up to 20

Aeronautics elements

All

Autoclave

Automobile parts

2

Stamping

1 10 and more

Pressurized tank

1

Filament winding

3 15

Tube, pipe

1

Centrifugal molding

Up to 4 Diameter from 5 cm to 25 m with specific equipment

a

Up to 30 a

Manufacture on specific material developed for a particular part.

RRIM, Reinforced reaction injection molding.

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sizes from virtually unlimited areas to common electrical parts. Certain parts are manufactured on specific equipment developed for those particular parts. Of course, there are many exceptions and different examples may be found in the literature.

8.2.2 Use of Cost Estimator Software Generally, the cost figures offered by cost estimators are only order of magnitude. Because of such variations as labor rate, overhead costs, production technique specificities, accounting procedures, available equipment, outsourcing possibilities, these estimates should not be construed as an accounting cost or a quotation for sale or manufacture. When using several software products, the computed costs may be dissimilar. Because of the multiplicity of possible effects during the processing and use of plastics, the information generated by these software estimators must be carefully tested. The chosen software must be well understood and tuned to compute costs in compliance with technical and economic rules of society.

• ProMax-One

PLASTIC PART COST ESTIMATOR (InjectNet: http://injecnet.com/ injecnet/CostEstimator.aspx—free at www. Injecneering.com)

• DFM Concurrent Costing and DFA Product Simplification (Boothroyd Dewhurst, Inc.: http://www.dfma.com/software/dfma.asp) include Injection Molding models and various other manufacturing cost models related to blow molding, plastic extrusion, and thermoforming, It is possible to customize the cost estimate and to compare alternative processes and materials.

• CalcMaster

Software (Schouenberg & Partners: https://schouenc.home.xs4all.nl/) is claimed to estimate injection molds, complete injection molding process, number of cavities, part cost, etc.

• CostMate (IDES Inc.) is a molding part cost estimator that has been integrated into an online plastics search engine (Prospector) (see https://plastics.ulprospector.com/).

• http://www.custompartnet.com/estimate/injection-molding/

8.2.2.1 Examples of Cost Estimator Software Cost estimator software may help to obtain estimates fast, but, of course, their accuracy is limited. The following quotes a few examples. The quoted software, company names, trademarks, and websites are provided “as they are” and do not constitute any legal or professional advice. The author isn’t responsible for possible technical, economical, typographical, or other errors.

• BASF Quick Cost Estimator for Injection Molding Thermoplastic Parts (free) is based on commercial grades marketed by BASF. The cost figures are intended only to indicate order of magnitude, based on preliminary design, to determine the feasibility of a specific plastic application. This estimate should not be construed as a firm cost figure or a quotation to manufacture.

• Autodesk Moldflow plastic injection molding simulation software, part of the Autodesk solution, includes Cost Adviser for estimating product costs based on material choice, cycle time, postmolding operations, and fixed costs.

• http://wjtassociates.com/site/?page_id 5 6 proposes The Quick-Sight Mold Estimator

• http://www.emold.net/view/Calculate.jsp

The Injection Molding quote includes special options such as, for example: • Mold needing mirror polish • Hot runner system • Number of high precision dimensions

Other cost part estimator software and cost mold estimator software may be found elsewhere.

8.2.2.2 Examples of Cost Estimator Results Agreement Between Different Cost Estimators

It should be pointed out that for various estimator software following apparently similar ways, the actual conditions are not exactly the same because of the structure of the estimators. For a simple part, two cost estimators used “as they are” lead to ranges of total costs in the order of: 9% for 10,000 parts 9% for 100,000 parts 26% for 500,000 parts

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26% for 1,000,000 parts 17% for 1,500,000 parts 11% for 2,000,000 parts These data demonstrate the need to test and adapt the software to the actual context of use. Example of Effect of Run Size

Following data are theoretical information, not rules and different figures may be found elsewhere. For similar injection conditions:

• Weight part: medium • Wall thickness: 2 mm • Plastic grade: common engineering thermoplastic One cost estimator computes estimated linked part costs versus run size as:

• 500,000 parts, 1 cavity: baseline for linked part cost

• 500,000 parts, 2 cavities, linked part cost: 75% of the baseline

• 1 million parts, 3 cavities, linked part cost: 69% of the baseline

• 2 million parts, linked part cost: 63% of the baseline. Check the Sensitivity and the Application Window of Variables of Interest

All software solutions have not the same structure and every user has his own requirements. So, check the actual application field and the sensitivity of the various variables. For example, wall thickness may have effects on:

• Cycle time • Part weight • Material cost and of course part cost, etc. According to the software, new input of wall thickness by the user may affect:

• Cycle time: it may be automatically updated exactly or step by step (5 seconds, e.g.,) or unchanged. In that case the user must input the new data if relevant.

• Weight: it may be automatically updated or unchanged. In that case the user must input the new weight.

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These are only examples and the software user must pay attention to the effects of each variable and all potential interactions between parameters. The numerous points to be examined, sometimes redundant, include, but are not limited to:

• Plastic • Polymer grade • Part weight • Specific gravity of the material • Material weight • Cost of the material (USD/lb or USD/kg, etc.) • Estimated material cost per part including losses, 3% or 5%, for example

• Part • Annual number of parts (net parts or pro• • • • •

duced parts) Tolerances Surface roughness Complexity of the part Wall thickness Projected area of part

• Mold • Complexity of the mold (side-action direc• • • • • •

tions, cores, inserts, unscrewing devices, etc.) Number of cavities: input data or estimated data according to other elements Hot runners Mold cost Lifetime of the mold Maintenance cost of the mold Setup of mold per run

• Process • Cycle time: input data or estimated data • • • • •

according to wall thickness Press size Parts produced per hour Scrap rate Press use cost (USD/h) Labor rate (USD/h)

• Others • Quality inspection • Maintenance • Inserts • Secondary process costs (surface finishing, printing, plating, and other special treatments, etc.) • Special features such as transparency, special color, special formulation • Packaging

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• • • • • • • •

Other personnel expenses Supplies Transport Facility costs Capital depreciation Overhead contingencies (%) Profits Report

• Material cost per part • Processing cost per part • Total estimated cost per part An important point is the possible interactions between certain parameters; be sure that the effect of each element is taken into account and also be sure it is taken into account only once. Some software solutions deal with limited windows and are ineffective out of that range, but display results anyway.

8.3 Examples of Costs The figures provided here for processing costs are some examples of the orders of magnitude for specific cases; different contexts can lead to different costs. For industrialized countries, in the past few years, the average cost of plastics parts is expected to be h4.9 (USD5.4) or in the range h4.4 (USD5) h6.6 (USD8)/ kg. For a given processing technology, the processing costs are highly dependent on:

• • • • • • •

the annual production the delivery volume the size and shape of the parts the precision level the material cost the processing difficulties the recycling possibilities

For extruded goods such as films, sheets, and tubes, the costs are of the order of:

• h3.3 (USD4) h4.5 (USD5)/kg for commodities • h7 (USD8)/kg for high-performance films Each different design with a profile requiring the machining of a specific tool is charged with the tool cost.

Table 8.4 Average Selling Prices Versus Market.

Market

Average Prices, h/kg (USD/kg)

Miscellaneous

4.5 (5.8)

Building and civil engineering

4.5 (5.8)

Electricity and electronics

4.5 (5.8)

Mechanics and industry

5.5 (7.1)

Automotive and transportation

6.5 (8.5)

Shipbuilding

6.5 (8.5)

Sports and leisure

10 (13)

Medical

16.5 (21.5)

Aerospace

45 (58)

8.3.1 Expected Costs by Market As a first approximation, the injection molding cost of a part roughly represents the price of the raw polymer. Secondary process costs (surface finishing, printing, plating, and other special treatments, etc.,) packaging, transport, facility costs, profits, and other overhead contingencies must be added. The average costs are expected to be of the order of:

• h4.5 (USD5) h5.5 (USD6.1)/kg for packaging • h4.5 (USD5) h8 (USD9)/kg for building purposes

• h12 (USD14)/kg for consumer goods • h14 (USD16)/kg for technical parts Each different design of parts requires the machining of a specific mold of which the cost [e.g., h55,000 (USD65,000) or much more] is charged to the series of parts manufactured. Table 8.4 displays some approximate average selling prices of thermoplastics per kilogram.

8.3.2 Expected Cost of Composites Composites may be manufactured:

• Generally, by molding by compression, injection, transfer, thermoforming, and the derived methods such as rotomolding, RIM, RRIM, RTM, etc.

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Table 8.5 Examples of Processing Methods and Relative Costs per Unit.a Units per Annum

Prototypes: Machining

1

150

10

125

Processing methods for small and medium annual production

Machining

Rotational Molding, Simple Tooling

Rotational Molding, Sophisticated

25

110

35

60

1000

15

100

10

10,000

7

7

7

Units per Annum

Hand Layup

100

Vacuum Forming

Blow Molding

Injection

40

15

80

200

10

20

Processing methods for high annual production

a

Units per Annum

Rotational Molding, Sophisticated Tooling

Blow Molding

Injection

100,000

3

2.5

2.5

1,000,000

2.5

1.5

1

Relative to the part cost for injection molding 1 million parts per year.

• For parts of constant section by extrusion, pultrusion, and derived methods.

• For parts of enormous size by boiler making, hand lay-up, spray lay-up, centrifugal molding, filament winding, etc. The composites, even those that are mass produced, always have a high added value, for example:

• injection molding is used with numerous thermoplastics with a few exceptions such as polytetrafluoroethylene The costs shown in this table are index linked and have no intrinsic value. The reference (base 1) is the part cost for injection molding 1 million parts per year. The comparison is only valid for this table.

• h4.5 (USD5)/kg h7 (USD8)/kg for massproduced parts

• h11 (USD13)/kg h45 (USD50)/kg and more for advanced composites Table 8.5 displays some examples of the relative processing costs versus the annual production in units. The baseline for relative costs is the cost of a part produced to 1 million items. The various technologies listed are not suitable for all materials or parts:

• • • •

machining is used with numerous materials rotational molding uses liquid resins vacuum forming uses thermoplastic sheets blow molding thermoplastics

uses

special

grades

of

8.4 Economics of Renewable Materials The economy is dominated by fossil energy (petroleum, coal, natural gas) producing fuels, electricity, power, chemicals, and materials. At current consumption levels, known recoverable crude oil reserves would be dried up in some tens of years for relatively easy extractable sources and 100 years or more if petroleum from sand is recovered. Potentially, that leads to a global energy crisis in a medium term. As a result, it is essential to replace crude oil sourced polymers with renewable ones. Now, in round figures, the global market for bioplastics (less than 1% of plastics as a whole) is set to grow by 8% 10% annually, increasing its value from

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USD1000 million (h800 million) in 2007 to USD11 million to USD22 billion or more (h10 billion h20 billion or more) by 2020. A bioindustry could produce energy and many chemical building blocks from biomass (crops, trees, grasses, crop residues, forest residues, animal wastes, agricultural residues, and municipal solid waste) Biomass is naturally abundant. For example, in the continental United States, it is expected that about 500 600 million tons of plant matter could be grown and harvested in addition to food and feed needs. A bioindustry can be encouraged by environmental regulations and could provide many benefits such as:

• Productive use of agricultural and forestry wastes

• Lower emissions of greenhouse gases (GHGs) and pollutants

• Growth in rural economies, but some parameters must be evaluated such as pollution by fertilizers and pesticides

• Rural development: A bioindustry will require an increase in production and processing of biomass and would require new processing, distribution, and service industries.

• Environment: A key benefit in the move toward bioproducts is the potential for reducing pollutants emitted into the environment. When comparable bioproducts are produced, the environmental impacts are sometimes less or eliminated since many bioconversion processes occur at or near room temperature, atmospheric pressure, and neutral conditions. However, water pollution can be an issue if plants are specially grown for bioindustry. Particulate emissions generated during grain crushing and grinding operations can be also an issue concerning air pollution. Deforestation is also an issue for cultivated sources of biomass.

normally used for food, feed, and industrial applications such as corn, textiles, etc. Organic products of municipal waste and agricultural wastes, food and feed industry by-products are ideal from this point of view. CO2 could also be an abundant feedstock with the advantage of sequestering a harmful GHG. Being emerging materials, bioplastics consumption data broadly vary with sources, depending on the concept of bioproducts, a certain confusion between consumption and production capacity, and the optimism of the forecaster. In any case, bioproducts are specialty materials that now represent less than 5% of the total products, but with a higher growth rate than fossil plastics. It is necessary to anticipate the growing scarcity and the possible drying up of petroleum, which is the source of virtually all plastics. In this context, many countries are studying the replacement of oil-based products by biosourced equivalent or innovative products. So, for example, in the “Vision for Bioenergy and Biobased Products in the United States,” published by the Biomass Technical Advisory Committee, a goal was set to produce:

• 12% of chemicals and materials from biomass in 2010

• 18% in 2020 • 25% in 2030 • compared with the 5% produced in 2000 Nonoil alternatives can be good or bad sustainable solutions depending on the renewability of the source and the competition with existing uses. From this point of view (but other parameters must also be taken into account):

• Replacement of crude oil by coal and minerals is not a true solution because the renewal of those sources is far from the human ability.

• Replacement by food crop sourced polymers is not a good solution because of the global lack of food crops.

• Plants sequester carbon via photosynthesis and

• Replacement by plants used by the textile

potentially reduce the amount of carbon dioxide (CO2) emitted into the atmosphere.

industry is not a good solution because of the competition with natural textiles and the risk of replacement with synthetic textiles.

A very important point for the bioindustry strategy is to avoid competition with crops that are

• Wild plants, natural waste, and algae are really true solutions because they are not exploited.

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• Polymer synthesis from overabundant CO2 consuming a harmful GHG is a true solution.

• Recycling and reuse of existing plastics wastes has several advantages such as to intelligently get rid of wastes, to decrease consumption of energy, and to reduce emissions of CO2 and other GHGs having a greenhouse effect. Remember that renewable plastics can be broken down according to their origin into biosourced polymers or recycled plastics. Although obeying similar targets, scenarios for recycled and biosourced plastics are extremely different.

8.4.1 Plastics Recycling The recycling and reuse of commodity plastics such as PE, polyvinyl chloride (PVC), styrenics, and engineering plastics lead to an average estimated CO2 saving of 50% with contrasted situations depending on the waste sources and reuse levels. Waste plastic recycling has several advantages such as to intelligently get rid of wastes, to decrease consumption of energy, and to reduce emissions of CO2 and other GHGs. One must consider recycled plastics in a completely new light. Wastes are an industrial feature to be considered as a valuable resource, a plastic mine needing new mining techniques, and the adaptation of designing and processing; for example, upgrading of recycled products, adaptation to unusual rheologies, performance differences, inherent coloration, etc. Weight estimates are rare and highly spread. Forecasts are in a broad range due to the lack of precise statistics, the accounting method possibly 100 90 80 70 60 50 40 30 20 10 0 2015

taking into account energy recovery, and the point of view and the optimism of the forecaster. Modeled weight data are quite different depending on whether they are based on the volume of recycled plastics or on the percent of overall plastics consumption. Based on some million tonnes (about some percent of total plastics today), modeling may lead to some tens of million tonnes by 2022. Of course, the gap grows for estimates covering longer terms. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other higher data may be found elsewhere, taking into account an increase in the percent of recycling versus the total consumption of plastics. This hypothesis is credible according to crude oil scarcity and the strengthening of environmental regulations. Revenue estimates are more frequent, but are also spread and may increase twofold or more for the same year. One reason is the cost variations according to the economic context. In addition, weight and cost per weight are contradictory perhaps because of the applications taken into account. Fig. 8.6A displays an example, among other hypotheses (without any guarantee), of a forecast (in billion dollars) of plastics recycling for the 2016 22 period.

8.4.2 Biosourced Plastics Consumption Biopolymers derived from renewable biomass sources ensure the conservation of fossil resources, the utilization of renewable vegetal resources with their geopolitics involvement, and (B) 20 15 MT

$ Bn

(A)

383

10 5

Year

2022

0 2010

Year

2020

Figure 8.6 (A) Forecast of plastics recycling for 2016 22. (B) Consumption forecast (MT) of Bioplastics for 2010 22.

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the consumption of CO2 instead of its emission. Several ways are exploited:

• Direct processing of natural polymers such as starch, polylactic acid (PLA), polyhydroxyalkanoate (PHA), and natural fibers (NFs). The bioplastics currently available contain more than 50% by weight of renewable sources, reaching 100% for polymers such as PLA, PHA, and NFs.

• The use of biocomponents partly replacing petroleum-based components. The used level can vary from 20% to more than 60%. Among the numerous examples are PA 11, thermoplastic elastomers (Hytrel, Pebax, Pearlthane, etc.), and acrylics containing 20% renewable carbon or more.

• Natural scraps are a smart solution to avoid food crop competition. However, honestly, it is possible that other competition appears between industrial uses of scraps and any industrial sector trying to value these cheap and limitless sources of raw materials. Natural wastes are sources of a multitude of chemical bricks and molecules, for example, cellulose, starch, lignin, proteins, albumin, blood meal, casein, glycerin (a by-product of biodiesel), soaps and fatty acids, and terpenes including limonene, citric, and succinic acids, etc.

• Polymers consuming CO2 and CO pump an abundant, undesirable, and cheap GHG to turn it into engineering thermoplastics. The general principle is to alternate sequences of CO or CO2 and another monomer. Using CO2 suffers from two drawbacks: 1000

• insufficiently efficient catalysts leading to expensive plastics properties of the obtained products However, steady progresses lead to higher catalyst activities and more viable products.

• inadequate

• The biofuel highway: During photosynthesis, algae and other plants capture CO2 and sunlight and convert it into oxygen and biomass. Biomass can be turned into vegetable oil, biodiesel, biogasoline, and other biofuels that can generate the same hydrocarbons as crude oil. Several companies and government agencies are funding efforts to reduce capital and operating costs and make algae fuel production commercially viable. The United States Department of Energy estimates that if algae fuel replaced all the petroleum fuel in the United States, it would require 40,000 km2 of land. This is less than one seventh the area of corn harvested in the United States in 2000. The main advantages of the biofuel way are: • The huge amounts of targeted biofuel and biogasoline (C6 to C12) production, several times the tonnage of conventional plastics • The use of conventional processing methods of the petroleum industry such as refining, hydrocracking, or hydrogenation • The use of conventional polymerization methods and existing chemical plants to produce conventional plastics based on renewable sources

MT

Total plastics (MT) Bio Plastics (MT) 500 Fossil Plastics (MT)

0 2000

2050 Year

Figure 8.7 Consumption forecast for bio- and fossil plastics for 2000 70.

2100

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Today, extraction costs (e.g., USD2 per gallon) and refining costs (e.g., USD3 per gallon) are too high, but larger scale refining operations would be competitive with fossil fuels. Projects run by the companies SAIC and General Atomic are expected to produce 1000 gal of oil per acre per year from algal ponds at competitive costs. Biosourced plastics consumption data broadly vary with forecasting sources, depending on the concept of bioplastics, a certain confusion between consumption, actual production, and production capacity, the retained data for partial biopolymers, the retained global economy hypotheses, and the optimism of the forecaster. According to various market studies (NovaInstitut, BCC Research, MarketsandMarkets, European Bioplastics), Fig. 8.6B shows the broad range of forecasts coming from the low levels of consumption for each bioplastic class, the lack of precise statistics, the accounting method [How is a polyethylene terephthalate (PET) based on 30% natural resources accounted?], the point of view and the optimism of the forecaster. Beware, scales are not the same as for Fig. 8.6A. Obviously these data are only a possible scenario among others that cannot be used to make economic predictions. Other data can be found elsewhere. In all cases, the consumption of bioplastics is on the order of 1% 2% of all the plastics and based on the production level of each family can be classified as specialty plastics. Of course, even for cheap feedstocks, the cost is higher than that of commodities. For more long-term forecast, a model is proposed taking into account several assumptions related to:

• the starting year being set to 2000 for significant commercialization

• the final level of fossil plastics replacement set to a cautious 80%, a consensual level according to experts

• the growing demand cycle valued to 70 years according to the growing demand cycles of fossil commodities

• the standard logistic law for modeling Modeling is a purely mathematical exercise, which doesn’t take into account unexpected technical and economic events, and doesn’t properly

385

foresee economic evolutions as soon as experimental limits are left behind. Thus the user takes a risk, so it’s all the more important that the real conditions are far from the experimental hypotheses used for the modeling basis. Being conscious of those drawbacks, Fig. 8.7 shows a plausible hypothesis (possibly false in light of the long forecasting period) for the replacement rate of fossil plastics by biosourced plastics. These forecasts are based on smooth evolutions that can be shattered by important parameters such as a petrol drying-up, a harsh stiffening of environmental requirements, and any other upheaval. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere. In that hypothesis, optimistically, bioplastics consumption accounts for:

• 10% of the total plastics consumption by 2023 • 50% of the total plastics consumption by 2035 According to a SpecialChem poll, “Bioplastics are growing fast but now their consumption is weak. In your opinion, bioplastics can catch 50% of the plastics market by. . .” The answer from respondents having a positive opinion of bioplastics was about 2040.

8.4.3 Market Shares by Bioplastic Family Table 8.6 (according to European Bioplastics) proposes a rating of the seven main bioplastics families valued at the actual natural content and total gross weight for bio-PET. In both cases, bio-PE, PLA, bio-PET and starch derivatives account for more than 75%. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere.

8.4.4 Production Capacities by Bioplastic Family Production capacities are questionable for marketing reasons. For example, the new projects are trumpeted but cancellation of old projects are generally discreet. In any case, bio-PET is, by far, the most promising due to Coca-Cola and other companies

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Table 8.6 Rating of the Seven Main Bioplastics Families. Actual Natural Content

Gross Weight %

Bio-PE PLA

%

11 20

Bio-PET

26 39

14 22

Bio-PE

10 17

a

12 16

PLA

10 16

Starch derivatives

12 16

Starch derivatives

11 19

Other polyester

14

Biodegradable polyester

10

Bio-PA

2 6

Bio-PA

1.5 7

PHA

2 3

PHA

1.5 2.5

Others

4 5

Others

4 9

Bio-PET

a

Total Bio-PET consumption data are affected of a reduction factor taking into account the low biocontent, 30%. PA, Polyamide; PE, polyethylene; PET, polyethylene terephthalate; PHA, polyhydroxyalkanoate; PLA, polylactic acid.

Table 8.7 Examples of Forecast Capacities by Bioplastics Families. Capacities

2016

Medium Term

Increase

MT

MT

%

Bio-PET

1

2 5

100 400

Bio-PE

0.2

0.2 0.6

0 200

PLA

0.2

0.5 0.8

150 300

Starch

0.3 0.4

0.4 0.5

0 to B100

Biodegradable polyesters

0.3

0.3 0.4

0 to B100

PTT

0.1

0.1

0

Bio-PA

0.1

0.1

B30

PHA

, 0.1

0.1 0.4

B100

0.5

NA

CA Regenerated cellulose

, 0.1

NA

Bio-PVC

, 0.1

NA

Bio-PP

, 0.1

NA

Bio-PU

, 0.1

NA

Thermosets

0.5

NA

Others

, 0.1

0.1

NA

Total capacities

B4

B6.7

B70

Total demand

4

5

B30

Production capacity usage rate

100%

75%

CA, Cellulose acetate; PA, polyamide; PE, polyethylene; PET, polyethylene terephthalate; PHA, polyhydroxyalkanoate; PLA, polylactic acid; PP, polypropylene; PTT, polytrimethylene terephthalate; PU, polyurethane; PVC, polyvinyl chloride.

deliberately designing and imposing renewable packaging. Table 8.7 displays examples of forecast capacities by bioplastics families. Obviously, these data are

only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere.

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Table 8.8 Examples of Forecast Capacity Shares by Region. Capacity Share in Recent Year (%)

Mid-Term Share Forecast (%)

Asia

35 50

46 76

South America

5 20

12 45

Europe

18 25

5 8

North America

14 25

3 4

Middle East and Africa

Negligible

Negligible

Total

100

100

8.4.5 Bioplastic Capacities by Region Data are inconsistent for some regions, but unquestionably Asia is the leader at short- and midterm followed by South America. Please note that capacity and consumption can be extremely different. Table 8.8 displays the production capacity shares for biopolymers based on renewable raw materials in the world in recent years and a mid-term forecast. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere.

8.4.6 Bioplastic Capacities by Market Table 8.9 displays production capacities by weight and shares including textiles for biopolymers based on renewable raw materials in the world in recent years and a mid-term forecast. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere. Packaging is the unchallenged leader with a market share higher than 75%. Other markets, one by one, account for less than 7%.

387

Table 8.9 Examples of Forecast Capacity Shares by Application Sectors.

Recent Year

MidTerm Shares

kt

%

%

Packaging

1618

39

40 60

Consumer goods

904

22

10 25

Automotive and transport

567

14

10 15

Building and construction

566

14

10 15

Textile

233

6

10

Agriculture

117

3

2 5

Electrical and electronics

27

,1

,1

Others

128

3

2

Total

4160

B100

100

8.4.7 Bioadditives Consumption The main reasons for developing and using bioadditives are:

• Production of 100% renewable compounds made out of renewable polymers and renewable additives.

• Replacement of oil-based additives with natural-sourced additives. According to market research reports, the global plastics additive market was estimated between USD35 and 48 billion in 2015. It is expected to increase at a compound annual growth rate (CAGR) superior to 4%, reaching between USD48 and 65 billion in 2021. At the same time, optimistic forecasts expect that the bioadditive market share could grow from a few percent to up to nearly 30%, leading to an annual consumption estimated of 15 million tons. Other expectations are much more pessimistic, predicting an annual consumption estimated at 5 million tons. Processing renewable biomass according to more or less complex treatments can lead to nonoil

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additives, chemical blocks, and raw materials for additives. Used with starch derivatives, PLA, PHA, polyhydroxybutyrate (PHB), green PE, green polypropylene (PP), green polystyrene (PS), green PVC, and biopolyurethane, bioadditives could allow for a total 100% renewable strategy to be reached. Bioadditives can be broken down into NFs including wood fibers, on the one hand, and other additives, on the other hand. Each category can be used with natural or fossil polymers.

Table 8.10 Natural Fiber Availability Compared to Cereals and Fiberglass.

Cereals

Vegetable

Industrial Fibers

kt/Annum

kt/Annum

2,000,000

Cotton Others

25,000 B4,000,000

Jute

2900

8.4.7.1 Natural Fiber Composite Market

Flax

770 830

Natural reinforcements have been used for a long time:

Corn stover

730

Rice straw

580

Wheat straw

570

Sisal

320

Sorghum stalks

250

Barley straw

200

Coir

100 650

Bagasse

100

Abaca/ banana

150

Hemp

83

• Wood flour was one of the first fillers to be used with phenolic resin.

• Wood

shavings particleboards.

are

used

in

wood

• Short cotton and other cellulosic fibers are commonly used in phenolic and melamine resins. NFs, for the activities within the scope of this work, are appreciated for general-purpose uses because of:

• Environmental and ecological criteria • Geopolitical motivations • Economic considerations that lead some nations to give priority to local materials

• Their fair mechanical performances • The fair balance of weight/performance/cost. Many plants grow in developing countries and need agricultural means instead of industrial ones. Apart from cotton, all other examined fibers weigh approximately 7 million tons. For comparison, GFs are estimated to be about 4 5 million tons, that is to say, half the production of all NFs used in industrial applications. One can imagine the effort needed to develop the agriculture, the risks of competition with industrial crops, and even the harsh competition with food crops. Main NF producers are developing in countries such as China, India, Bangladesh, Nepal, and others, but the European Union, Canada, and the United States cultivate some plants such as flax.

Pineapple leaf fiber Total

B6,000,000

B32,000

Cultivation can be sophisticated using selection, cloning, fertilization, and other treatments or it can use hardy plants needing no work except harvesting. Of course, fertilization can be harmful to the environment. The NF consumption for polymer reinforcement is not known, but it is increasing at an estimated CAGR of about 10% 13%. In all likelihood, the most often quoted fibers derive from wood, flax, kenaf, hemp, jute, sisal, but many others are proposed such as, for example, cotton, bamboo, abaca banana, ramie, coir (coconut). Table 8.10 displays some estimated data concerning NF cultivation. Industrial fibers relate to all industrial applications including, but not limited to, plastic reinforcement. Table 8.11 displays some estimated data concerning NFs used for composites in the European automotive industry. Other regions can use other

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Table 8.11 Main Natural Fiber Used for Composites in European Automotive Industry. Source

Tonnage (T)

Natural Fiber Sharing

Tonnage (t)

Shares (%)

Natural fibers

30,000

Flax

15,000

19

Kenaf

6000

7.5

Hemp

3600

4.5

Jute, coir, sisal, and abaca

5400

6.5

(Subtotal natural fibers)

(30,000)

Recycled cotton

20,000

25

Wood fiber

30,000

37.5

Total

80,000

100

NFs depending on the local cultivation or abundance of agricultural wastes (remember that GF demand for composites is estimated to 4 5 MT). In terms of composite volumes in the European automotive industry, tonnages are roughly estimated as: NF composites (NFCs): 60,000 t Wood plastic composites (WPCs): 60,000 t Recycled cotton composites: 30,000 t Total: 150,000 t Average fiber level is estimated at about 50%. A report published by MarketsandMarkets projected the market size for NFCs to reach USD6.5 billion by 2021, at a CAGR of 11.7% between 2016 and 2021. For comparison, the global glass fiber reinforced plastic composites market is estimated to grow at a CAGR of 7.4% from 2014 to 2019 to reach a value of USD45 billion.

8.4.7.2 Other Bioadditives Used at 5% 7% in terms of weight, but at about 10% by cost, additives contribute to the success of plastics. Apart from common fillers, plastics additives are expensive products with an average cost of about USD3/kg. Bioadditives are consumed in bioplastics and in oil-based plastics at a CAGR on the order of 30% and a 2020 consumption estimated at 15 million tons in optimistic hypotheses. Pessimistic expectations expect a 2020 consumption estimated at 5 million tons with a CAGR of 11%. The bioplasticizer market, according to MarketsandMarkets (http://www.marketsandmarkets. com/) could be about USD0.7 billion in 2015, and is projected to reach USD1.1 billion by 2020, registering a CAGR of 9.8% between 2015 and 2020.

Bioplasticizers Market Overview (http://news. bio-based.eu/bio-plasticizers-market-global-opportunity-analysis-and-industry-forecast-2014-2022/) quotes a CAGR of 3.3% from 2016 to 2022 leading to USD1.4 billion in 2015 and USD1.7 billion by 2022.

8.4.8 Wood Plastic Composite and Natural Fiber Composite Markets According to the sources, the WPC market is expected to be on the order of 1.2 to up to 3.5 million tons in 2015, and is projected to reach about 2 5 million tons by 2020, registering a CAGR of 10% 11% between 2015 and 2020. According to a report by Grand View Research, Inc., the global WPC market is expected to reach USD9.77 billion by 2024. According to InkWood Research (https://www. inkwoodresearch.com/reports/wood-plastic-composites-market/) the global WPC market is anticipated to grow from USD3.7 billion in 2017 to USD10.8 billion by 2026, at a CAGR of 12.79% between the forecast period of 2018 and 2026. Demand is rising in the construction industry (decking, fencing, and molding and siding applications) and the automotive industry (door panels, seat cushions, cabin linings, backrests, and dashboards). The NFC market including WPCs is expected to be on the order of more than 3.5 million tons in 2015, and is projected to reach about 7 million tons by 2020, registering a CAGR of 12% 13% between 2015 and 2020. According to a report by Grand View Research, Inc., the global NFC market is expected to reach USD11 billion by 2024. Other forecasters quote other CAGRs, for example 8.2%.

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The United States and China are the leaders with individual market shares between 35% and 47%, followed by Europe (about 10%), and other regions accounting for less than 3% each. The different types of WPCs available on the market are based on PE (leading), PVC (rapidly growing), PP, PS, PLA (renewable), and acrylonitrile butadiene styrene (ABS).

management consultancy, finding that while 8 out of 10 respondents said they use biodegradable products, more than half felt the cost was too high. Generally speaking, according to various global market studies, the average price of bioplastics was valued on the order of USD2.2/kg USD2.9/kg, that is to say, 1.4- to 1.6-times the average price of commodity thermoplastics. More optimistic forecasters value the premium at 25%. Table 8.12 proposes a statistical analysis of expected prices for raw resins versus market shares. Considered bioplastics are PLA and thermoplastic starch (TPS). Fossil plastics include commodities (PE, PS, PP, PET, and PVC). ABS and PA 66 represent engineering plastics. Cost differences are on the order of USD1/kg for the raw materials and the end products. The reader must be cautious of the broad range of prices for the same family depending on the origin, annual volume, actual grade, quality, possible incorporation of recycled matter, etc. Generally speaking:

8.4.9 Biomaterial Costs Of course, the data provided here are theoretical and vary with the economic context. They cannot be used to make economic predictions. Other different figures can be found elsewhere.

8.4.9.1 Bioplastics Costs The plastic cost structure includes research and development costs, raw material purchase, synthesis and processing costs, marketing, and other related expenses. For commodities and similar bioentities, the production volume is an important factor of the overall cost. For example, Fig. 8.8 shows the cost of various regular bioplastics and fossil polymers versus the product market share with a harsh jump for low market shares. Altogether bioplastics have a market share on the order of 1%, but the consumption must be divided by more than five families and inevitably prices are those of niche plastics even if raw material and processing costs are cheap. Price is an obstacle to the growth of bioplastics, which is confirmed, for example, by a poll conducted by Brilliant Little Planet, a bioplastics supplier, and Adapt Low Carbon Group, a

• The average premium for TPS is on the order of 50% with broad variations.

• For PLA, the premium is higher, but the cost compared to regular plastic products is becoming more competitive as the consumption rises. The disparity in prices could be about 15% in the near future.

• Currently, the price of bio-PE is claimed to be about 50% higher than that of fossil PE, but as production volumes increase the price premium should decrease.

5 4.5 4 3.5 $/kg

3 2.5 2 1.5 1 0.5 0 0

5

10

15

20

Market share (%)

Figure 8.8 Plastics costs versus market share.

25

30

35

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Table 8.12 Statistical Analysis of Expected Prices for Raw Resins Versus Market Shares. Commodity Thermoplastics Market share (%)

PE

PP

PVC

PS

PET

30

20

10

7

7

Cost (USD/kg) Mean

1.9

1.8

1.7

2.1

1.6

Standard deviation

0.59

0.66

0.75

0.83

0.52

Minimum

0.5

0.65

0.72

0.55

0.65

Maximum

2.5

3

2.6

2.9

2.5

Engineering Thermoplastics ABS

PA66

,5

1

Mean

2.6

3.6

Standard deviation

1.12

1.02

Minimum

0.8

2

Maximum

5.3

5.5

Market share (%) Cost (USD/kg)

Biothermoplastics Starch-Based

PLA-Based

,1

,1

Mean

2.8

4.75

Standard deviation

1.0

1.0

Minimum

1.5

3.5

Maximum

5

6

Market share (%) Cost (USD/kg)

ABS, Acrylonitrile butadiene styrene; PE, polyethylene; PET, polyethylene terephthalate; PLA, polylactic acid; PP, polypropylene; PVC, polyvinyl chloride; PS, polystyrene.

• According to the sources, PHA prices vary between USD3.8 and USD5/kg depending on the production capacity of existing plants. PHA prices are expected to be about 50% higher than commodities at comparable scale.

• PHB prices are claimed to be in the range USD4 USD6/kg.

• Soy protein isolate price is estimated to be 2.4USD/kg approximately in the same order as starch-based bioplastics. Of course, these data cannot be used to make economic predictions. Other different figures can be found elsewhere.

8.4.9.2 Natural Fiber Costs Costs per kilogram are in a broad range according to the vegetable fiber, the level of

quality, the country, and the form (long or short fibers, fabrics, etc.). Without any guarantees, Table 8.13 proposes a statistical analysis of expected prices for raw NFs. For comparison, the cost of E-GFs could be in the range of USD1.5 to more than USD5/kg with an average of USD2.2/kg. For the end cost of composites, these data must be corrected because of the lower reinforcement performance of NFs.

8.5 Survey of Main Bioplastics Markets By far, packaging prevails over consumer goods, automotive and transport, and building and construction. Electrical and electronics account for 1% or less.

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Table 8.13 Examples of Expected Prices for Raw Natural Fibers. Cost (USD/ kg)

Cotton

Hemp

Flax

Sisal

Recycled Cotton

Coconut

Wood Flour

Mean

1.8

1.7

1.5

1.2

1.2

1.1

0.2

Standard deviation

0.43

0.91

0.44

0.48

NA

NA

NA

Minimum

0.9

0.8

0.8

0.5

0.75

0.28

0.15

Maximum

2.8

2.8

2.5

1.75

1.95

3.2

0.22

All applications quoted here are potential ones; the reader must verify the suitability for their own case and is responsible for their choice.

8.5.1 Packaging Packaging, the market leader, consumes derivatives of starch and PLA for the main share of traditional packaging applications. Partially, biobased PET is a special case issued from the will of a few companies led by Coca-Cola to develop biomaterials for environmental and marketing purposes. Engineering or durable bioplastics are used for specific applications accounting for a low market share. Without any guarantees, Table 8.14 displays some industrial or potential examples without claiming to be exhaustive. Some bioplastics may be discontinued for economic or technical motives. Some bioplastics being locally produced aren’t quoted.

8.5.2 Consumer Goods For consumer goods such as serviceware, toys, and others, bioplastics offer an opportunity to move away from oil-based plastics, responding to consumer trends becoming increasingly aware of their impact on the planet and appreciating more environment-friendly alternatives. This gives brand owners a unique opportunity to meet consumer demand, increase corporate sustainability, and improve resource efficiency. Without any guarantees, Table 8.15 displays some industrial or potential examples of bioplastics used in the consumer goods sector. Many grades are partially produced from renewable resources.

8.5.3 Automotive and Transportation Car makers and their suppliers push renewable plastic and composite use for a variety of reasons depending on environmental, economic, regulatory, societal, and marketing purposes. As for fossil materials, the main challenge lies in a subtle balance between the strengths and weaknesses of natural materials. Among targeted goals are:

• environmental advantages • an increase of the environment-friendly profile of end products

• • • •

a move away from oil dependency cost saving possible weight saving respond to emerging industrial, policy, or societal needs

However, such benefits are not automatically linked to natural product uses:

• Some bioplastics such as PLA have a higher density than their petroleum-based counterparts.

• Weight saving induced by NF use can be canceled out by lower mechanical performances needing an overconsumption of the used composite.

• Environmental benefits can be offset by pollution due to fertilizers used for plant growing or by pollution induced by long transport distances.

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Table 8.14 Examples of Industrial or Potential Applications of Bioplastics in Packaging. Biobased PET: Generally Partially Biobased Bottles, containers, jars BIOFRONT: Stereocomplex PLA Films Fibers Biolice Made From Whole Cereal Grains Flexible applications: 12 200 µm, mono layer and coextrusion films Bags, dustbin bags, green waste bags, compost bags, retail shopping bags, liners for wheeled bins, and heavy-duty sacks Industrial films (single layer or coextrusion): packing films and laminating films, stretch film and stretch hoods, protective sheaths and covers, netting, and safety tapes Mulch films for agricultural, horticultural, and garden use, and films for seaweed and mud therapy (thalassotherapy) Rigid applications: shatter proof, temperature resistant

40°C 80°C

Thermoformed products: thin wall packaging, trays, containers, and plant pots, and multicell and standard seed trays Extruded products, cotton buds Biomer: PHB Food, industrial, agriculture packaging Bionolle: Aliphatic Polyester Bottles, containers Laminated paper Trash bags Foam BIOPAR: Starch-Derived Bottle blowing Film, cast film, or thermoforming Injection molding Short-life products and food packaging Bioplast: Starch-Based, PLA-Based Short-life packaging Film Multiuse bags (e.g., carrier bags, loop-handle bags, etc.), single-use bags (e.g., refuse bags, bin liners, etc.) Food packaging Thermoformed products (e.g., food trays) Extruded products: tubes Cutlery (Continued )

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Table 8.14 Examples of Industrial or Potential Applications of Bioplastics in Packaging.—Cont’d Biopur: Starch-Based Foam Cardia Biohybrid: Starch and Polyolefin Film, over wrap, shrink wrap Closures Bottles, containers, blow molding Extruded and thermoformed trays, foam sheets, sheets Shopping bags, waste bags Cellulosics: Esters Dry food without fat Aesthetic packaging Films, transparent wrapping, blister packaging, etc. Containers, bottles, boxes and tubing, etc. Bin liners Healthcare, cosmetics, perfumery and personal care, supply containers and packaging, etc. Disposable cutlery CNF by Sappi Plastic films Cornstarch: Starch-Derived Cornstarch polymer for chocolate tray Ecovio: PLA and Biodegradable Copolyester Waste bags, shopping bags Mulch films, shrink films Paper-coating Foam packaging Thermoformed packaging Compostable packaging Fasal: Composed Primarily of Wood and Corn (WPC) Injected urns Gaialene: Starch-Derived Packaging film, barrier layers of multilayer films Foamed Gaialene for packaging Bottles and flasks by extrusion blow molding, translucent to opaque, flexible to rigid, small to large volumes. Stability in contact with shampoos, detergents, oils and fats, alcohols, etc. Ingeo: PLA Food and beverage bottling applications including water bottles Keystone Water Company unveiled its 100% plant-based bottle made from Ingeo (NatureWorks) Wrap, films, labels, and laminates (Continued )

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Table 8.14 Examples of Industrial or Potential Applications of Bioplastics in Packaging.—Cont’d Folded carton packaging laminates Deli, fruit, and food containers Disposable plastic cups Wide variety of food and beverage bottling applications including water bottles Blister packaging used to wrap such products as Sony Walkman radios and DVDs Ingeo plastic can be industrially composted Jeluplast by Jelu Werk: Fossil and Renewable Plastics Filled With Wood and Cellulose Fiber Wine capsules Pallets Lifocork (by Hexpol Tpe): Thermoplastic and Cork Bowls, trays, boxes, and plant pots Mater-Bi: Starch-Derived Biodegradable and compostable bags, shopping bags, separate waste collection of organic waste Transparent film for packaging fruit and vegetables, film for packaging different types of nonfood products such as toilet paper, kitchen rolls, napkins and tissues, nappies, sanitary towels, or magazines Thermoformed trays for foodstuffs (fruit, vegetables, meat, etc.) Plates, beakers, cups, boxes for transporting prepared food Flexible packaging for frozen food, cheese, etc. Packaging of small electrical items (mobile phones, razors, etc.) Coated paper and cardboard for food wrapping paper, packaging for freshly cut products such as cheese, sliced meat, meat products and bags for bread, chicken, flour, single-use packets for sugar, etc. Coated cardboard to make cups for hot and cold drinks, plates, cups for ice cream, trays for food or containers for frozen food Packaging of perishable food products or variable shelf-life products such as prewashed salads, bakery goods, biscuits, snacks, cereals, croquettes, or coffee Extruded and woven nets for packaging food products like citrus fruit and garlic Foam packaging as an environment-friendly alternative to polystyrene, polyurethane, and polyethylene Containers for dry cosmetics such as face powders, eye shadow, lipstick, etc. Various grades of Mater-Bi (starch) can be combined with each other or with other biodegradable and compostable materials to obtain multilayered structures with higher levels of performance in terms of processability and barriers to moisture and gas. They can be used for packaging of perishable food products or variable shelf-life products such as prewashed salads, bakery goods, biscuits, snacks, cereals, croquettes or coffee Trays and other rigid containers for various products such as cheese, fruit, etc. Mirel and Mvera: PHA Blown and cast films, retail bags, organics and yard waste collection bags (Continued )

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Table 8.14 Examples of Industrial or Potential Applications of Bioplastics in Packaging.—Cont’d Miscellaneous Undefined Materials Milk bottles Transparent containers for olive oil and other cooking oils Na Pac: Sugar Cane and Reed Derivatives Disposable food packaging, bowls, retail packs, plates, containers, lids, snack boxes, hamburger clams Natureflex: Cellulose-Based Tea packaging PBS, PBSA: Polyester Food or nonfood packaging PHB/PHV, PHBH: Polyester Biodegradable containers, shampoo bottles, and other articles difficult to recycle Flexible grades, target films, and other packaging uses Rigid grades, disposable cutlery, and thermoformed blisters Plantic: Starch-Derived Environment-friendly, biodegradable, and compostable food packaging Biodegradable packaging for White Ballotins Chocolate Box Iinjection molded bucket (HDPE-like) for insecticide attractant for mosquitos laying eggs, water resistant, and biodegradable Sheet grade suitable for thermoforming applications (e.g., for packing foods and goods with water activity of 35% 70%). Also suitable for direct contact with fatty foods Marks & Spencer, Haigh’s Chocolates, Cadbury Schweppes sell chocolates with environmentfriendly packaging Customized advertising product in the form of plants seeds packaged in a compostable blister S2PC

PP and fibers derived from sunflower seed hulls (golden-compound) Cosmetic packaging

Solanyl: Starch-Derived, Mainly Based on Reclaimed Side Stream Starch From Potato Processing Industry Grain, Root, or Seed and/or Flour-Based Resources Food packaging, for example, blister packaging, shopping bags Solanyl can be used for food packaging, for example, blister packaging, shopping bags TREEPLAST: Wood Chips With Crushed Corn and Natural Resins (WPC) Promotional articles, packing Trellis Earth (Cereplast): Starch and Fossil Plastic Compostable packaging Cereplast Compostables resins are industrially compostable substitutes (according to ASTM) Cereplast Compostables film grades are for use on blown film extruder lines for the manufacture of compostable bags, carry bags, and trash bags Vegemat: Starch-Derived Disposable cutlery (natural fibers, starch, proteins, lipids) (Continued )

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Table 8.14 Examples of Industrial or Potential Applications of Bioplastics in Packaging.—Cont’d Vegeos: Starch and Polylactic Acid Biodegradable plastics compliant with standard EN 13432 and certified OK Compost for flexible applications including refuse bags and shopping bags Biodegradable plastics compliant with standard EN 13432 and certified OK Compost for rigid applications such as disposable tableware Green PE Blow-molded liquid food bottles, household chemical bottles, motor oil cans, etc. Blow-molded drugs, cosmetic, and toiletry containers, etc. Crates, totes, drums, etc. Food and beverage containers, etc. Houseware Industrial and shipping pails, etc. Basins, bottles, stoppers, hollow parts, pallets, etc. Large-sized objects such as cisterns, tanks, septic tanks, industrial drums, etc. ASTM, American society for testing and materials; CNF, cellulose nano fibrils; HDPE, high-density polyethylene; PE, polyethylene; PET, polyethylene terephthalate; PHA, polyhydroxyalkanoate; PHB, polyhydroxybutyrate; PHBH, polyhydroxybutyrate-hexanoate; PHV, polyhydroxyvalerate; PLA, polylactic acid; PP, polypropylene; WPC, wood plastic composite.

Table 8.15 Examples of Bioplastics Used in Consumer Goods. ARBOFORM: Lignin-Derived Consumer articles, molded parts Jewelry, toys Musical instruments BIOFRONT: Stereocomplex PLA Molded parts, eyeglass frames Biograde: Cellulose-Based Heat resistant cutlery Bionolle Aliphatic Polyester Gloves, combs, pegs Bioplast: Starch-Based, PLA-Based Injection-molded articles, cutlery, cups for hot and cold drinks Cardia Biohybrid: Starch and Polyolefin Injection-molded closures, utensils, pens Cornpole: Starch-Derived Ballpoint pens Fasal: WPC Ceiling boxes for different lights (Haba Cy) Furniture legs for bathroom furnishings (Villeroy and Boch Badmo¨bel in Mondsee) Gaialene: Starch-Derived Durable and semi-durable consumer goods (Continued )

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Table 8.15 Examples of Bioplastics Used in Consumer Goods.—Cont’d Ingeo: PLA Gift cards, hotel key cards, loyalty and transactional cards Mobile phone cases, appliances, cosmetics, laptops, and other durable goods Disposable plastic cups, cutlery, and plates Mater-Bi: Starch-Derived Disposable cups, plates, and cutlery that can be biodegraded and composted Nappies, sanitary towels, and panty liners Range of articles for public catering including cutlery, plates, beakers, cups, even boxes for transporting prepared food Pens, pencil sharpeners, rulers Children’s toys Containers for dry cosmetics such as face powders, eye shadow, lipstick, etc. Antistatic combs PBS, PBSA Polyester Utensils, disposable cups, and flushable hygiene products PHB/PHV Polyester Disposable razors PHBH Polyester Rigid grades for disposable cutlery PLA (See Also Ingeo) Office equipment and supplies Housings of cell phones and other mobile devices and digital consumer electronics Plantic: Starch-Derived Injection#-molded biodegrade bucket Resound Biopolymers: PLA, PHB, PHBV, and Biopolyesters Combined With ETP reSound NF: Natural Fiber Reinforced Formulations Consumer durable goods Solanyl: Starch-Derived Identification cards, displays Promotion articles Sorona: Trimethylene Terephthalate Residential and commercial carpets, apparel and automotive mats and carpets Treeplast: WPC Multiuse laptop stand, brush handle, ice-drink holder Trellis Earth (Cereplast): Starch and Fossil Plastic Consumer goods Vegemat: Starch-Derived Coffee machine capsules, disposable cutlery Dog treats (Continued )

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Table 8.15 Examples of Bioplastics Used in Consumer Goods.—Cont’d PBS, PBSA: Polyester Foam Wood Plastics Composites Outdoor furniture, picnic tables, and benches Indoor furniture, chairs, rocking chairs, packing case Hot tub siding Various Materials Apinat

iPhone 6 cover

Traverse TF4000

Smartphone case

ETP, Engineering thermoplastics; HDPE, high-density polyethylene; PBS, polybutylene succinate; PBSA, polybutylene succinate-adipate; PHBH, polyhydroxybutyrate-hexanoate; PHBV, polyhydroxybutyrate-co-hydroxyvalerate; PHV, polyhydroxyvalerate; PLA, polylactic acid; PP, polypropylene; WPC, Wood plastic composite.

Among others, the automotive industry industrially uses biopolyurethane foams based on soya polyols to produce seats, headrests, armrests, and soundproofing. Ford Motor Company first debuted soy-based polyurethane foams in the seats of its 2008 Ford Mustang. Ford’s use of soy-foam seat cushions has allowed its supply chain to reduce petroleum usage in production by more than 2300 t annually while lowering CO2 emissions by some 9000 t. Foam seat backs and cushions can contain up to 24% renewable material and 75% of Ford vehicles produced annually contain soy-based foam in headrests including the 2013 Fusion, the F-150, the Taurus, and the Explorer. Fiat cars in Brazil contain polyurethane seat foams with about 5% soy polyol. Many Toyota vehicles have soy-based seat cushions including the Prius, Corolla, Matrix, RAV4, and the Lexus RX 350. Without any guarantees, Table 8.16 displays some industrial or potential examples of bioplastics used in the automotive sector. Many grades are partially produced from renewable resources. Without any guarantees, Table 8.17 displays some industrial or potential examples of NFs used in the automotive sector. Some grades may be partially produced from renewable resources.

8.5.4 Building and Construction Building and construction was the first outlet of WPCs, a fast-growing family. The list provided

below of industrial or potential application examples is not exhaustive:

• • • • • • • • •

Decking and boardwalks Flooring Cladding (siding) Fencing and railings Imitation wood shingles Window profiles and door profiles Exterior building trim (soffits, fascias, etc.) Interior building trim (doors, skirting boards) Sill plates construction

and

interface

elements

in

• Structural elements and marine/waterfront structures

• • • • • • • • •

Infrastructure House shingles Cabins Posts Landscaping timber Garden structures (gazebos) Bathroom and kitchen cabinets Beams and lumbers Decorative trim and moldings, etc.

Without any guarantees, Table 8.18 displays some industrial or potential examples of bioplastics

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Table 8.16 Examples of Bioplastics Used in Automotive and Transportation Market. Amorim Cork Composites: Thermoplastics or Rubbers Filled With Cork Seals, gaskets Arboform: Lignin-Derived Automotive interior parts BIOFRONT: Stereocomplex PLA Molded parts for automobile Cellulosics Furniture trims, sun visors, face shields, etc. Resound Biopolymers by PolyOne: PLA, PHB, PHBV, and Biopolyesters Combined With ETP; reSound NF: Natural Fiber Reinforced Formulations Interior automotive components Sorona: Trimethylene Terephthalate Automotive parts and other products Apparel and automotive mats and carpets Trellis Earth (Cereplast): Starch and Fossil Plastic Used in a range of markets including automotive Green Polyethylene Fuel tanks for the automotive industry Fluid containers Fibers: removable protective panels for armored cars Polyethylene rotomolded panels for the Think car produced in Norway Layer for multilayer films and sheets used in fuel lines PA11 Hydraulic, fuel, and water hoses and truck air brake hoses Monolayer and multilayer plastic fuel lines, etc. EcoPaXX Polyamide 410 Under-the-hood applications Engine covers for turbo engines (due to its high heat resistance of up to 230°C) Dimensionally stable crankshaft covers Fuel line connectors Cooling system applications including radiator endcaps, thermostat housings, and cooling tubes Automotive E-connectors Diesel exhaust fluid (AdBlue) systems VESTAMID TERRA PA610, PA 1010, PA 1012 Engine covers of cars High-stress housings and similar applications Transparent and extreme applications AgriPlast: PP, PE, Bioplastics, and Cellulose Fiber Injection-molded parts (Continued )

Table 8.16 Examples of Bioplastics Used in Automotive and Transportation Market.—Cont’d Biowert FlaxPP: PP Flax Fiber Injection-molded parts FibriPlast: Natural Fiber Mat and Fossil or Bioplastic Automotive interior parts such as parcel shelves, door panels, headliners, trunk side trims, etc., for all kinds of vehicles (cars, small cars, trucks, agricultural and industrial vehicles, etc.) Fibriboard: Preconsolidated Sheets Made in PP GF or PP NF Thermoformed or compression molded automotive interior parts, parcel shelves, door panels, headlining, trunk trims, etc. FibriPreg: Bioplastics Flax Fiber Composites, faces of sandwich composites SMC and BMC From Unsaturated Polyester and Jute, Sisal, Coconut, Banana, or Palm Fibers Scooter bodies Interior automotive panels Polyurethanes and Thermoplastics Reinforced With Coconut, Jute, Banana, or Cotton Truck parts Biopolyurethane: Foam Soy Based Seats, headrests, armrests Soundproofing Flax Nonwoven Interior trims, soundproofing Cereal, Corn, Barley into Matrices of PP, PE, ABS, PVC Composites Mats of Flax, Hemp, or Jute Interior trims, soundproofing Flax-, Hemp-, or Jute-Reinforced PP General-purpose composites ABS, Acrylonitrile butadiene styrene; BMC, bulk molding compound; ETP, engineering thermoplastics; GF, glass fiber; NF, natural fiber; PA, polyamide; PA11, polyamide 11; PE, polyethylene; PHB, polyhydroxybutyrate; PHBH, polyhydroxybutyrate-hexanoate; PLA, polylactic acid; PP, polypropylene; PVC, polyvinyl chloride; SMC; sheet molding compound.

Table 8.17 Examples of Natural Fiber Applications. Seat backs, seat padding

Audi, BMW, Citroen, Daimler-Chrysler, Ford, Lotus, Mercedes-Benz Trucks, Peugeot, Renault, Rover, Saab, Seat, Toyota, Vauxhall, Volkswagen, Volvo

Side and back door panels, headliner panels, boot lid finish panels, body panels, parcel shelves

Audi, BMW, Citroen, Daimler-Chrysler, Ford, Lotus, Peugeot, Renault, Rover, Saab, Seat, Toyota, Vauxhall, Volkswagen

Insulation, noise insulation panels, interior insulation, engine insulation

BMW, Mercedes-Benz Trucks, Renault, Toyota

Lining, boot lining, spare tire lining, molded foot well linings, roof cover, pillar cover, rear parcel shelf, interior carpet

Audi, BMW, Daimler-Chrysler, Ford, Lotus, Mercedes-Benz Trucks, Toyota, Vauxhall

Miscellaneous applications, hat rack, business table, dashboard, spoiler, bumper, wheel box, sun visor, cargo floor tray

Audi, Daimler-Chrysler, Lotus, Mercedes-Benz Trucks, Vauxhall, Volvo

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Table 8.18 Claimed Examples of Bioplastics Used in Building, Construction, and Civil Engineering. AgriCell: Foam Based on Cellulose Fibers From Grass Blown-in or blown-on insulation for walls, floors, and ceilings Amorim Cork Composites Solutions for acoustical and vibration issues, wall bearing material, underlay, under screed, floating screed, cork wall (final coating to protect houses) Core materials for lightweight sandwich composites for thermal, acoustical, or fire performance. Used in residential and industrial constructions ARBOFORM Lignin-Derived Products for construction industry BIOFRONT Stereocomplex PLA Molded parts for civil engineering and construction Cellulosics Lighting, signs, diffusers, lighting devices and accessories, profiles, etc. ProFi and Formi (by UPM): Natural Cellulose Fibers and Virgin or Recycled Plastic Injection molding and extrusion products including outdoor products Solanyl: Starch-Derived Brushes, honeycomb structures (tiles), level indicator tubes Sorona: Trimethylene Terephthalate Residential and commercial carpets Trellis Earth (Cereplast): Starch and Fossil Plastic Construction products Biosourced Polyamides Anticorrosion protection including lined pipes, buried gas pipelines, coextruded pipes, dirty water and effluent pipes used in aggressive environments, etc. Potable water transportation equipment and water treatment plants including powder-coated metal parts, etc. Green PE Films, vapor, and moisture barrier films, etc. Pipes, conduits, and fittings, gas, water, or sewer pipes, sheaths, etc. Large-sized objects such as cisterns, tanks, septic tanks, etc. Fiber and film such as removable protection for panels, etc. Pipes, tubes and protective conduits Insulation of electric wires Geomembranes basal liners, capping systems, cushioning layers, strengthening layers for soil reinforcement, containment liners, waterproofing membranes Renewable Unsaturated Polyester Cure-in-place pipes Wood Plastic Composites Based on PVC

Extruded in wood-like profiles that can be sawn, nailed, and screwed just like natural wood, etc. Doors and windows (Continued )

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Table 8.18 Claimed Examples of Bioplastics Used in Building, Construction, and Civil Engineering.—Cont’d Based on polyethylene

Deck boards, landscape timbers, picnic tables, and industrial flooring

Based on various polymers

Decking and other elements for construction such as industrial flooring, window and door profiles, hot tub siding, office accessories, landscape timbers, railings, molding, fencing, and others Infrastructure including boardwalks, marinas, and guardrails Interior architectural products such as floors, ceilings, walls, skirting, doors, cladding, panels, and decorative trims, etc. Technical profiles such as cable channels, supporting poles, fixing elements

PE, Polyethylene; PLA, polylactic acid; PVC, polyvinyl chloride.

Table 8.19 Examples of Bioplastics Used in Agriculture Market. Bionolle: Aliphatic Polyester Net, filament, yarn Mulching film Plant pot, tray BIOPAR: Starch-Derived Injection#-molded or thermoformed articles for garden, landscape gardening, and agriculture parts Film and bottle blowing, cast film, for products in the garden, landscape gardening, and in agriculture Bioplast: Starch-Based, PLA-Based Film Cornpole: Starch-Derived Mulching films Agricultural paints Ecovio: PLA and Ecoflex Mulch films Mater-Bi: Starch-Derived Mulching film Plant pots, bindings, clips, and devices for the controlled release of pheromones Extruded and woven nets for potatoes, onions, etc. PBS, PBSA: Polyester Mulch film PLA Lawn and garden products Plantic: Starch-Derived Seedling and planter pots for dispose into domestic compost Advertising product in the form of plants seeds packaged in a compostable blister (Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 8.19 Examples of Bioplastics Used in Agriculture Market.—Cont’d Solanyl: Starch-Derived Tree nursery, clips, tree protection spirals, pots, trays Horticulture articles Vegemat: Starch-Derived Vineyard fasteners Biosourced Polyamides Antifriction parts such as bearings, rods, etc. Hydraulic, fuel, and water hoses, air brake hoses, monolayer and multilayer plastic fuel lines, etc. Technical parts including pneumatic and hydraulic hoses, fuel handling, and hydraulic applications Technical parts such as gears, screws, and bolts, pulleys, collars, valve casings, rings, clips, ventilators, cooling fans, tanks, and containers, etc. Tubes for pneumatic control Green Polyethylene Tubes for pneumatic control Ensilage films, tunnels, greenhouses, punched films, mulching films Large-sized objects such as cisterns, tanks, etc. Membranes for water reserves PE fibers for ropes for fish-farming, anchorage, etc. PE foam for impact and vibration damping, etc. PE foam for machine soundproofing, etc. Tubing for agricultural pulverization of weed killers, insecticides, fertilizers Water or sewer pipes, sheaths, etc. Renewable Unsaturated Polyester Molded parts for the Model 9750 John Deere Harvester Combine made from SMC based on Ashland bio-UP Tractor hoods PBS, Polybutylene succinate; PBSA, polybutylene succinate-adipate; PE, polyethylene; PLA, polylactic acid; SMC; sheet molding compound.

used in building, construction, and civil engineering. Some grades are partially produced from renewable resources.

used in the agriculture market. Some grades are partially produced from renewable resources.

8.5.6 Other Markets 8.5.5 Agriculture Without any guarantees, Table 8.19 displays some industrial or potential examples of bioplastics

Without claiming to be exhaustive, Table 8.20 displays some industrial or potential examples of bioplastics used in some other markets. Some grades are partially produced from renewable resources.

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Table 8.20 Examples of Bioplastics Used in Various Markets. Trade Name

Family

Example of application

Electrical and Electronics Equipment, Household, Entertainment, and Office Appliances ARBOFORM

Lignin-derived

Electrical and electronics equipment

BIOFRONT

Stereocomplex PLA

Molded parts for electrical and electronics equipment

BIOFRONT

Stereocomplex PLA

Housings of Panasonic cell phones, other mobile devices, and digital consumer electronics

Biograde

Cellulosebased

Technical electronic parts

Biograde

Cellulosebased

Household equipment

Cellulosics

Cellulosics

Lighting, diffusers, lighting devices and accessories, etc.

Cellulosics

Cellulosics

Profiles, etc.

Cellulosics

Cellulosics

Household appliance items, etc.

Cellulosics

Cellulosics

Hairdressing items, etc.

Ecodear

PLA

Electric, commodity appliances

EcoPaXX

Polyamide 410

Frames in handheld devices like mobile phones

EcoPaXX

Polyamide 410

Connectors, low voltage switchgears, and other power distribution applications

Gaialene

Starch-derived

Steam generator cover

Ingeo

PLA

Mobile phone, laptops cases, appliances, ancillaries

PLA

Consumer electronics products

PLA

Personal computer housings, notebook computer housings

PLA

Housings of electronic products

PLA

Computer mouse

PLA

Office equipment and supplies

reSound

Bioresin and ETP

Electronics housings and equipment

Trellis Earth (Cereplast)

Starch and fossil plastic

Various products for electricity and electronics

Biopolyamides

Electricity, electrical household appliances such as electrical cables, special wires and cables, flexible telephone cables, inlet and outlet cable channels, etc.

Biopolyamides

Housings of microscopes, connectors, etc.

Biopolyamides

Optical fibers, etc.

Bio-PE

Molded electrical accessories, electrical connectors, etc.

Bio-PE

Wire and cables

Bio-PE

Tubing, etc.

Furniture and Bedding ARBOFORM

Lignin-derived

Furniture industry

Cellulosics

Cellulosics

Decorative rods, bands, profiles, etc. (Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 8.20 Examples of Bioplastics Used in Various Markets.—Cont’d Trade Name

Family

Example of application

Fasal Wood

WPC

Ceiling boxes from Fasal for different lights

Fasal Wood

WPC

Furniture legs for bathroom furnishings

Biopolyamides

Antifriction parts such as bearings, rods, etc.

Bio-PE

Seats of bus shelters

Bio-PE

Highly colored structures of play areas (ladders, stationary motorbikes, labyrinths, huts, etc.)

Bio-PE

Bottom-of-the-range small storage units and medicine chests

Bio-PE

Bathroom stools

Bio-PE

Inflatable furniture using sheets or films of PE

Bio-PE

Street and bathroom furniture, seats, etc.

Bio-PE

Accessories such as pegs, dowels, nuts, spacers, inserts, plate bearings, casters, etc.

Mechanical Engineering Bionolle

Aliphatic polyester

Foamed tube

Bionolle

Aliphatic polyester

Frame of fan

Cellulosics

Trims, etc.

Cellulosics

Hand tools, screwdriver handles, buttons, handles, hammer heads, etc.

Cellulosics

Metallized parts, vacuum metallized parts, reflectors, etc.

Biopolyamides

Anticorrosion, protection including offshore drilling, offshore oil and gas production and test lines, gas and water injection lines, gas lift lines, pipes, fittings, valves, lined pipes, powdering within health care equipment, oil industry, internal coating in new and refurbished injection tubing, production tubing and flow lines, production risers, choke and kill lines, nitrogen lines, hydraulic lines, buried gas pipelines, coextruded pipes, dirty water and effluent pipes used in aggressive environments, etc.

Biopolyamides

Antifriction parts such as bearings, rods, etc.

Biopolyamides

Pneumatic and hydraulic hoses, petrochemical, fuel handling, and hydraulic applications gears, collars, valve casings, rings, clips, etc.

Biopolyamides

Powdering, etc.

Bio-PE

Large-sized objects such as tanks, cisterns, hydraulic tanks, septic tanks, chemical tanks, etc.

Bio-PE

Chemical pipes, etc.

Bio-PE

Cross-linked foams, extruded and molded parts, etc.

Bio-PE

Gears, bearings, antifriction parts for light loads, etc.

Bio-PE

Foam: Machine soundproofing, etc. (Continued )

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Table 8.20 Examples of Bioplastics Used in Various Markets.—Cont’d Trade Name

Family

Example of application

Bio-PE

Foam: Impact and vibration damping, etc.

BIOFRONT

Stereocomplex PLA

Eyeglass frames, medical care

BIOFRONT

Stereocomplex PLA

Molded parts for medical care

Bioplast

Starch-based, PLA-based

Injection#-molded articles for medical devices

Cellulosics

Cellulosics

Packaging, containers for healthcare, cosmetics, perfumery and personal care supplies, etc.

Cellulosics

Cellulosics

Ophthalmic, optical safety frames, spectacles, sunglasses, etc.

Mater-Bi

Starch-derived

Nappies, sanitary towels, and panty liners

PHB

Polyester

Injected and extruded articles

PHB/PHV

Polyester

Medically contaminated articles

PLA

PLA

Medical devices

reSound

Bioresin and ETP

Medical devices and equipment

TephaFLEX

Polyester

Medical devices such as sutures, films, and textile products

Trellis Earth (Cereplast)

Starch and fossil plastic

Medical supplies

Bio-PE

PE foam for the waterproof layers of sanitary towels and nappies

Bio-PE

Implants, instruments used to insert suture clips, casings of apparatus of paramount importance

Bio-PE

Films and sheets, etc.

Bio-PE

Blow-molded containers, bottles for drugs, etc.

Bio-PE

PE foam for electrode pads for electrocardiogram testers

Medical

Sports and Leisure EcoPaXX

Polyamide 410

Sports shoes, ski- and snowboard bindings, or stiffeners and fasteners, dynamically loaded applications

ARBOFORM

Lignin-derived

Consumer articles, jewelry, toys

ARBOFORM

Lignin-derived

Musical instruments

Bionolle

Aliphatic polyester

Golf tees

Cellulosics

Pens, stationery supplies, pen barrels, writing instruments, squares, etc.

Cellulosics

Recreational parts, etc.

Cellulosics

Costume jewelry, etc.

Cellulosics

Toys and sporting goods, etc.

Cornpole

Starch-derived

Ballpoint pens

Fasal Wood

WPC

Toy cars (Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 8.20 Examples of Bioplastics Used in Various Markets.—Cont’d Trade Name

Family

Example of application

Fasal Wood

WPC

Musical instruments

Fasal Wood

WPC

Games such as Cuboro, Schloss Schlotterstein, Ubongo

Fasal Wood

WPC

Company Art Peter produces injection-molded urns

Fasal Wood

WPC

Trappings for Christmas trees

Fasal Wood

WPC

Golf tees

Gaialene

Starch-derived

Bike mudguard

Mater-Bi

Starch-derived

Pens, pencil sharpeners, rulers, children’s toys

Mater-Bi

Starch-derived

Combs

Undefined

Toys and leisure including golf balls and tees, hunting cassettes

PLA

Gift cards, hotel key cards, loyalty and transactional cards

PLA

Sporting goods, toys

Solanyl

Starch-derived

Sports, toys, and leisure, for example, airsoft bullets, golf balls and tees, hunting cassettes

Treeplast

WPC

Mosaic-jigsaw-puzzle, promotional articles, Christmas tree decoration

Treeplast

WPC

Multiuse laptop stand, brush handle, golf tees, ice-drink holder

Vegemat

Starch-derived

Golf tees

Vegemat

Starch-derived

Parachute links

Vegemat

Starch-derived

Dog treats

Biopolyamide

Wheels, saddle stems, crank gears for bicycles, etc.

Biopolyamide

Ski boots, etc.

Biopolyamide

Roller skates, toys, etc.

Biopolyamide

Snowmobile bumpers, etc.

Biopolyamide

Hovercraft propellers, etc.

Biopolyamide

Grass and leaf blower parts and housings, etc.

Biopolyamide

Filaments for fishing, etc.

Bio-PE

Hulls of boats, canoes, buoys, sailboards, fun boards, etc.

Bio-PE

Luges, ski pad, etc.

Bio-PE

Beach shoes, etc.

Bio-PE

Swimming pool covers, etc.

Bio-PE

Toys, etc.

Bio-PE

Foam for life jackets, life suits, etc.

Bio-PE

Foam for safety padding, etc.

Bio-PE

Foam for buoys, etc.

Bio-PE

Foam for gym mats, padding, damping and insulating mats, etc.

Bio-PE

Foam for stuffing of rucksacks in foam-coated textiles, etc.

Bio-PE

Foam for toys, 2D and 3D puzzles, floating toys, etc.

Ingeo

ETP, Engineering thermoplastics; PHB, polyhydroxybutyrate; PHV, polyhydroxyvalerate; PLA, polylactic acid; WPC, wood plastic composite.

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Further Reading Technical Guides, Newsletters, Websites ABA—Australasian Bioplastics Association; Adapt Low Carbon Group; API Applicazioni Plastiche Industriali Spa; ASTM; Audi; Axion Polymers; BASF SE; BCC Research; Because We Care Pty Ltd.; Biodegradable Products Institute; BIO-FED, Branch of AKRO-PLASTIC GmbH; BIOME BIOPLASTICS Ltd.; BIOTEC GmbH & Co. KG; BMW; Brilliant Little Planet; CABOPOL; CEPLAST S.r.l.; Citroen; Coca-Cola; CORBION Group Netherlands B.V.; Daimler-Chrysler; DaniMer Scientific; Deceuninck; Decodeck; DIN CERTCO; DM; DONGAH CHMICRONICAL Co Ltd.; DONGGUAN XINHAI Environment-Friendly Ma; EFSA; Eidai Kako Co; EIN Engineering; ENYAX Srl; European Bioplastics; European bioplastics; FDA; FIPLAST Srl; FKuR Kunststoff GmbH; FLINT GROUP Europe; Ford Motor Company; FUTURAMAT; Gevo, Inc.; GIOSOLTECH CO, Ltd.; GRABIO Greentech Corporation; GREENLIFE Srl; Guangdong Shangjiu Biodegradable Plastics; HUBEI Guanghe Biotechnology Co Ltd.; ISO; Japan BioPlastics Association (JBPA); JINHUI ZHAOLONG HIGH TECHNOLOGY Co L; John Deere; KAFRIT INDUSTRIES (1993) LTD.; KANEKA Corporation; KINGFA SCI. & TECH. CO., LTD.; KUREHA Corp.; LIMAGRAIN CEREALES INGREDIENTS; Lotus; MarketsandMarkets; Mercedes-Benz; MEREDIAN Inc.; METABOLIX, Inc.; MICROTEC srl; MINIMA TECHNOLOGY CO Ltd.; MITSUBISHI CHMICRONICAL Corp.; Morssinkhof Plastics Zeewolde BV; MULTIBAX Public Company Ltd.; NINGXIA

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QINGLINSHENGHUA Technology Co; North Wood Plastics Inc.; NORTHERN Technologies Intl. Corp.; Nova-Institut; NOVAMONT S.p.a. Unita Di Novara; NUREL; Pepsico; PERSTORP AB; Peugeot; PLASTICOS HIDROSOLUBLES SL; Plastics News; Polima; Polyplank; PONTEX Group; PTL; PTT Research and Technology Institute; Renault; RODENBURG BIOPOLYMERS; Rover; Saab; Seat; SHANDONG FUWIN NEW MATERIAL Co Ltd.; SHOWA DENKO K.K.; SpecialChem; Sphere; TIPA Corp; Toyota; Twinson; UL; Vauxhall; Vegeos; Vinc¸otte; VinylPlus; Virent Cy; Vivos; Volkswagen; Volvo; Werzalit; wikipearl; WUHAN HUALI; XINJIANG BLUE RIDGE TUNHE POLYESTER; YIFAN XINFU Pharmaceutical Co Ltd.; ZHEJIANG HISUN BIOMATERIALS Co, Ltd.

Papers and Books Biron, M., 2015. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2014. Thermosets and Composites. Elsevier Ltd. Biron, M., 2013. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. JEC Composites: http://www.jeccomposites.com/ Plastics Additives & Compounding, Elsevier Ltd. Modern Plastics Encyclopaedia, McGraw-Hill Publications. Modern Plastics International, Canon Communications LLC, Los Angeles, CA, USA. Plastics News.com, Crain Communications. Reinforced Plastics, Elsevier Ltd.

9 Recycling Plastics: Advantages and Limitations of Use From a sustainability point of view, recycling is ranked as close to “repair and reuse” options (see Fig. 1.3) but from a practical standpoint recycling offers a much wider perspective. The recycling of plastics has been used for a long time but faces various obstacles that can be overcome thanks to more or less constraining and innovative countermeasures as those suggested by examples in List 9.1. Today, without going into details, recycling of plastics is the first source of renewable plastics. The plastics product market is valued in US$ trillion while recycling of plastic products is valued in some tens of billions according to three sources:

• Transparency MarketResearch (https://www. transparencymarketresearch.com/plastic-recyclingmarket.html) in a recent report states that the global plastic recycling market, which was valued at US$31.5 bn in 2015 is expected to reach a figure of US$56.8bn by 2024. During the forecast period of 2016 24, the global market is expected to grow at a compound annual growth rate (CAGR) of 6.9%.

• MarketsandMarkets (https://www.marketsandmarkets.com/PressReleases/recycled-plastic.asp) estimates the global recycled plastics market at about US$37 bn in 2017 and is projected to reach about US$50 bn by 2022, at a CAGR of 6.4% between 2017 and 2022.

• BusinessWire

(https://www.businesswire. com/news/home/20171106006076/en/RecycledPlastics-Market-2017 2022-Global-IndustryTrends) expects the global recycled plastics market reached a value of US$37 bn in 2016 and US$51 bn by 2022, exhibiting a CAGR of about 6% during the period 2017 22.

In weight, some estimates quote a recycling rate of about 10% of the plastics used in round figures. Today, from a practical point of view, recycling is generally the most sustainable end-of-life for

plastics. Theoretically, reuse could be a more sustainable solution but outlets are limited. High research activity open the door to a steady growth. Energy recovery consumes a lot of plastics waste but generally is less satisfying from a sustainability standpoint and is, therefore, slowly declining. The following information deals with the recycling of plastics that is on the rise.

9.1 Recycling Outline It is estimated that in round figures, plastic wastes produced per year represent about 50% 60% of the produced plastic goods in the same year, that is to say approximately 200 million tonnes per annum around 2020. Plastic wastes represent a phenomenal source of polymers, difficult to exploit because of practical, technical, psychological, and economic barriers. However, it is also a phenomenal source of pollution that must be carefully treated. In any case it is necessary to pay for the treatment of the wastes. Plastic recycling can have several advantages:

• Conservation of nonrenewable fossil oils: Plastic production uses about some 8% of the world oil production, 4% as feedstock, and 4% for manufacture.

• Reduced consumption of energy. • Reduced emissions of carbon dioxide (CO2), nitrogen oxides (NOx) and sulfur dioxide (SO2).

• Reduced amounts of solid waste going to landfill. According to the Bureau of International Recycling (BIR—http://www.bir.org/industry/plastics/):

• One tonne of recycled plastic saves: • 5774 kWh of energy. There is an 80% 90% reduction

in

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00009-4 © 2020 Elsevier Ltd. All rights reserved.

energy

consumption

by

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List 9.1 Proposition Examples for Broader Spreading of Recycling Cons

Pros

Negative image

Performance advancements Quality improvement Economic benefits Environmental benefits

Lack of legislation

Mandatory legislation

Limitation of recyclate use or level

Performance advancements Quality improvement

Lack of waste management system

Launch of new product waste streams, corporation waste streams

Lack of collection

New collection scheme

Sorting issues

Sorting improvement Specialized collection Direct recycling of waste without sorting

Insufficient performance

Design to ease recycling Sorting improvement Recycling technique improvement Upgrading improvement

Lack of competitiveness versus new resins

Design to ease recycling Improve recycling chain

Lack of recycler responsibility

Empower recyclers

Lack of quality standards

Development of quality standard and certification

Low demand

Outlet growth Performance enhancement Mandatory legislation Better competitiveness

producing recycled plastic compared to producing fossil plastic from virgin materials (oil and gas). • 16.3 bbl (2604 L) of oil, • 98 million Btu’s (B103 GJ) of energy, • 22 m3 of landfill.

• Worldwide trade of recyclable plastics is valued at US$5 billion per year and is estimated to represent a total of 12 million tonnes. Andreas Kicherer, head of the Eco Efficiency Group at BASF, says that the US$4.6 bn cost for recycling 50% of plastics waste in the EU could

save 9 million gigajoules of energy and 6 million tonnes of carbon dioxide, as well as creating up to 40,000 jobs in plastics sorting. A review of life cycle analyses has concluded that recycling plastics saves about 1.5 2 tonnes of carbon dioxide per tonne of plastic recycled, when compared to alternatives of landfill and incineration with energy recovery. Currently plastic recycling ratio is very variable according to the nature of wastes and the countries. Generally, the used ways are not really satisfying, with landfilling and incineration shares being too large.

9: RECYCLING PLASTICS: ADVANTAGES

AND

LIMITATIONS

To summarize, end-of-life plastic wastes can be classified as:

• Municipal solid wastes (MSWs) including: • Packaging, containers; water, soft drink and shampoo bottles; lids, etc.

• Nondurable goods such as diapers, trash bags, cups and utensils, medical devices, etc. • Durable goods, for example appliances, furniture, refrigerators, etc.

• Selected streams, principally automotive, beverage bottles. Worldwide, about 27 million end-of-life cars are recovered each year. Plastic parts can be: • Identified and sorted for large parts such as bumpers, battery trays, etc. • Mixed with other materials such as rubbers, glass, metals, fabrics, etc. and dirt into the so-called auto shredder residues (ASR) weighing 5 million tons, or 185 kg/car. Other waste streams can be more or less easily collected and sorted according to the opportunities by, for example:

• Market or application Packaging, automotive, building, agricultural, beverage, domestic, electricity, electronic, garden, house, toys, IT, etc.

• Type of parts Containers, films, bags, bottles, boxes, sheets, foams, body parts, cans, dolls, children’s toys, crates, wheelie bins, batteries, generators, phones, wallpapers, tapes, tires, window frames, etc.

• Polymer Polyethylene (PE) [high-density PE (HDPE), low-density PE (LDPE)], polypropylene (PP), PE terephthalate (PET), polyvinyl chloride (PVC), polystyrene (PS), expanded PS, acrylonitrile butadiene styrene (ABS), acrylic, polycarbonate (PC), polyurethane, nylon, rubbers, fluorinated elastomers, etc. Sometimes it is possible to combine the polymer recycling with another material recycling, for example lead of batteries, precious metals in electronics, copper of wires and cables, among others.

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It is necessary to distinguish reused polymer parts, recyclable polymers (virtually all polymers), and effectively recycled (and reused) polymers. At the end point, outlets may be as diverse as, for example:

• Reuse of polymer parts. Reuse means any operation by which components of end-of-life vehicles are used again for the same purpose for which they were conceived. Reuse, if conducted under good conditions, is the best recovery solution.

• Recycling means the reprocessing in a production process of the waste materials for the original purpose (closed loop) or for other purposes (open loop) excluding energy recovery. Reprocessing in the production for the original purpose is the best recycling solution.

• Energy recovery means the use of combustible waste as a means to generate energy through direct incineration with or without other waste, but with recovery of the heat.

• Recovery means any of the applicable operations provided for in annex IIB to Directive 75/442/EEC. Landfilling of unrecovered wastes is the worst solution. Recycled plastics are difficult to exploit for several reasons. According to two polls (see Table 9.1) launched by Omnexus (http://www. omnexus.com/), “Which factor limits the increase in the use of postconsumer recycled polymers, the most?” and “What is the most critical issue in using recycled engineering thermoplastics?” the main issues are the “Reliability of supply, the Variation of performances” and the “Limited processing stability” for 60% and 72% of voters. The cost is also an issue for 11% and 17% of voters. Two main benefits of polymer recycling include a cost saving of 10% up to 50% versus the same virgin material, and an environmental advantage concerning a lower consumption of nonrenewable resources and lower emission of greenhouse gases (GHGs). Some regulations or specifications limit the level of recycled material in certain end products.

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Table 9.1 Issues Limiting the Use of Recycled Polymers. Commodity and Engineering (%) Reliability of supply

22 27

Variation of performances

26 41

Cost

11 17

Limited processing stability

9.3 9.1

Commodity (%)

Engineering (%)

Limited performances

9.3

Ban by some specifications

6.8

Risk of polluting substances

14

Lack of regulations

8

Table 9.2 Examples of Greenhouses Gases (GHG) Emissions and Fossil Resource Consumption. Fossil Resource Consumption GHG (kg CO2-eq./ tonne) PE, virgin

1200

PE, recycled

400

PP, virgin

1250

PP, recycled

400

PS, virgin

1600

PS, recycled

400

Saving (kg CO2eq./tonne)

Saving (%)

Crude Oil-eq. per tonne

Saving, Crude Oileq. per tonne

Saving (%)

2 1400

96

2 1400

96

2 1450

96

1450 2 800

67

50 1450

2 850

68

50 1500

2 1200

75

50

PE, Polyethylene; PP, polypropylene; PS, polystyrene.

9.1.1 Environmental Benefits of Recycling It is worth noting that by changing the assumptions in environmental studies, results may be different. So various studies lead to different figures but point out that recycling is beneficial from an environmental point of view. Some examples are quoted below and others are quoted in Section 9.4 for GHGs. S.N.M. Menikpura, Totoki Yoshiaki and Janya Sang-Arun (Conference Proceeding, 3R International Scientific conference on Material Cycle and Waste Management, March 10 12, 2014, Kyoto, Japan “The Implications of Packaging Plastic Recycling on Climate Change Mitigation and Fossil Resource Savings A Case Study in Japan”) find virgin resin

production contributes to higher GHG emissions and fossil fuel consumption than the recycling process. The estimated GHG emissions and fossil resource consumption amounted to 2 853 kg CO2-eq. and 2 1374 kg crude oil-eq. per tonne of recycled waste packaging plastic. For PE, PP, and PS, Table 9.2 displays some examples of GHG emissions and Fossil resource consumption. EPA (US Environmental Protection Agency— www.epa.gov/) calculated (see Table 9.3) the difference between:

• GHG emissions from manufacturing 100% recycled material and 100% virgin material

• Energy per kilogram plastic manufacture from manufacturing 100% recycled material and 100% virgin material

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Table 9.3 Differences in Emissions and Energy Between Recycled and Virgin Plastics. Manufacture (MTCO2E/Short Ton) Product/Material 100% Virgin Inputs

100% Recycled Inputs

GHG Emission

Difference Between Recycled and Virgin Manufacture CO2 eq. MT/Short Ton

%

HDPE

1.95

0.18

-1.77

91

LDPE

2.33

0.18

-2.15

92

PET

2.13

0.18

-1.95

91

MJ/kg

%

Energy HDPE

33.6

5

2 28.6

85

LDPE

37.8

5

2 32.8

87

PET

38.5

5

2 33.5

87

GHG, Greenhouse gas; HDPE, high-density polyethylene; LDPE, low-density polyethylene; PET, polyethylene terephthalate.

Thomas Astrup, Thilde Fruergaard, Thomas H. Christensen, Technical University of Denmark, “Recycling of plastic: accounting of greenhouse gases and global warming contributions” study major GHG emissions related to plastic waste recycling with respect to three management alternatives—recycling of clean, single-type plastic, recycling of mixed/contaminated plastic, and use of plastic waste as fuel in industrial processes. They concluded that substitution of virgin plastic should be preferred. If this is not viable due to a mixture of different plastic types and/or contamination, the plastic should be used for energy utilization. Recycling of plastic waste for substitution of other materials such as wood provided no savings with respect to global warming. Potential downstream savings (60 1600 kg CO2-eq. per tonne of plastic waste) arising from substitution of virgin plastic, wood, and energy fuels highly depend on substitution ratios and CO2 emissions from electricity production. The Waste & Resources Action Programme (WRAP—http://www.wrap.org.uk/), which was created as part of the British Government’s waste strategy, presented in autumn 2006 a report concerning an international review of life cycle analysis carried out in the recycling area. The Technical University of Denmark conducted the study commissioned by WRAP. The report studied 55 life cycle analyses, with a total of 200 different scenarios, carried out in a dozen European countries including Sweden, as well as the United States and Australia. A comparison between recycling and

incineration reported the average climate benefits of plastic to 2 tons of CO2 per ton of recycled plastic. The crude oil consumption was also reduced by 1000 L. Franklin Associates (Life Cycle Impacts for Postconsumer Recycled Resins: PET, HDPE, and PP) edit (December 2018) a study dealing with the effects of recycling for three common plastics namely HDPE, PET, and PP. Life cycle scenarios are very diverse and some assumptions are used, which leads to broad ranges of results but apart from three cases, the use of recycled polymers is attractive. Table 9.4 displays for each topic the % reduction due to the replacement of virgin resin with recycled resin of the same type. Negative data are damaging, the recycled resin use having a harmful effect of the considered environmental indicator. The statistical analyses for the three plastics processed according to all the methods demonstrate the significant reduction of pollution with a broad range of data whose three are not beneficial. Overall results by plastic type are not significantly different. In contrast, results for the three plastic types by environment indicators are more differentiated with two groups:

• High reduction (superior to 40%) for energy, GHG, acidification potential, smog potential

• Low reduction (about 20%) for water, eutrophication potential, solid wastes.

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Table 9.4 Environmental Benefits of Recycled Resin Use. All Plastics, All Indicators, All Methods

HDPE All Methods, All Methods

PET All Methods, All Methods

PP All Methods, All Methods

Mean

38

32

42

41

Median

36.5

32

38

39.5

Standard deviation

25

28

26

21

Minimum

24

22

24

12

Maximum

88

88

79

88

Samples

42

14

14

Energy

GHG

14 Acidification Potential

Water

Solid Wastes

Eutrophication Potential

Smog Potential

Mean

63

52

43

25

20

21

40

Standard deviation

24

19

18

25

22

21

20

Minimum

39

34

23

24

21

22

18

Maximum

88

71

70

59

58

46

75

GHG, Greenhouse gas; HDPE, high-density polyethylene; PET, polyethylene terephthalate; PP, polypropylene.

9.1.2 Economics of Recycling As for any industrial activity, all the processes used to convert plastics produce scraps resulting from the startup and shutdown periods of the processing machinery, from out of specification products and from quality control samples. Almost all molders recycle their thermoplastics waste inhouse. The plastics recyclers also recycle this type of material, particularly waste from thermoforming and off-specification parts and products. These recovered materials are often referred to as “reprocessed” while “recycled materials” is often used for postconsumer parts and products. Of course, recycling of postconsumer plastics is much difficult especially for mixed or comingled waste or single-stream collection. After mechanical recycling and eventually upgrading, residual plastic waste can possibly be converted into heat and power. The recycling market has a direct relationship with virgin plastics production, demand, and cost. A drop in virgin plastics costs leads to a decrease in prices and trade volume of plastic wastes.

9.1.2.1 Market Overview by Region Table 9.5 displays a brief overview of the plastics waste market. China, including Hong Kong is

by far the biggest importer with about 50% of the global trade. It is also the biggest recycler with 23 million tonnes of recycled plastics. That is changing because China bans the import of plastics wastes. For the first time, wastes may pile in the exporting countries but later the recycling may be boosted in those countries. Europe, the biggest exporter worldwide of waste plastic intended for recycling, mainly depends on China: 87 wt.% is exported to China. The exported quantity is 46% of the overall quantity collected for recycling, and 12% of the entire plastic waste arising in Europe. USA produces a high level of plastics waste but the recycling rate is low. Those data are questionable because of the uncertainty of statistics and the fact that some data are counted two times: once by the exporter and again by the recycler. Globally, the recycled rate could be approximately 15%. Let us remember that figures of BIR are very different. Worldwide trade of recyclable plastics is valued at US$5 billion per year and is estimated to represent a total of 12 million tonnes. Overview of Plastic Wastes in United States

Table 9.6 displays for the United States, an example of a breakdown of various plastic waste streams. MSW, commonly known as trash, garbage,

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Table 9.5 Overview of the Plastics Waste Market.

EU 2012 USA 2012

Postconsumer Plastic Waste

Recycling

Energy Recovery

Landfill

MT

25.2

6.6

8.9

9.7

%

100

26.3

35.6

38.1

MT

32

3

%

100

9

China

MT

23

Total

MT

32.6

Table 9.6 Plastic Wastes for the United States in 2003. Million Tons

%

Packaging wastes

11

37

Durable goods wastes

8

27

Nondurable goods wastes

6

20

Others

2

6

(Subtotal MSW)

(27)

(90)

Subtotal other streams

3

10

Estimated total plastic wastes

30

100

MSW

Other streams

MSW, Municipal solid waste.

refuse, or rubbish is the main stream containing 37% of packaging waste. The recycling level broadly fluctuates with the type of end product. For example, in 2009, the plastic bottle recycling rate reached 1.2 million tonnes, that is to say 28% of all plastic bottles consumed in the United States. Overview of Plastic Wastes in Europe

Only around 12% of the total plastic wastes generated within the EU is actually recycled inside its borders while some 38% is still going to landfill. The total for the EU is the result of very different country situations. Switzerland, Germany, Austria, Luxembourg, Belgium, Denmark, Sweden, the Netherlands, and Norway have a high level of recycling and energy recovery, while Cyprus and Malta value less than 15% of their plastics wastes.

Table 9.7 displays an example of a breakdown of the collectable plastic wastes with a recovery accounting for a low 38% including energy recovery. Landfilling and incineration, expensive and polluting, count for a large majority, 62%. Situations are dissimilar according to the considered markets. Considering the recovery percentages, “agriculture” and “industry” are the right candidates with about 50% recovery. MSW is an ambiguous category with the highest weight of recovery, a slightly lower recovery percentage, and a particularly high percentage (90%) of energy recovery. “Automotive”, “building and construction”, and “electrical and electronic (EE)” recycle a very small share of their wastes. Table 9.8 displays for Europe, an example of a breakdown of the plastic waste recoveries. The most exciting ways, mechanical and feedstock recovery, are the minority with a 40% share including “export” which is reused after mechanical recycling. Let us remember that these data are linked to the collectable plastic wastes accounting for 38% of total plastic wastes, that is to say the real recovery is only in the order of 15%. Feedstock recovery is marginal.

9.1.2.2 Recovery Costs: A Severe Obstacle to a Self-Growth Recycling is an environmental concern but it can also be a cheaper source of polymers as we can see in Table 9.9 comparing the costs of virgin and recycled materials. Virgin materials are general purpose grades and recycled polymers are claimed clean and of natural color. Colored and less clean grades are cheaper.

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Table 9.7 Europe: Breakdown of Collectable Plastic Wastes. Collectable Plastic Waste Total

Landfill and Incineration

Recovery

3 1000 t

3 1000 t

3 1000 t

% Share of Total

Agriculture

311

145

166

53

Industry

4190

2145

2045

48

MSW

13,671

8246

5425

40

Automotive

959

895

64

7

Building and construction

628

574

54

9

EE

848

811

37

4

20,607

12,816

7791

38

EE, Electricity and electronics; MSW, municipal solid waste.

Table 9.8 Europe: Breakdown of Plastic Waste Recovery. Energy

Mechanical

Export

Feedstock

3 1000 t

%

3 1000 t

%

3 1000 t

%

3 1000 t

%

Industry

444

9

1332

54

269

79

0

0

MSW

4222

90

843

35

54

16

330

100

Agriculture

1

B0

149

6

16

5

0

0

Automotive

7

B0

58

2

0

0

0

0

Building and construction

0

0

52

2

2

B0

0

0

EE

3

B0

32

1

0

0

0

0

Total

4677

100

2466

100

341

100

330

100

% of collectable plastic wastes 60

32

4

4

EE, Electricity and electronics; MSW, municipal solid waste.

Table 9.9 Estimated Costs of Polymers (h/kg). Virgin Standard

Clean Recyclate, Natural

Polyethylene, LDPE

1.3 1.7

0.4 1.4

Polyethylene, HDPE

1.4 1.7

0.6 1.8

PP

1.5 2.1

0.4 1.6

PS

1.7 1.9

0.55 1.9

PET for bottles

1.3 1.6

0.65 1.6

PVC

1.2 1.6

0.4 0.5

ABS

1.4 2.1

1.2 2

ABS, Acrylonitrile butadiene styrene; HDPE, high-density polyethylene; LDPE, low-density polyethylene; PET, polyethylene terephthalate; PP, polypropylene; PS, polystyrene; PVC, polyvinyl chloride.

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As examples, before the recent oil crisis:

1

• The price of recycled linear LDPE (LLDPE) €/kg

was estimated by several sources between 85% and 105% of the virgin PE price.

• For a certain part with production volumes of 3000 t/year, it was shown that the economic equilibrium was between h0.6 and h0.7 per kg for the recyclate. 0 1995

2000

2005 Year

2010

2015

Figure 9.1 Price examples of a recycled commodity between 2000 and 2014.

Prices are sensitive to time, quantities, quality, demand, and prices of virgin polymers. Fig. 9.1 shows examples of the variations of prices for a commodity between 2000 and 2015. This is an example only, and not a general rule. The high recovery costs slow down the selfdevelopment of recycling by lowering its economic interest versus its lower technical performances. In the worst-case scenario, the cost of recycling is a combination of the operations of collecting, dismantling, sorting, treatment, and recycling. From an economical point of view, the cost assessment of the recyclate depends primarily on the price retained for the waste. The recycling cost is in the range of:

• US$0 per kg for a recyclate of processing scrap whose grinding cost balances the cost it would have been necessary to pay to eliminate it.

• To more than US$1.4 per kg if one has to take into account the combined costs of collecting, dismantling, sorting, grinding and recycling treatment. To decrease the dismantling and sorting costs of plastic parts it is necessary to anticipate these steps at the design stage:

• To consider methods of assembly to make dismantling easier.

• To standardize the plastics to be used. The monomaterial concept is the most attractive but is sometimes unrealistic for technical and economic reasons. The compatible material concept is more realistic but less attractive.

• For various methods and end-of-life products, the claimed equilibrium costs vary in the range h0.5 h1 per kg.

• For the solvent process, Wieteck (http://www. wietek.com/wietek.htm)—a commercial operator of a 4000 t facility—estimates that the process is economically viable for a polymer price exceeding h1 per kg. Of course, a recycled polymer must be cheaper than the same virgin polymer. Fig. 9.2 displays examples of ratios—recycled polymer cost/virgin polymer cost—without indications concerning the polymer type and the level of purity and upgrading. Obviously other figures may be found elsewhere. The range of recycled polymer costs is broader than the range of homologous virgin polymer costs depending on recyclate quality, upgrading, demand on defined grades, polymer type, and general economic situation. According to this graph, the cost saving evolves between 50% and 90% of the virgin material cost with usually a 20% advantage. The polymer cost is an important parameter but lower recyclate quality and possible processing troubles or adaptations may partially or totally annihilate this advantage. So, two polls show that more than 10% of voters are not economically satisfied by recyclate use. Often a recycled material is mixed with a virgin polymer. Producers’ recommendations vary with the polymers and the reinforcement. For example, recycled engineering thermoplastics (ETPs) can be used from 15% up to 30% and TPE from 10% up to 50%. Recycled LFRT use is the most limited, for example 5%. These levels are not rules and certain products can be entirely made out from recycled materials. For an ETP, the far lower cost of the plastic waste leads to a beneficial structure of the ready to be injected or extruded material cost as shown in Fig. 9.3 material-cost-composition.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Frequency

420

0

0.2

0.4

0.6

0.8

1

Ratio

Figure 9.2 Ratio of recycled cost to virgin cost.

Margin Compounding Additives Virgin (left) or waste (right)

Cost per unit

Figure 9.3 Material cost composition.

9.1.3 Reliability of Recycling Reliability of recycling may be uncertain for several reasons, the main being:

• Homogeneity of plastics wastes is not well defined, conditions of use being uncertain for postconsumer wastes even if parts are well defined.

• Plastic wastes are scattered: bags are light and Incentive Effect of High Crude Oil Price

For numerous virgin polymers, crude oil is used both as feedstock and as energy source for production. For recycled polymers, crude oil used as feedstock for virgin polymers is saved and crude oil is only used for energy production. To simplify, if crude oil cost is doubled and if the energy cost is 25% of the total cost of the virgin or the recycled polymer, for a theoretical and purely hypothetic case:

• The increase of the virgin polymer cost may be about 50%

• The increase of the recycled polymer cost may be about 35%. For another hypothetic case concerning a lowcost commodity such as LLDPE, if the recycled polymer cost is 85% up to 105% of the virgin PE price for a low-crude oil price, after this one has doubled, the recycled PE cost becomes 60% up to 75% of the virgin PE. Under these conditions, recycling becomes more economically interesting.

dispersed into municipal wastes (or flying in the wind), bumpers are included in 1 or 2 tons of other materials of a car, bottles may be made out of PVC, PET, PE, etc.; PVC wallpapers are shredded and recoverable in small quantities, etc.

• Postconsumer plastics are degraded by their service life: long exposures to air, heat, light, and chemicals modify the chemical composition and alter the chemical structure of the basic polymer.

• Plastics are often intimately commingled with incompatible materials and separation is difficult, for example wire coating, waterproof fabrics, reinforced belts, etc.

• The most-used plastics are cheap and competitiveness of recycling is difficult to obtain. Conversely expensive plastics are little used in small parts included in sets made of other materials. Research costs for recycling are not easily paid off.

• Thermosets are crosslinked, which creates an irreversible 3D-network and prevents reprocessing contrarily to thermoplastic polymers.

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From an environmental point of view, reprocessing of plastic wastes is an efficient solution that can be considered according to two ways:

• Reuse in the same production, or primary or closed-loop recycling

• Reuse in another application which is less performing, less demanding, and, of course, less lucrative (open loop recycling) Reliability depends on the history of waste. An efficient recycling requires to think recycling since the design and to apply some design guidelines such as, for example:

• Simplify component design. • Reduce the number and types of materials in a device, and favor use of monolithic plastic. If possible, use polymer materials of the same type in a single device, or if that is not possible for reasons of functionality then use materials that are readily separable.

• Verify the actual recyclability of polymer materials. Hypothetical recyclability is not interesting from industrial, environmental, and economical points of view.

• Favor the use of recycled polymers • Ban or reduce the use of hazardous substances. • Build products for easy disassembly and recycling.

• Write and convey dismantling procedures. • Avoid high performance laminates or biodegradable polymers if they are not recyclable.

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• Avoid strongly pigmented polymers where possible. Recoup (www.recoup.org/) in its fact sheet “Design for Recyclability” concerning packaging provides some examples:

• Avoid PVC labels on PET bottles, or PVC seals in the closures of PET bottles.

• Avoid PET labels on PVC bottles. • Avoid colored coatings on PET bottles, which influence the economics of recycling and the marketability of recyclate. Minimizing color of bottles typically increases the value of the material to be recycled.

• Avoid thermoset and metal closures. • Favor water-soluble adhesives, paper sleeves, or shrink sleeves of an appropriate material. Avoid hot-melt adhesives, solvent adhesives, heavy-metal inks, and direct printing.

• Favor the use of recycled polymers. There are stringent requirements regarding the standards of food grade packaging but in a number of cases, recycled plastic bottles have been able to meet these exacting standards and there is a growing use of recyclate in food packaging. For example, more than 10% of the PET recycled from bottles is reprocessed in bottles. In conclusion, in descending order, give priority to the different streams of wastes:

• Processing wastes (if suitably treated) are of premium interest.

• Mark parts weighing more than a defined

• Suitable postconsumer wastes are of second

threshold according to ISO 11469 to speed up material identification.

interest if they can be economically collected and cleaned.

• Use molded-in colors instead of paint, coat-

• Favor sources of known origins. • All other things being equal, municipal wastes

ings, or plating.

• Differently color parts made of different materials to ease sorting.

• Eliminate glue and adhesives by using, for example, snap-in features or if that is not possible, use adhesives that can be removed in typical washing processes within the recycling plant. Avoid hot-melt adhesives and solvent adhesives difficult to eliminate.

are the most difficult to work and often lead to uncertain reliability. To give a rough idea of reliability of ready-touse recycled plastics, Table 9.10 displays detailed and statistical analyses of 23 batches of sorted bottles. That is an intermediate case between monomaterial, postconsumer wastes and MSW. Batches include natural HDPE, pigmented HDPE, and

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Table 9.10 Analyses of 23 Batches of Sorted Bottles. Statistical Analyses Fair Sorted Polymer

Fair Polymer False color

Total: Fair Polymer, All Colors

Other Organic and Inorganic Materials

Polymer

Good

Good

Good

False

Color

Good

False

Good and false

False

Mean

95.2

2.4

97.6

2.4

Median

94.7

1.7

99.4

0.6

Standard deviation

3.4

2.3

3.1

3.0

Minimum

87.4

0

92.5

0

Maximum

99.7

8.9

100

7.5

Samples

23

23

23

23

Batch

Fair Sorted Polymer

Fair Polymer False Color

Total: Fair Polymer, All Colors

Other Organic and Inorganic Materials

1

87.4

5.1

92.5

7.5

2

92

0.5

92.5

7.5

3

93

0

93

7

4

91.3

2

93.3

6.7

5

93

0.5

93.5

6.5

6

90.9

3.1

94

6

7

93.1

0.9

94

6

8

94.6

1.5

96.1

3.9

9

94.7

3.3

98

2

10

98

0.9

98.9

1.2

11

92.8

6.3

99.1

1

12

95.1

4.3

99.4

0.6

13

97.6

2

99.6

0.4

14

98.1

1.7

99.8

0.2

15

99.7

0.1

99.8

0.2

16

97

2.9

99.9

0.1

17

91.1

8.9

100

0

18

94.5

5.5

100

0

19

98.1

1.9

100

0

20

98.9

1.1

100

0

21

99.3

0.7

100

0

22

99.6

0.4

100

0

23

99.1

0.9

100

0

Raw Results

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natural PET sorted by manual, automatized, or combined sorting systems. The level of the right polymer may be as low as 92.5% with 5% of unwanted color and 7.5% of other contaminants including other plastics possibly incompatible, glass, paper, aluminum, steel, and so forth. Another study (WRAP 2008) finds other figures in a similar range for near IR spectroscopy sorting: 97%, 96%, 94%, 94%, 93%, and 87% of right sorting for polylactic acid (PLA), PP, PE, PET, PVC, and PS, respectively. The same study reports lower data for float sorting: 94%, 90%, 75%, and 57% of right sorting for PP, PE, PET, and PS, respectively. Some measures can improve reliability. For example, the Underwriters Laboratories’ (UL’s) (http://ul.com/) recognition program for recycled plastics uses proven scientific analysis and testing to evaluate plastic compounds with postconsumer or postindustrial content for compliance to UL 746D (Standard for Safety for Polymeric Materials—Fabricated Parts). This rigorous and innovative testing approach enables a recognized resin to have the same level of acceptability in an end-product application as a virgin compound. In essence, it allows for a resin which has been made with a certain percentage of recycled plastics to be substituted for a virgin plastic in end-use applications where compliance to UL 746C (Standard for Safety of Polymeric Materials—Use in Electrical Equipment Evaluations) is required. The certification process for recycled plastics includes three parts, the initial certification, quality assurance (QA) program, and follow-up services. The reader must visit the website of the UL (http:// ul.com/) to complete the following information. The initial certification for compliance to requirements is described in UL 746D. There are two paths for evaluating a recycled plastic according to its origin. Path 1: Recycled plastics with consistent identification. This is typically postindustrial regrinds that are traded between different companies. Several batches are required with the following properties tested: IR—infrared analysis, thermogravimetric analysis, differential scanning calorimetry, flammability, short term properties [i.e., HAI (high arc ignition), HWI (hot wire ignition), CTI (comparative tracking index), etc.], colors, elevated relative thermal index (RTI) through long term thermal

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aging (LTTA); a generic RTI can be assigned based on a positive IR comparison to a generic plastic. Path 2: Recycled plastics without consistent identification. This is typically postconsumer plastics that have been used in consumer products that are considered waste. The plastic in these products is recovered and reprocessed to be reused again in consumer products. Several batches are required with the following properties tested: flammability, impact strength, tensile strength, heat deflection temperature, dielectric strength, HWI or glow wire ignition, infrared analysis (IR), short term properties (i.e., HAI, HWI, CTI, etc.), colors, elevated RTI through LTTA; A generic RTI can be assigned based on a positive IR comparison to a generic plastic. The QA program involves establishing the traceability of plastic sources. Traceability is a very important part of producing a high quality, safe, reliable recycled plastic because this program ensures that the manufacturer is maintaining good control of their many plastic sources. In the QA program a number of tests can be conducted as indicated in UL 746D. Several tests are required based on the flammability rating. These tests are to be conducted on an ongoing base as deemed required by the Quality Management System. During Follow-Up Inspection visits, the inspector will review records for compliance with these test methods. The follow-up services verifies compliance with safety requirements as it is being produced on an ongoing basis through regular manufacturing visits and sample selection with testing. In order to complete the UL Recognition, a recycled plastic manufacturer must have a registered Quality Management System that is compliant with ISO 9001 or an equivalent internationally recognized standard. Regrind from reclaimed scrap from molding, such as sprues or runners that are reused in-house at a molding facility can be reintroduced into the molding hopper; with up to 25% where the rest of the 75% is comprised of the same virgin grade that was used to mold the parts where the regrind came from.

9.1.4 Example of Recycling Loop Effects on Performances One of the main impediments for plastic waste reuse is the poor image of performance. As always, this is partly objective and partly subjective.

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• The retention ratio of a property P is the same after each life cycle, that is: Pn11 5q Pn

• The second hypothesis is that the blend of recyclate and virgin plastic obeys the law of mixes. Fig. 9.4 property versus recyclate levels of 25%, 50%, and 100% for a retention ratio of 90% shows the property retention versus the number of life cycles. It is necessary to have a recyclate level as low as possible for a satisfactory performance level, which reduces the economic and environmental benefits. Fig. 9.5 shows property retention versus loop number using 25% recyclate with 0.8%, 0.9%, and 0.95% property retention ratios. In spite of high-retention ratios (0.9 and 0.95),

1.2 25%

Property retention

1

50% 0.8

100%

0.6 0.4 0.2 0 0

5

10

15

Loops

Figure 9.4 Property retention versus loop number for 25%, 50%, and 100% recyclate levels. 1.2 Property retention

After processing and use, plastics are aged, damaged, dirty, and polluted. Recycling can eliminate some dirt and pollution and upgrading can enhance some properties, but to be economically sustainable, cleaning and upgrading options are somewhat limited. The produced plastic parts can suffer from weak spots caused by micro- or macro-heterogeneities inducing the initiation of cracks under mechanical or chemical constraints. Then the crack propagation is easy under elongation, creep, fatigue, thermal cycling, environmental stress cracking, and so forth. More generally, the plastic parts can suffer, in the bulk, from a loss of certain or all performances, tensile strength, impact behavior, dielectric properties, and so forth. Lastly, optical properties, clarity and color, and odor can be affected, which disturb the use of recyclates in parts requiring certain esthetic properties for marketing reasons or clarity for functional reasons. To be viable, recycling must be efficient for a number of years or even decades. Intuitively, we can think that the properties continuously decrease as the number of cycles grows. The modeling of property retention confirms that the property level can rapidly become unacceptable. The cumulative retention of properties can be easily modeled through two simplifying hypotheses:

0.95

1

0.9

0.8

0.8

0.6 0.4 0.2 0 0

5

10

15

Loops

Figure 9.5 Property retention versus loop number using 25% recyclate with 0.8%, 0.9%, and 0.95% property retention.

the decrease of the property P with the number of cycles may be unacceptable. Unfortunately lowering the recyclate level is detrimental from economic and environmental points of view. This figure shows the interest of highretention levels even for a low-recyclate level, which is often suggested by polymer producers. Of course, recyclate upgrading allows to improve the retention of properties. The previous model points out the necessity to have a retention ratio between two consecutive cycles as high as possible and the nearest to 1. Five factors can contribute to minimize the issues impeding the everlasting reuse of plastics waste:

• smart design • gentle processing

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• careful recycling • upgrading • high cost of virgin polymers Let us remember some rules of good sense, without claiming to be an exhaustive list:

• A smart design, e.g., must facilitate recycling by easing component separation and avoiding the use of incompatible plastics in a same stream of waste. Combinations of materials such as PVC and PET are particularly hazardous. A low level of PVC in the PET is disastrous for the recycling of PET. For mechanical recycling, the acceptable PVC level in a PET stream is claimed to be as low as 0.25%.

• Coatings, labels, seals, closures, colorants, inks, glues, and other subcomponents must be chosen to ease recycling and reprocessing. The color also influences the marketability of the recyclate.

• Gentle

processing minimizes processing machine residence times, processing temperatures, and shear. Inline compounding suppressing a step of melting and mechanical work is particularly favorable.

• Careful

recycling minimizes temperature and mechanical treatments. For example, bottles can be recycled as flakes instead of pellets avoiding remelting and pelletization.

• Upgrading improves recyclate properties and retention of properties after each recycling loop.

• High costs of virgin polymers encourage the use of recycled matter. For thermoset composites, concerns are intensified. For instance, an experimental recycling process targeting thermoset composites leads to retentions of:

• About 80% after the first recycling loop for modulus and failure stress.

• 40% 60% after the first recycling loop for the failure strain.

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9.1.5 Recycling: Legislation, Standards, and Related Publications The following information (according to the British Plastics Federation—http://www.bpf.co.uk/) is only a brief shortened picture of the subject. Of course, plastics activities must obey general and specific policies, directives and regulations. The reader is the sole responsible of his or her own problem and must study the requirements of the countries concerned by formulation, manufacture, commercialization, application and waste disposal.

Legislation, regulations, directives, specifications can limit or favor the use of recycled plastics according to their goals. They counterbalance the lack of economic interest and push recovery on the one hand and, on the other hand, establish some safeguards related to health, safety, environment, performance, pollution, and so forth. Economical interest of recovery is, generally speaking, insufficient to power up growing of recycling and recovery. Worldwide, international, national and even local laws, directives, regulations, and so on are edited to force producers, manufacturers, consumers, and other actors to facilitate and oblige the recovery of all materials and parts, devices or goods. In the framework of this chapter we quote only some examples of the innumerable texts, articles, annexes, amendments, and so forth, that are available in the literature. Obviously, it is the responsibility of everybody to obtain from official sources, to read, study, and obey such worldwide, international, national and local laws, directives, regulations, and so on. We have retained as examples three European Directives concerning:

• Automotive • Packaging • EE equipment (EEE) These directives deal with:

• Some general points related to presorting by end users generating the wastes, collection, storage, prevention, reuse, and recovery.

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Directives

Schedules

Actor responsibilities

Design recommandations

Information of actors

Precautions

Collection

Environmental

Ease of repairing and reuse

Sorting

Health and safety

Recovery

Technical

Ease of dismantling

Dismantling

Environment

Recycling

Financial

Ease of recycling

Health and safety

Landfilling ban

Polymer coding

Figure 9.6 Examples of regulation subjects.

• Specific considerations related to concerned wastes and materials.

• A schedule for the execution of the various steps. Fig. 9.6 shows some general subjects of these types of regulations. The following information is voluntarily truncated and it is the responsibility of everybody to study the most recent official full texts.

9.1.5.1 EU Waste Legislation Examples EU directives, as do other regulations, continuously evolve making the following information probably lapsed. The reader must review the related subjects for any changes.

• Framework waste legislation • Waste Framework Directive, or Directive 2008/98/EC of the European Parliament and of the Council of November 19, 2008 on waste and repealing certain Directives. This Directive repealed Directive 2006/12/ EC of the European Parliament and of the Council of April 5, 2006 on waste (the codified version of Directive 75/442/EEC as amended), hazardous waste Directive 91/689/EEC, and the Waste Oils Directive 75/439/EEC. It provides for a general framework of waste management requirements and sets the basic waste management definitions for the EU.

• Decision 2000/532/EC establishing a list of wastes. This Decision establishes the classification system for wastes, including a distinction between hazardous and nonhazardous wastes. It is closely linked to the list of the main characteristics which render waste hazardous contained in Annex III to the Waste Framework Directive above. • Regulation (EC) No 1013/2006 of the European Parliament and of the Council of June 14, 2006 on shipments of waste. This Regulation specifies under which conditions waste can be shipped between countries. • Waste legislation and policy of the EU Member States shall apply as a priority order the following waste management hierarchy: • Manufacturing: waste prevention • Waste: Preparing for reuse Recycling Recovery Disposal • The Directive introduces the “polluter pays principle” and the “extended producer responsibility”. It incorporates provisions on hazardous waste and waste oils (old Directives on hazardous waste and waste oils being repealed with the effect from December 12, 2010), and includes two new recycling and recovery targets to be achieved by 2020: • 50% preparing for reuse and recycling of certain waste materials from households

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• • • •

•

•

AND

LIMITATIONS

and other origins similar to households, and • 70% preparing for reuse, recycling and other recovery of construction and demolition waste. The Directive requires that Member States adopt waste management plans and waste prevention programs. EEE [waste EEE (WEEE) and RoHS Directives] End-of-life vehicles Packaging and Packaging Waste Regulations The Publicly Available Specification (PAS) 103 enables plastics waste to be classified according to its polymer type, its original use and any contaminants. Plastics recycling companies will be able to set purchasing specifications based on this PAS and collectors, sorters and traders of plastics waste will be able to maximize the value of their material by understanding the precise needs of the recycling industry. PAS 103 was sponsored by DTI, Biffaward, WRAP, EMR and Fujitsu Services. European Commission Regulation No (EC) 282/2008: Recycled Plastic in Food Contact Applications: European Commission Regulation No (EC) 282/2008 on recycled materials and articles intended to come into contact with foods and amending Regulation (EC) No. 2023/2006 entered into force on April 24, 2008 and is directly applicable throughout the EU. The new regulation sets out the requirements for recycled plastics to be used in food contact materials and establishes an authorization procedure of recycling processes used in the manufacture of recycled plastics for food contact use. It establishes requirements as regards the materials that can be recycled and the efficiency of recycling process to reduce contamination. The regulation aims to create a more efficient and practical system for regulating the use of recycled plastics in food packaging. COMMISSION REGULATION (EU) 2015/ 1906 of October 22, 2015 (https://www.zm. gov.lv/public/ck/files/reg%201%20EN.pdf)

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•

•

•

•

amends the Regulation (EC) No 282/2008 on recycled plastic materials and articles intended to come into contact with foods. Approval from the European Food Safety Agency (EFSA—http://www.efsa.europa.eu/ fr/): Any company wishing to use recycled plastics in food contact applications will need to gain approval from the European Food Safety Agency (EFSA), which will base its safety assessment on factors such as the quality of the recycled raw material, the efficiency of the decontamination process and the plastic’s intended use. Once EFSA has evaluated a particular case, its verdict will be forwarded to the EC. If the EC authorizes the case, it will then be added to the register of approved recycling processes. Guidelines for applicants for the safety evaluation of recycled plastics to be used in contact with food have been published by EFSA. In 2015, EFSA (https://www.efsa.europa.eu/ en/topics/topic/plastics-and-plastic-recycling) published a Scientific Opinion on the safety assessment of two processes used to recycle HDPE plastic bottles for use as food contact materials. In 2017, EFSA (https://www.efsa.europa.eu/ en/topics/topic/plastics-and-plastic-recycling) published for PET several Safety Assessment of recycling processes with possibly some limitations.

9.1.5.2 Automotive The following information is voluntarily truncated and it is the responsibility of everybody to study the most recent official full texts. Directive 2000/53/EC of the European Parliament and of the Council of September 18, 2000 on end-of-life vehicles treats of general-purpose considerations and specific ones related to plastics. The entire directive and its amendments must be considered by everybody but among the prior considerations, articles and annexes let us quote in the framework of this chapter only some specific points, the others having to be respected:

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Among the numerous articles let us quote for example: Schedule

These dates are examples and other ones can be quoted in the Directive, annexes and amendments. It is the responsibility of the reader to obtain original texts, to study and obey them.

• This Directive shall enter into force on September 2000. As of January 1, 2015, for all materials, the targets for EOL vehicles, unless otherwise stated, are:

• Reuse and recycling 85% • Reuse and recovery 95% 9.1.5.3 Packaging The following information is voluntarily truncated and it is the responsibility of everybody to study the most recent official full texts. Council Directive 94/62/EC of December 15, 1994 on packaging and packaging waste treats of generalpurpose considerations and specific ones related to

plastics. The entire Directive, annexes and amendments must be considered by everybody but among the prior considerations, articles and annexes let us quote in the framework of this book only some specific points, the others having to be respected: Directive 94/62/EC, entry in force 30.06.1996 is completed by amendments and Commission Decisions such as, among them: The interim report provides the Council and the European Parliament with some information such as:

9.1.5.4 Electrical and Electronic Equipment DIRECTIVE 2002/96/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of January 27, 2003 on WEEE concerns a multitude of components containing plastics resumed in ANNEX IA: 1. Large household appliances 2. Small household appliances 3. IT and telecommunications equipment 4. Consumer equipment 5. Lighting equipment

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6. Electrical and electronic tools (with the exception of large-scale stationary industrial tools) 7. Toys, leisure and sports equipment 8. Medical devices (with the exception of all implanted and infected products) 9. Monitoring and control instruments 10. Automatic dispensers The following information is voluntarily truncated and it is the responsibility of everybody to study the most recent official full texts. The entire directive and its amendments must be considered by everybody but among the prior

considerations, articles and annexes let us quote in the framework of this book only some specific points, the others having to be respected: In December 2008, the European Commission proposed to revise the Directive in order to tackle the fast increasing waste stream. The new WEEE Directive 2012/19/EU entered into force on August 13, 2012 and became effective on February 14, 2014. REPORT FROM THE COMMISSION TO THE EUROPEAN PARLIAMENT AND THE COUNCIL on the review of the scope of Directive 2012/19/EU on waste EEE (the new WEEE Directive) and on the reexamination of the

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deadlines for reaching the collection targets referred to in Article 7(1) of the new WEEE Directive and on the possibility of setting individual collection targets for one or more categories of EEE in Annex III to the Directive COM/2017/0171 final. Information above is incomplete and out-of-date so that the reader will have to accurately study his own case and to update information.

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damaged and must be upgraded to satisfy functional requirements.

• Adjust the durability affected by natural aging, high-temperature exposure, sunlight irradiation, and other factors. Molecular weight, chemical structure, and protective agent levels must be taken into account.

• Enhance fire behavior, electrical, and other specific properties using conventional methods.

9.2 Recycling Methods Many plastics products are discarded although their properties are still right because their useful life is finished. For example packaging such as water bottles are dispose of because their contents are used; Fascias and other plastics parts of cars are discarded because the cars are in the end of their life. The degradation level can be negligible needing only a careful cleaning, or more damaging requiring an intelligent upgrading. Considering recycled plastics as a valuable plastic resource, some best practices must be met to improve the chances of success, for example:

• Compatibilize the other possible polluting polymers.

• Adapt the rheology to get closer to virgin polymers. Generally, used polymers have a lower viscosity.

• Tune the color as it may need a shade adjustment or a complete change of tint.

• Enhance mechanical properties to get closer to the original ones or to reach suitable levels for the targeted application. Impact strength and elongation at break are often the most Practical obstacles

Technical obstacles

These requirements being fulfilled it may be necessary to adapt the reprocessing to the characteristics of the recycled material. Plastic wastes represent a phenomenal source of polymers, but are difficult to exploit because of practical, technical, psychological, and economic barriers (see Fig. 9.7 Impediments to plastic recycling). However, it is also causes extensive pollution that must be carefully treated. Fig. 9.8 schematizes some valid ways for plastic recycling and proves that the dark picture of the situation can be dramatically lightened in the case of processing waste. Currently the plastic recycling ratio is highly variable according to the nature of wastes and the country. Generally, the used ways are not really satisfying— landfilling and incineration shares being too large. To summarize, end-of-life plastic wastes can be classified as:

• Processing scraps being easily reprocessed • MSWs, the most difficult to recycle, including: • Packaging, containers; water, soft drink and shampoo bottles; lids; etc. Economic obstacles

Scattering of end-of-life goods

Commingled incompatible materials

Treatment cost

Collection difficulties

Degradation of end-of-life goods

Low cost of commodities

Sorting difficulties

Pollution Regulation restrictions

Figure 9.7 Impediments to plastic recycling.

Psychological obstacles

Negative connotation of recycled plastics

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Plastic goods

Processing scraps

End-of-life goods

Selective collection

Sorting

Shredding

Cleaning

Energy generation

Mechanical recycling

Upgrading

Grinding

Municipal wastes

Chemical recycling

Energy recovery

Sorting

Reprocessing

Mechanical recycling

Feedstock recovery

Re-processing

Re-use

Primary recycling In the original production Secondary recycling In less performing production

Repolymerization Reformulation

Reprocessing

Primary recycling in original production Secondary recycling In less performing production

Figure 9.8 Diagram of the main recycling routes.

• Nondurable goods such as diapers, trash bags, cups and utensils, medical devices, etc. • Durable goods, e.g., appliances, furniture, refrigerators, etc.

• Selected streams, principally automotive and beverage bottles. Worldwide, about 27 million end-of-life cars are recovered each year. Plastic parts can be: • Identified and sorted for large parts such as bumpers, battery trays, etc. • Mixed with other materials such as rubbers, glass, metals, fabrics, and dirt into the socalled ASR weighing about 5 million tons that is to say about 185 kg/car. Several ways are conceivable for the recycling method on the one hand and for reuse on the other hand. For example, chemical ways can be adopted for depolymerization and a new synthesis giving satisfying technical results, which can lead, theoretically, to an ideal and endless loop. However, the carbon footprint is not necessarily the best. Reuse can be for the same goods as original ones or in different, less sophisticated or demanding parts, which leads, always in theory, to less exciting solutions. For the “easy to collect” wastes it is possible to build two scenarios among others as shown in

Fig. 9.9 mechanical or chemical- recycling and reuse solutions, where postuse plastic parts are first collected and then dismantled, sorted, and cleaned. The second steps are very different concerning mechanical treatment, possible upgrading, and pelletization for the first case on the left side of the figure, and a depolymerization followed by a repolymerization of the same polymer or the polymerization of another polymer for the second case on the right side of the figure. Obviously, in this last case, the loop is open. The third steps are identical concerning the reprocessing in the same type of parts (closed loop) or in another less demanding type of parts (open loop). These routes have two indubitable merits, saving raw materials of fossil origins and intelligently discarding scraps. But it is necessary to ask some questions concerning energy consumption, pollution, carbon footprint, cost balance, and performance levels. At a glance, we can see on the middle and right side of Fig. 9.9 showing the higher complexity of the scenarios, and the probable overconsumption of energy and correlated fossil fuel, and surplus of pollution. However, chemolysis and repolymerization are exciting because of the possible purity of the obtained raw materials and the theoretically

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Post use plastics

Sorting

Washing drying

Crushing

Chemolysis

Monomers

Formulation upgrading

Extrusion pelletization

Reprocessing

Closed loop same end product

Open loop other end products

New polymerization of the same polymer

Polymerization of another polymer

Formulation compounding

Formulation compounding

Extrusion pelletization

Extrusion pelletization

Processing

Processing

Closed loop same end product

Open loop other end products

Open loop

Figure 9.9 Mechanical or chemical recycling and reuse solutions.

better performance. However, some experiences display that the idyllic purity of chemical depolymerization is unrealistic because of economic issues and the end performances can be poorer than that of equivalent polymers made of virgin monomers. Mechanical recycling without upgrading can lead to unacceptable performances if the virgin polymer is only used at a low level to compensate for the material loss during recycling. Cost savings are generally established for mechanical recycling. For chemical ways, they depend on the outputs and used methods. Please note that there are always some losses of material during recycling.

9.2.1 Reprocessing of Processing Scraps and Mechanical Recycling If recycling of processing wastes is thought of at the start, this is the ideal and real case leading to

perfect closed-loop recycling: sprues, runners, and defective moldings or profiles are not mixed and are safely stored before separate grinding for reuse in the same part or profile.

9.2.1.1 Overview Most manufacturers use the scheme illustrated in Fig. 9.10, perfect closed-loop recycling. To be successful, the process must obey some basic rules:

• Do not damage the material during processing with excessive temperatures, residence times, shear strains, etc.

• Sort materials at the exit of processing machines.

• Separate streams of different materials. • Keep equipment clean by avoiding dust and other pollutants,

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Figure 9.10 Perfect closed-loop recycling.

• Keep material safe during storage by avoiding

• Hide the recycled material with one or two

moisture, high temperature, sunlight, UV, and other aggressive environments.

layers of virgin material by coinjection or coextrusion. This technique is used for films, tubes, and injected parts.

• Dry the material before reprocessing if necessary. Generally heat, moisture, and shear damage processed polymers. Often macromolecules are shortened but sometimes there is also a crosslinking; materials are oxidized and eventually hydrolyzed leading to alteration of all the properties, such as:

• Rheology is modified and often viscosity decreases, but sometimes it increases.

• Mechanical and thermal performances often decrease with tensile strength and modulus decay. When reinforced with fibers, shortening of fiber length magnifies the phenomenon. Natural fibers and, to a lesser extent, synthetic and glass fibers can be chemically damaged by the service life.

• Aging resistance, chemical behavior, flammability, and electrical properties are altered by the loss of protective additives, the alteration of chemical structure, and the uptake of chemicals during the service life.

• Color is often modified notably for white and light-colored compounds.

• Unwanted odors may be emitted. There are several ways to hide the property shortfalls if they are not upgraded by compounding:

• Use recycled material at tuned concentrations in place of the virgin material. Generally speaking, 20% or 25% is often chosen but according to the requirements of the new manufactured parts or goods, lower or higher rates can be used.

• Use the recycled material as inert filler: this solution is often used for thermosets that cannot be decrosslinked. Thermal damages are cumulative and depend on the temperature and time for a given polymer. Yarahmadi et al. (2001) study the color degradation of a white profile made out of rigid PVC. The same color degradation is obtained after recycling by aging of about:

• 168 days at 65°C • 92 days at 70°C • 45 days at 75°C. These data are rather well fitted by an Arrhenius plot (see Fig. 9.11) displaying the log (aging time in days) versus 1000/T. Prediction of lifetime at room temperature for the same change of color is in the order of 100 years and is more but for a higher temperature where the lifetime is very short, for example 30 seconds at 200°C (if the nature of degradation does not change at this temperature). Certain polymers are sensitive to hydrolysis and are altered by it during processing and reprocessing, the more so as the processing time and temperature are higher.

9.2.1.2 Effect of Pollutants Pollutants can be another polymer used in the same plant or various chemicals used during the service life or accidentally added to the recyclate.

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2.4

Log (days)

2.2 y = 6.726x–17.665 R2 = 0.9967

2 1.8 1.6 1.4 1.2 1 2.5

2.6

2.7

2.8

2.9

3

1000/T

Figure 9.11 Arrhenius plot of log (aging time) versus 1000/T.

Kallel et al. (2003) studied the effects of low concentrations (a few percent) of a motor oil and ethylene glycol (EG) on properties of alloys of PE and PS. Generally the two pollutants, notably mineral oil, act as a plasticizing agent, thereby decreasing dynamic viscosity and mechanical performances. Mechanical damages are generally well known but rheology changes are less known, and sometimes the effects on specific properties are ignored. From this point of view, fire retardancy and smoke emission of FR grades are good examples.

9.2.2 Recycled Material Upgrading by Additives 9.2.2.1 Overview The use of better performing and, consequently, more expensive additives or the use of conventional additives at higher levels is efficient, for example:

• Rheology can be modified by reactive extrusion with peroxides.

• Mechanical performances can be enhanced by expensive carbon fibers, nanoclays, or carbon nanotubes.

• Aging resistance can be improved thanks to better performing protective agents used at higher levels.

• Flammability can be restored by the addition of more expensive fire retardants.

• Color can be adjusted by additional purification steps and colorant addition, etc. The basic and structural changes after recycling (see Fig. 9.12, possible visible damages after

Recycled plastics before upgrading

Processing difficulties

Viscosity change

Flow disturbing

Performance decrease

Mechanical properties

Electrical, fire properties

Sensorial property changes

Colour, transparency, gloss

Figure 9.12 Possible recycling.

visible

Unpleasant odors

damages

after

recycling) result in real and visible defects if the recyclate is processed as is. Fire behavior of FR grades may be deeply modified. For example, Almeras et al. (2004) study the effects of several recycling cycles on the properties of intumescent alloys of PP and polyamide (PA) rated V0 according to UL94 requirements. Table 9.11 displays property changes after one recycling cycle. The main fact is the poorer fire behavior with a lower limit oxygen index, a higher CO emission, and the loss of V0 rating, but a decrease in smoke emission. The drop in viscosity is significant and can disturb some processing methods. The modulus increase can be beneficial or detrimental according to the concerned requirements. For recycling without problems it is necessary to protect the original compound and use an optimized process.

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Table 9.11 Examples of Property Variations After the First Recycling Cycle.

Variations

Beneficial

Undefined

Detrimental

(%)

(%)

(%) 2 20

Viscosity Mechanical Properties 1 17

Young modulus

2 33

Elongation at break Fire Behavior LOI

2 20

CO emission

1 40 to 100

Smoke emission

2 20 to 2 25

V0 UL94 rating

Not compliant

LOI, Limit oxygen index.

Table 9.12 Examples of Property Variations After the First Recycling Cycle. Optimized Process

Other Processes

Variation (%)

Variation (%)

14

5 118

Young modulus

23

2 8 to 2 15

Tensile strength

B0

2 10 to 0

Elongation at break

22

2 12 to 0

Viscosity (MFI) Mechanical Properties

MFI, Melt flow index.

It is possible to avoid or mitigate viscosity, mechanical, and some other physical damage during the first processing and the first recycling by using careful protection of the original compound. The economic efficiency is limited to parts being identified and sorted after endof-life and returning to the initial producer or processor. Technically speaking efficiency can be realistic, leading to a reduction of the recycling steps and cost of upgrading additives. For example, mixtures of phosphites and hindered phenolic antioxidants (Ultranox for example) allow to run the first recycling cycle of certain plastics without significant degradation. La Mantia et al. (2003) studied several processing and recycling methods for compounds based on PC. Table 9.12 shows property variations according to the used process. For the optimized

one, all the properties are in a range accepted by most plastic manufacturers. For the other first processing and recycling processes, at least one characteristic is unacceptable for standard industrial applications. An important feature of the plastic waste stream is its pollution that can come from:

• External chemical pollution due to a chemical environment during the service life.

• Internal chemical pollution due to the polymer itself or the used additives such as chlorine, bromine, heavy metals, etc.

• Paints, varnishes, and metallic coatings such as, e.g., painted bumpers, metallic coating of CDs, etc.

• Pollution due to a mixture of polymers such as PE and PS in packaging wastes, etc.

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Additives

Polymer enhancers Polymer compatibilization

Compatibilizers

Processing improvers

Rheology modifiers

Lubricants

Property enhancers

Sensorial properties

Colorants

Mechanical performances

Brighteners

Impact modifiers

Reinforcements

Long-term behavior

Heat ageing

Weathering

Others

Specific characteristics

FR

Conductive

Tribologic

Miscellaneous

Figure 9.13 Additives for recyclate upgrading.

• Mixture of commingled polymers in the parts to be recycled: multilayer films, overmolded parts such as five- or even seven-layer films for packaging, bottles with a barrier layer, etc. There are two strategies: depollution or integration of the pollutant into the recycled material. Depollution is used, for example, for the recycling of battery trays polluted with acids. Integration is used for multilayer films, mixtures of polymers, and metallic coatings of CDs. Mechanical resistance is not sufficient in these cases and the use of compatibilizers is needed. To upgrade the other properties, the additives are similar to those generally used in compounding but levels must be adapted.

Fig. 9.13 (additives for recyclate upgrading) shows an array of additives but the most used are:

• • • • • • •

compatibilizers impact enhancers plasticizers protective agents, thermal and UV stabilizers viscosity modifiers reinforcements sensorial property improvers, e.g., colorants, etc.

Several additive specialists market packages for upgrading recyclates.

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Table 9.13 Examples of Properties of Mixtures 50/50 of Polystyrene/Polypropylene Compatibilized and Noncompatibilized. Without Compatibilizer

Best Compatibilizer

Other Compatibilizers

Tensile strength (MPa)

18

22

12 17

Elongation at break (%)

2

3.5

1 3

Young’s modulus (GPa)

1.4

1.5

1.1 1.4

Impact strength (J/m)

108

233

103 199

9.2.2.2 Compatibilizers Compatibilizers are made of two parts: one compatible with one of the two polymers to be compatibilized and the other part compatible with the other polymer. They can be reactive and link with polymers or nonreactive and only miscible with polymers. Compatibilization is a difficult exercise and the following information must be verified and tested before an eventual application. Examples of reactive compatibilizers: acrylic functions grafted on polyolefin, PE and PP, allow compatibilization with PAs, EVOH, polybutylene terephthalate (PBT), and PET. Acrylic functions are often maleic anhydride and glycidyl methacrylate. Such compatibilizers are marketed, for example, as Amplify GR-MA (Dow), Elvaloy PTW, and Fusabond (DuPont). Examples of nonreactive compatibilizers: Vistamaxx (Exxon) can compatibilize PP and PE for recycling without sorting, ethylene-ethylacrylate copolymers for PP/PA recycling, ethylenebutylacrylate, and ethylene methacrylate (EMA) copolymer for compatibilization of PP, PE, PBT, PA, ABS, and PC. Polymethylmethacrylate (PMMA); PS grafted on PP (Interloy) can compatibilize prolypropylene with PMMA, styrene acrylonitrile, acrylonitrile styrene acrylate, ABS, PVC, PC, and PPE. Acrylic-imide copolymers (Paraloid) can compatibilize PPE/PA and PC/PE. Styrenic block copolymers can compatibilize PP/HDPE, PPE/PA, olefins, and styrenics SB, PS, and ABS. Some processing aids can also ease the recycling of PA/PET, for example fatty acids and their salts or esters, and amides by Struktol or polyolefins containing a fluoropolymer by Spectratech. Halimatudahliana et al. (2002) studied the compatibilization of PS and PP with a SEBS, an EMA

(by DuPont), an ethylene vinylacetate (EVA), and a salt hydrate of a styrenesulfonic acid. Table 9.13 displays property examples of mixtures 50/50 of PS/PP compatibilized and noncompatibilized. In the most interesting cases, almost all the properties are improved with the best compatibilizer leading to increases of more than 20% for tensile strength and more than 100% for impact strength.

9.2.2.3 Impact Modifiers Independently of the plasticization, the impact strength of recycled materials can be improved at ambient temperature and embrittlement at subzero temperatures can be reduced using impact modifiers. The basic principle is to finely disperse and distribute tiny particles of an elastomer or a rubbery polymer in the plastic. If the elastomer is compatible with the polymer to be enhanced, strongly adheres on it, and then spreads out and dampens the energy of an impact. Simultaneously the rigidity of the plastic decreases and some other properties can be somewhat altered, for example hardness, heat deflection temperature (HDT) (see Table 9.14) but also, eventually, weatherability and thermal stability. The impact strength remains operational at lower temperatures, the more so as the glass transition temperature of rubber is low. Numerous polymers are used, for example ABS (already containing polybutadiene), MBS, CPE, SBS, SEBS, polyacrylate, polybutadiene, EPDM, ethylene acrylate, modified polyolefins, and so forth. Some inorganic impact modifiers are also marketed such as amorphous silicon dioxide. Table 9.14 displays examples of effects of impact modifiers on performance ratios of ETPs.

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9.2.2.4 Plasticization Plasticizers can desorb during service life or can be insufficient for the new functions targeted after reprocessing. It is possible to add new plasticizers to enhance flexibility and impact strength at ambient and subzero temperatures, and to ease processing, compounding, and shaping. Unfortunately plasticizers can also have some harmful effects on thermal, electrical, chemical, and mechanical or optical properties. Heat, humidity, light, and UV aging are generally negatively influenced. Fire behavior depends on the chemical natures of the involved plasticizer and recycled material. Plasticizers lead to some environmental risks because of their eventual toxicity and the propensity to migrate toward other neighboring materials that could induce discoloration, stress cracking, and fogging. In addition, one must be vigilant for regulations concerning contact with food and medical articles. The most common plasticizer chemical structures, polar or nonpolar, are, for example: phthalates, phosphates, carboxylic acid esters, epoxidized fatty acid esters, polymeric polyesters, modified polymers; liquid rubbers, and plastics, Nitrile Butadiene Rubber (NBR), chlorinated PE, EVA, etc.; paraffinic, aromatic, or naphthenic petroleum oils. Nonpolar plasticizers are preferably used for nonpolar recycled polymers and, conversely, polar plasticizers are preferably used in polar recycled polymers. However, some plasticizers are multifunctional with other specific characteristic such as having an antistatic effect or being flame retardant (chloroparaffins and other halogenated plasticizers). Fig. 9.14, examples of tensile strength versus brittle point, displays examples of the beneficial effect of plasticizer on the brittle point and detrimental effect on tensile strength for PVC. A high plasticization leads to a brittle point as low as 2 45°C but tensile strength is lower than 10 MPa.

9.2.2.5 Additives for Aging Protection The first processing and the service life consume antioxidants and other protective agents. To compensate for this consumption and eventually to upgrade the recyclate to be used in better performing applications, the chosen protective additives depend on the targeted goal.

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Table 9.14 Examples of Effects of Toughening on Performance Ratios of Upgraded Recyclates. Performance of Impact Upgraded Recyclates Divided by the Same Performance of Unmodified Recyclate Impact strength

2 5

Hardness, Rockwell M

0.7 0.8

Tensile strength

0.6 0.8

Elongation at break

1 3

Tensile modulus

0.4 0.6

HDT B

0.9

Ratios , 1 are indicative of a performance deterioration HDT, Heat deflection temperature.

Processing stabilizers are antioxidants incorporated into the (recycled) polymer to avoid heat degradation during recycling and reprocessing. Therefore thermal stabilizers in PVC formulation are essential to prevent dehydrochlorination and discoloration (i.e., yellowing, darkening, etc.). These stabilizers can also provide the necessary stabilization required for the entire service life. Antioxidants are added into the (recycled) polymer compound to decrease thermooxidation during the service life avoiding molecular weight changes and loss of mechanical, physical, and esthetic properties. Light stabilizers decrease degradations initiated by sunlight or UV exposure. Certain fillers and organic UV-absorbers act as filters protecting the polymer from UV exposure. Hydrolysis stabilizers added to the polymer avoid hydrolytic degradation during service life. Antioxidants and protective agents are a broad family. A few examples are acid scavengers, amines, phosphites, hindered amine light stabilizers, nickel quenchers, phenols, UV absorbers, and so forth. Often, two or three protective additives are combined to reinforce their efficiency but polymer degradation can never be totally inhibited.

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25

MPa

20 15 10 5 0 –50

°C –40

–30

–20

–10

0

10

Figure 9.14 PVC: examples of tensile strength versus brittle point. PVC, Polyvinyl chloride. Table 9.15 Examples of the Efficiencies of Anti-UV Stabilization. % Degradation PC white PE

Tensile Strength

Elongation at Break

Impact Strength

Unstabilized

4

78

9

UV stabilized

7

22

15

Unstabilized

44

41

48

UV stabilized

24

22

5

PC, Polycarbonate; PE, polyethylene.

Sensorial property enhancers

Colours

Transparency opacity

Gloss/mat modifiers

Odour

Colorants pigments

Clarifiers

Glossy additives

Deodorants fragrances

Brighteners

Fillers

Mating materials

Bactericides preservatives

Figure 9.15 Additive solution examples improving sensorial property of recyclates.

This depends on the length of time of its exposure to heat, light, water, and other aggressive environments. Table 9.15 displays degradation following weathering of PC and PE, unstabilized and UVstabilized. Results and efficiency of anti-UV protection depend on the examined property and polymer. In the same sample, some properties may be enhanced while others are degraded.

9.2.2.6 Sensorial Property Enhancers The first processing and the service life affect coloration, transparency, gloss/mat balance, smell, and so forth, that can be counterbalanced by the judicious addition of active additives as we can see

in Fig. 9.15, additive solutions examples improving sensorial property of recyclates. For coloration, two cases can be distinguished:

• A slight yellowing can be compensated for by the addition of a white pigment, e.g., titanium dioxide, a blue colorant, or brightener.

• A strong coloration cannot be masked and the only solution is to amplify it in the same shade or in another, e.g., black, dark brown, or green. Colorants and pigments, inorganic or organic, differ by their chemical nature, form, stability to reprocessing and recycling temperatures, and their fastness.

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To a limited extent, clarifiers can be used to improve transparency of inherently transparent polymers. Matting can be obtained by adding special mineral fillers or by making an alloy with another secondary polymer more or less miscible with the main polymer, or using proprietary additives. Unpleasant odors during and after reprocessing can be masked by the addition of deodorants or specific fragrances marketed for polymers. Bactericides or preservatives can be used to avoid the development of microorganisms, fungi, and so on during service life.

9.2.2.7 Special Additives and Packages for Recyclate Upgrading Packages or specific additives are proposed, for example, by AmeriHaas, Ampacet, Arkema, BASF, Brueggemann, Chemtura, Ciba, Crompton, Dexco Polymers, Dow, DuPont, GE Specialty Chemicals, Hoechst, Kraton Polymers, MA Polymers, Optatech, Quantum, Struktol, and others. There are multiple possibilities according to the main polymer, polluting or associated polymer, degradation level, residual pollution, targeted applications, and so forth, including for example:

• Brueggemann proposes its BRUGGOLEN H 14, H 10, H 320, H 321, H 3373, H 3374, L11, L 20, P 30, P 31, M 1420. It is claimed: • A heat Stabilizer and Antioxidant package can assume an efficient processing stability, a good melt flow, a fair mold release and a long term heat stability without yellowing • Another Heat Stabilizer and Antioxidant package can provide a long term heat stability up to 180°C maintaining mechanical properties and toughness, protection against aggressive chemicals (glycols, hot oils . . .), a better extraction resistance • A melt processing stabilizer of lower volatility and higher heat stability compared to organic phosphites can protect against discoloration and degradation during processing and during service life • A Processing Auxiliary can enhance the melt flow, shorten cycle times, improve crystallization and mold release, reduce yellowing, upgrade the processing stability, mechanical properties (tensile strength,

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modulus, etc.), and the dimensional stability, and reduce warpage in glass fiber reinforced grades • A Chain Extender, thanks to the molecular weight increase without crosslinking, can improve the mechanical properties (tensile strength, elongation, impact strength) • On the contrary, a Chain Scissors cuts polymer chains decreasing molecular weights and viscosities • Light Stabilizers can improve optical brightness, reduce yellow discoloration, protect against long term UV and heat degradation in outdoor applications.

• BASF Plastic Additives (previously Ciba Specialty Chemicals Inc.) develops its RECYCLOSTAB 411, 451, 550, 660 and other additive packages to upgrade recycled plastics for high-value applications. It is claimed: • RECYCLOSTAB 411 increases long-term thermal stability of recycled HDPE, PP and polymer blends. The recyclates can be used in applications such as containers, bottle crates, bottles or waste bins and plastic profiles for the construction industry. • RECYCLOSTAB 451 AR has been developed for recycled PP and PP-blends to reach the property level of virgin polymers. Furthermore it helps to neutralize acids and impurities of the previous life such as battery cases. • RECYCLOSORB 550 combines weatherability, processing and thermal properties required for outdoor applications such as bottle crates, garbage bins and plastic pallets. • RECYCLOBLEND 660 has been designed to minimize the effect of residual lacquer particles and fillers. This additive package can regenerate the original properties of PP/ EPDM and PC/PBT recycled from bumpers and other automotive parts.

• Using Elvaloy HP661 by DuPont in PVC recyclates improves durable strength and flexibility even when exposed to outdoor conditions, low temperature or chemicals. Low temperature tests can reach 2 50°C and over.

• The ultralow temperature ( 2 60°C) 1500 series of Abust and Mebust impact modifiers from PolyChemAlloy can be easily mixed

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MFR

446

0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0

Package Antioxidant None

Extrusion runs 0

1

2

3

4

5

6

7

Figure 9.16 PE MFR upgrading.

with a wide variety of high temperature ( . 250°C) engineering resins such as PBT, PC, PA and polyester.

• Stryroflex, a BASF styrene-butadiene block copolymer can bring a solution to ABS, PS, PP, and PE scraps recycling. Styroflex acts as styrenics and polyolefins blends compatibilizer for: • PS and PE • PS and ABS • ABS, PS, PP, PE

• Arkema launches Apolhya, a nanostructured thermoplastics family combining the properties of PA with those of polyolefins thanks to cocontinuous morphologies on a nanometric scale. As a recycling additive, Apolhya can be used as a compatibilizer or an adhesion promoter during the recycling of polyolefins and PAs. It can also boost the thermomechanical properties of polyolefinbased thermoplastic elastomers (TPEs), or improve the impact properties of PA 6 and 66 formulations.

• Recyclates of PA/PE and PA/PP multilayer films can be compatibilized with some percent of PE or PP grafted with maleic anhydride. For a PET/PE structure, addition of 5% of an epoxidized modified polyolefin should provide significant improvements in performance.

• Joncryl Chain Extenders by BASF enhance recyclability, productivity, melt strength, tensile strength, impact properties, hydrolytic stability of PET, RPET, PETG, APET, PC, PA, PLA, PBT, TPU and other polycondensation polymers. Intrinsic viscosity of PET can be increased by 20% up to 40% in extruders and reactors.

Table 9.16 Reinforcement Ratio Examples for a 2% Nanosilicate-Filled Polyamide. Reinforcement Ratios Density

1

Tensile strength

1.25

Flexural modulus

1.3

HDT A (1.8 MPa)

1.9

HDT, Heat deflection temperature.

Fig. 9.16, PE MFR upgrading, shows the efficiency of different upgrading solutions. As we can remark, the highest MFR is obtained with the specific additive package. Mineral nanofillers, used at levels as low as 2% or 3% do not significantly change the density and can efficiently enhance the mechanical properties of recyclates allowing to get back the original properties of the virgin polymer (see Table 9.16). As we can see:

• Density is not significantly affected. • Mechanical performances are 25% 30% higher

• HDT is far higher. Into the bargain, gas permeability and fire behavior are often enhanced.

9.2.2.8 The Purity Enhancement Many purification methods are well-known but their use depends on the economic context. For example:

• Recycling by solvent extraction (see specific Section 9.2.4)

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application. This is, technically and economically, a difficult method that has been industrialized in only a few cases. Chemolysis is made up of several steps:

under pressure to remove physical impurities, treatment with carbon to remove chemical impurities, distillation, crystallization, and other chemical posttreatments. The degree of purity of recovered materials is of paramount importance in the mechanical recycling process.

• First cleaning, leading to a relatively clean waste stream, which reduces pollution of end products and corrosion of the recycling equipment.

• Multiple washing is very simple but isn’t

• Depolymerization obtained by reaction with

always economically viable.

active chemicals in the presence of catalysts at relatively high temperatures to speed up the reactions. According to the nature of the used chemicals, we can distinguish: • Glycolysis using EG, propylene glycol (PG), diethylene glycol (DEG), triethylene glycol (TEG). • Methanolysis using methanol. • Alcoholysis using other alcohols such as butanediol (BD). • Hydrolysis using water or acids. • Saponification using alkalis having also the advantage to wash the surface pollutants. • Aminolysis using amines. • Final cleaning: purification by melt filtration under pressure to remove physical impurities, treatment with activated carbon to remove chemical impurities, distillation, crystallization and, sometimes, chemical posttreatment.

9.2.3 Chemical Recycling Mechanical recycling basically consists in “repairing” the compound to reuse it as a new finished material. The opposite way, consisting in “dismantling” the polymer in its original monomers to rebuild a new identical polymer, is intellectually very exciting. Theoretically this method could lead to the perfect endless loop, however some losses will occur. Fig. 9.17, the everlasting loop polymerization/ depolymerization, shows a theoretical example of closed-loop recycling thanks to depolymerization/ repolymerization. This very happy story is not always workable but can be adapted to produce other raw materials such as intermediate products, oligomers, oils, carbon blacks, or energy. Plastic recycling by chemolysis is possible for certain polymers such as polyurethanes leading to initial monomers that can be polymerized again to produce new virgin polymers. When it is really feasible, and if the performances of the original material are truly recovered, this is the best recycling solution allowing reprocessing in the same

Fig. 9.18, chemical recycling, schematizes recycling by chemolysis. Polyester bottles or fibers and polyurethane foams are relatively easily available and can be depolymerized by chemolysis.

A & Bmonomers Polymerization

-A-B-B-A-A-A-

Depolymerization

First processing Parts

Figure 9.17 The everlasting loop of polymerization/depolymerization.

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Wastes

Cleaning

Chemolysis

Alcoholysis

Glycolysis

Methanolysis

Hydrolysis

Other alcohols

Water

Saponification

Aminolysis

Alkalis

Alkalis

Amines

Crystallization

Chemical post treatments

Acids

Depollution purification

Melt filtration

Carbon treatment

Distillation

Reuse

Blend with virgin monomers

Saturated polyesters

Feedstock for other polymers

Unsaturated polyesters

Polyurethanes

Others

Antifreeze

Figure 9.18 Chemical recycling.

9.2.3.1 Thermoplastic Polyesters Several processes are usable to depolymerize waste of PET and obtain the monomers or intermediate products suitable for polymerization of other polymers. Alcoholysis, generally glycolysis, is carried out with an alcohol, generally ethylene or PG in the presence of a catalyst, for example, zinc acetate, at high temperatures in the range of 170° C 245°C under pressure. There is intensive research concerning the nature of the alcohol, type of catalyst, temperature range, use of solvent, and outlets for end products. For example, without claiming to be exhaustive, among the various investigated ways are:

• Nature of the alcohol: • Y. O¨ztu¨rk et al. (Department of Chemical Engineering, Istanbul University, Avcılar, Istanbul, Turkey) compare the efficiencies of EG, PG, DEG, and TEG in the presence of zinc acetate as catalyst. They react glycolysis products with maleic anhydride and styrene monomer to produce unsaturated polyester (UP) resins. • Mansour, S. H., et al. (Department of Polymers and Pigments National Research Center Dokki, Giza, Egypt) use 1,4-BD and

TEG in the presence of zinc acetate as a transesterification catalyst. The glycolyzed products consist mainly of bis-(hydroxybutyl terephthalate) monomer and dimer by using 1,4-BD.

• Type of catalyst: • Farahat (2002) uses manganese acetate as catalyst.

• Use of a solvent: • Guclu et al. (1998) study the use of xylene in glycolysis to improve yield and purity of obtained dimer fractions.

• Outlets for the end products: • Monomers or oligomers of a few repeat units are blended with virgin monomer to polymerize a new virgin polyester. • O. Saravari, B. Vessabutr, V. Pimpan (Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand) use PG and zinc acetate as a catalyst. The glycolyzed product, is reacted with soybean oil and toluene diisocyanate to obtain urethane oils. • O¨ztu¨rk et al. already cited react glycolysis products with maleic anhydride and styrene monomer to produce UP resins.

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Glycolysis and methanolysis are the most used processes. Saponification is simpler and doesn’t need pressure, which simplifies the equipment needed and reduces investment, but has not yet been industrially developed.

the production of PUR-based products more environment-friendly.

For example, SABIC’s VALOX iQ technology uses chemical processes to unzip PET bottles into their precursor chemicals, purify them, and then use these to create new PE or PBT (PET or PBT). The resulting VALOX iQ resin contains up to 60% recycled content with performance that is nearly equivalent to virgin resins.

Recycling by solvent extraction of polymers from shredder residue is only suitable for soluble thermoplastics and is a difficult method that has been industrialized in only a few cases. Thermoplastic wastes are dissolved by organic solvents without chemical damage to their molecules but with extraction of their organic additives such as plasticizers, antioxidants, and so on. The selection of the right solvents and processes allows to separate and purify polymers by physical means such as crystallization, precipitation, and filtration. To be economically attractive, the solvents must be easily recovered. Safety and health conditions must satisfy local, regional, national, and global requirements, regulations, and so forth. There are many patents, research works, and development studies for this method that can lead to pure polymers, even starting from mixed thermoplastic. Muegge, J., et al. (Vestolit and Solvay) quote several cases:

9.2.3.2 Polyurethanes To be successful, chemolysis of polyurethanes must process sorted wastes; the best results being obtained with industrial wastes. Several methods are competing:

• Glycolysis: polyurethane foam is reacted with glycols into a single-phase or multiphase process. Posttreatments can be applied to reduce the aromatic amine level and to purify the end products used in rigid, semirigid, and, in some cases, soft foams. Glycolysis is particularly adapted to recycling of processing wastes.

• Hydrolysis: polyurethane foam is reacted with water at elevated temperatures under pressure, producing the original polyols and diamines coming from the breaking of the original diisocyanates. Industrially, hydrolysis is less advanced than glycolysis.

• Aminolysis: polyurethane foam is reacted with dibutylamine, ethanolamine, lactam, and derivatives at elevated temperatures under pressure. This is the least advanced chemolysis process. For example, RAMPF (http://www.rampfgruppe.de/en/companies-and-products/eco-solutions/ plant-engineering/) proposes inhouse recycling technology (RAMPF Eco Solutions). Customized recycling facilities are designed and built for PUR manufacturers with high volumes of waste material. These plants enable customers to manufacture their own cost-effective, high-tech polyols at their own production location that can then be fed straight back into the production process. This cuts raw material, transport, and disposal costs, and makes

9.2.4 Solvent Recycling

• Interior trim of end-of-life vehicles (ABS, PVC, PP, PA) mixed with glazing (PMMA, PC) and other thermoplastics. Laboratory tests show the possibilities of separation.

• PVC from cables can be swollen or completely dissolved by adequate solvents to produce high quality recycled polymers.

• PVB from windscreens can be recovered. • PC from CDs can be recycled. The recycling cost can be estimated at about 1h/kg. (about US $ 1.1/kg) Industrially, selective extraction has made a breakthrough with PVC: Solvin, Adriaplast, Vulcaflex, and Tecnometal have combined their efforts in Vinyloop Ferrara SpA (http://www.vinyloop.com/en/) to regenerate 76,000 tons of raw material with an 85% extractable compound weight, representing 65,000 tons of regenerated PVC compound. The main sources of the plant raw material are postconsumer wire and cable waste (over 70%). CO2 saving is about 70,000 tonnes. The process includes three steps: pretreatment, dissolution, and separation.

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9.2.4.1 Pretreatment Physical operations turn the waste into raw material suitable to be extracted. These physical operations may include:

• a cleaning step: washing, decontamination, etc. • a size reduction step for fast dissolution: cutting, grinding, milling, etc.

• a homogenization step. 9.2.4.2 Selective Dissolution The solvent selectively dissolves the PVC compound and not the other materials. It is carried out at a temperature adapted to the raw material to be regenerated in the absence of air in a closed process. Of course, all the solvents are recycled.

9.2.4.3 Separation The nature of the insoluble materials determines the used techniques such as centrifuging, decanting, cycloning, and so forth. Table 9.17, property examples of recycled PVC compared to virgin compounds, shows property examples obtained from recycled wire coating. Targeted applications are, for example:

• • • • • • •

replacement of 10% up to 100% of virgin PVC splash guards back layers of tunnel membranes geomembranes

Unfortunately the closure of Vinyloop operation in Italy was announced by 2018. Another industrial example is the recovery by Wietek (http://www.wietek.com/wietek.htm) of engineering plastics from compounds including ABS, PMMA, PS, PP, PE, and many others supplied as shredded, grinded, meshed, or as filter dust. Recovering ABS parts by using adapted selective solvents involves typical ABS applications, including galvanized parts from the sanitary industry, furniture parts, esthetic strips, logos, rear lights, front grills, and consoles from the car industry. Recycling technology enables the separation of the metal coating from the ABS support. This results in a metal-free ABS that can be reprocessed in new ABS parts. The solvents that are specifically chosen for the products to be recycled remain in the closed-loop process and are, therefore, recovered.

9.2.5 Thermal Recycling There are many more or less sophisticated processes, often in development. The thermolysis, liquefaction, gasification, pyrolysis, catalytic pyrolysis, hydrocracking or hydrogenation process, the Texaco process. . . can produce petrochemical feedstocks for steam-cracking, alternative fuels or basic raw materials for the chemical industry. Their development depends on the economic context. Fig. 9.19, thermal recycling, shows some examples without claiming to be exhaustive:

rods

• Pyrolysis or thermal cracking in kilns or fluid-

internal layers of hoses coated textiles for outdoor furniture and building interiors, etc.

ized beds at about 800°C in air-free or oxygen-controlled environment produces liquid and gaseous hydrocarbons

Table 9.17 Property Examples of Recycled Polyvinyl Chloride (PVC) Compared to Virgin Compounds. Recycled PVC

Virgin PVC Soft

uPVC

Density

1.4 1.5

1.1 1.5

1.3 1.5

Shore hardness (A)

81 86

55 96

90 99

Stress at break (MPa)

13 14

10 25

30 60

Elongation at break (%)

180 200

200 500

2 120

Tensile properties at 23°C

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Wastes

Cleaning

Thermal processes

Catalytic pyrolysis

Thermal cracking

Liquefaction

Hydrocarbons

Gas

Distillation

Hydrocracking

Gasification

Residue

CO

H2

Cracking

Fuel gas

Chemical feedstock

Power generation

By products

Ammonium choride

Oils

Gas

Residue

HCl

Chemical feedstock

Fuels

Cracking

Chemical feedstock

Residue

Figure 9.19 Thermal recycling.

• Catalytic pyrolysis limits the temperature range at much lower levels, 400°C for example. After melting and extrusion, plastics are liquefied at 200°C/300°C and thermally cracked at 400°C on a catalyst bed. Overall yield is about 80% consisting of 50% gasoline, 25% kerosene, and 25% gas. Eventually steam cracking at elevated temperature produces ethylene and propylene that must be purified through careful distillation.

• Thermolysis carried out in the presence of a controlled amount of oxygen can lead to a mixture of carbon monoxide and hydrogen suitable for synthesis of methanol, acetic acid, etc.

• Hydrocracking or hydrogenation is a thermal decomposition in hydrogen atmosphere at high temperature and under pressure producing hydrocarbon oils.

• Gasification at 1300°C, a higher temperature than pyrolysis, in an atmosphere of a controlled level of O2 produces a gas used as a substitute for natural gas.

9.2.6 Energy Recovery Energy recovery methods do not produce renewable materials and are, therefore, not in the framework of this book. Currently technologies allow to recover the energy contained in plastics. Plastics have a high energy content that can be converted into electricity, heat, or power by incineration with energy recovery, for example, MSW incineration, cement kiln, and substitution of oil/coke in power generation. Recovering this abundant energy also reduces waste sent to landfills. Energy recovery by burning plastic waste as a replacement for coal or other fossil fuels is of interest if burning conditions are safe, and landfilling is partly eliminated. In the EU, energy recovery accounts for about 9% of plastic waste use. Energy recovery versus landfill saves about 26 37 MJ/kg of plastic. Burning 1 tonne PE, only made of carbon and hydrogen, produces a weight of CO2 greater than 3 tonnes. Heating value is an important characteristic of solid fuels (see Table 9.18, heating values of various fuels and wastes).

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Table 9.18 Heating Values of Various Fuels and Wastes. Fuel or Waste

Typical Heating Value (kcal/kg)

Plastics (polyethylene)

11,000

Heavy oil

9500

RPF

6000 8000

Coal

6000 8000

RDF

4000 5000

Wood/paper

4300

Typical municipal wastes

1000 1500

RDF, Refuse-derived fuel; RPF, refuse-derived paper and plastic fuel.

9.2.7 Anaerobic Biodegradation of Biodegradable Plastics With Gas Recovery

warmed to temperatures appropriate for enzymatic hydrolysis. Through enzymatic action, biodegradable materials are liquefied to permit easy separation of nondegradable solids, mainly plastics and metals. After washing, plastics can be recycled by traditional ways. A first plant built in 2017 to treat 120,000 tons of municipal waste separates clean plastics and metals suitable for recycling; generates 5 MW electricity, clean gravel for road construction, a liquid suitable for biogas production, and a by-product usable as fuel.

9.3 Sectorial Routes for Recycling The choice of recycling method is not free but depends on the nature of the waste. For example:

• Polymers in rubbish cannot be sorted and reprocessed.

This method does not produce renewable materials. Anaerobic digestion is a biological waste treatment process that is environment-friendly if gas recovery is correctly assured and valued. Obviously, plastics must be biodegradable and compatible with the anaerobic digestion process. Currently anaerobic biodegradation of bioplastics is in the research phase.

• Presorted polymers such as bottles can be

9.2.8 Enzymatic Depolymerization of Polylactic Acid

• Some polymers are relatively easy to repro-

Carbios (http://www.carbios.fr/) claims it has successfully depolymerized 90% of PLA material within 48 hours, with the help of its proprietary enzymatic process. The enzyme patented by Carbios induces the catalytic depolymerization of PLA waste at a rate that comes close to industrial performance. Such catalytic activity was tested on consumer goods made of PLA, including cups, trays, plastic films, and flatware whose semicrystalline properties make it difficult for the enzyme to operate.

9.2.9 The REnescience Process Recovering Plastics and Metals From Municipal Solid Waste Without Sorting In the REnescience process (http://www. renescience.com/en/), unsorted MSW is wetted and

reprocessed with optimized methods.

• All polymers, conventional or biodegradable, are not necessarily compatible with each other and a small percentage of one can disturb the quality of the recyclate and make it unsuitable for practical applications. This is an important parameter for biodegradable polymers. cess, others are not and lead to poor performances.

• Thermosets, because of the crosslinking, are difficult to recycle. Finally there is not one answer but several answers and multiple ways, as we can see through a few examples. Sectorial routes lead to specific streams with general advantages, such as:

• Presorting resulting from the specificity of each stream, e.g., bumpers of cars, bodies of fridges, etc.

• A limited number of probable polymers. For example, the most frequently used polymers for bottles are PVC, PET, and PE.

• The opportunity to study the most accurately methods

of

dismantling

and

sorting.

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Washing Sorting Shredding Open loop

Bottle-to-bottle

Building materials

Reprocessing

Collection

Bottles

Fibers

Strapping Sheets

Figure 9.20 Open- and closed-loop recycling and reuse.

Carmakers provide procedures for each main part, bumpers, instrument panels, etc., of each car model.

• Better knowledge of the possible pollutants resulting in more efficient washing and cleaning processes.

• The possibility of better industrialization and more efficient marketing of the recyclates.

9.3.1 Used Polyethylene Terephthalate Bottles: Realities of Everyday Life The first issue to recover PET is to find an “easy-to-collect” PET waste source. PET bottles enter in this class but are mixed with other bottles or, worse, with other plastic wastes. Fig. 9.20, open- and closed-loop recycling and reuse, schematizes collection, mechanical recycling, and reuse of postconsumer bottles.

9.3.1.1 Collection of Bottles Currently the majority of cities have a collection scheme to recover plastic bottles mainly made of PVC, PET, and PE. The schemes request citizens to dispose of plastic bottles or goods into specific bins that are then collected separately from the rest of the household waste. The bins containing recyclables are sent to a sorting plant.

9.3.1.2 Sorting of Plastic Bottles Bottles can be sorted manually or automatically. Manual sorting is labor-intensive as operators use sample features to identify the bottles that are hand-picked from the sorting line. Automatic sorting uses high-speed X-ray and infrared sensors to select each polymer and reject

contaminants. In addition, automatically rejected bottles are checked by operators. Recovered PET, PVC, and PE bottles are then punctured and separately baled before being sent to reclaimers that sort the bottles once again.

9.3.1.3 Bottle Recycling Bottles are prewashed and shredded into flakes. The flakes are washed thoroughly with water and detergents and then dried, resulting in clean flakes free of contaminants such as labels and glue. Flakes are ready to be used as such or blended with a virgin polymer. PET can be also recycled by depolymerization, which leads to monomers used to polymerize new PET. Currently, recycled PET is used to produce fibers (polar fleece for example), strapping, sheets, and bottles made of high-quality, recycled PET. Recycled plastics used in food packaging, containers, and other food-contact materials may only be obtained from processes that have been assessed for safety by EFSA (European Food Safety Authority) and authorized by risk managers. The European Commission have prepared a register of authorized processes. Scientific studies have been published (https://www.efsa.europa.eu/en/topics/ topic/plastics-and-plastic-recycling) for various processes including, for example, without claiming to be exhaustive:

• process ‘Krones’ • process ‘Veroniki Ecogrup SRL’, based on Starlinger Decon technology

• process ‘Ma¨rkische Faser’, based on NGR technology

• process ‘PEGRA-V’, based on Starlinger IV 1 technology

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• process ‘Plastienvase’, based on EREMA Basic technology

• process ‘Coexpan Montonate’, based on Starlinger Decon technology

• process ‘4PET’, based on EREMA Basic technology

• process ‘EREMA Recycling (MPR, Basic and Advanced technologies)’,

• process ‘Alimpet’, based on EREMA MPR technology

• process ‘Coexpan Deutschland’, based on EREMA Basic technology

9.3.1.4 Bottle-to-Bottle Recycling The reuse of PET recycled from used bottles, starting from a cautious 10%, has made rapid progress in beverage and industrial packaging. Obviously, the cost, performances and CO2 emissions depend on the recycling method and the reuse level. For example:

• Rexam Prescription Products is the first packaging company to develop and market a pack for liquid prescription made from 100% postconsumer recycled (PCR) PET resin. This package meets the same government standards as its current virgin PET line, including US Pharmacopoeia requirements for light transmission and moisture permeation, the Consumer Product Safety Commission’s childresistant and senior-friendly protocol requirements, and FDA resin standards.

• Method Products, Inc has converted three of its US product lines to 100% PCR PET bottles from Amcor PET Packaging. By using 100% recycled PET, the carbon footprint was reduced by a significant 60%.

• Nestle´ Waters uses 50% recycled PET in its water bottle ReBorn, used for its Arrowhead brand of water.

• Danone has progressively introduced recycled PET (at 25% recyclate) in its Evian water bottles. By the end of 2008, Danone’s aim is to commercialize all its 75 cl up to 1.5 L bottles into RPET. 100% RPET is hoped by 2025. Danone aims to make Evian its first, major carbon-neutral mineral water brand by 2020.

• Coca-Cola targets a 100% bottle-to-bottle recycling at long-term after a 25% recycled step by 2015.

• One manufacturer says the use of RPET (Recycled PET) allows the company to reduce a bottle carbon footprint by 17%.

9.3.1.5 Bottle to Engineering Thermoplastic Polyester Grades Valox iQ resin is made of thermoplastic polyesters wastes using a proprietary process. The material consumes less energy and yields less carbon dioxide (CO2) than traditional resins through its entire manufacturing process from cradle (65% discarded PET bottle) to gate (Valox iQ resin pellet). Its carbon footprint is 50% 85% lower than a new virgin resin. Applications for Valox iQ resin include furniture, computers and consumer electronics, transportation, and automotive components like connectors, mud guards, lighting bezels, and more.

9.3.2 High-Density Polyethylene Bottles Nextek (nextek.org/), European manufacturer of food-grade milk bottle resin from postconsumer milk bottles, uses the process developed by WRAP UK. Bottles containing up to 50% recycled content have met all EU and UK food contact requirements for minimal migration and organoleptic performance. The Dairy Roadmap (formerly known as the Milk Roadmap) has set targets for the use of rHDPE in new milk bottles of 10% by 2010 (achieved), 30% by 2015, and 50% by 2020.

9.3.3 Electricity and Electronics: Closed- and Open-Loop Recycling Waste from fridges and WEEE brings together large household appliances (about 50% in weight) as well as IT and telecom devices including computers, smartphones, and other electronic devices. One of the various challenges is the hazardous components (heavy metals, brominated flame retardants, etc.) that require special handling precautions fulfilling global and local legislation related to plastics and waste.

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Electronics with its high ratios (i.e., cost to weight) makes reuse and refurbishment very attractive thanks to environmental benefits and the highadded value. A suitable scheme of device collection and resale could allow to capitalize on this opportunity, the resale value of a reusable or refurbished device being considerably higher than the material value recovered from the resale of the recyclable materials. Some specific obstacles facing repair include data security issues for phones, computers, and peripheral devices. The complete destruction of data including personally identifiable information is challenging and hazardous. Examples of other issues are the feasibility of installing a new version of the operating system, intellectual property, transferring ownership, manufacture of replacement parts, and so forth. There are many examples of recycling and use of recyclates relating to WEEE, for instance:

• High grades of recycled polymers from Axion’s Salford processing plant were used to create the 100% recycled plastic keyrings, which resulted in a 50% saving in carbon emissions compared with using virgin raw materials

• Sony’s televisions, in spring 2008, started the use of recycled plastics from a Sony closedloop recycling program. The first program of its kind for flame-retardant plastic materials used in televisions enables the recovery of some plastic parts from TVs and of PS foam scrap generated during the production of LCD televisions. Under strict quality control, the program ensures high-quality, closed-loop, resource recovery for some TV parts, reducing the amount of new resources needed and emitting nearly 30% less CO2 compared to using virgin resins. Digital Europe (http://www.digitaleurope.org/ DesktopModules/Bring2mind/DMX/Download.aspx? Command 5 Core_Download&EntryId 5 2276 &language 5 en-US&PortalId 5 0&TabId 5 353) provides examples such as:

• Dell claims using currently about 35% recycled-content into new parts.

• In 2005, HP developed a closed-loop PET that met the specification requirements for original

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HP inkjet cartridges. The recycled PET (rPET) recipe is based on a combination of HP product take-back, recycled PET water bottles, and a suite of upgrading additives. Since 2005, HP has closed the plastics loop into a number of additional inkjet supplies families using PP. Recycled PP includes a combination of HP product return, recycled PP clothing hangers, and additives. An HP Inc. funded, externally reviewed, life cycle analysis concluded that HP’s first closed-loop plastics rPET material in comparison to virgin resin provided a 33% carbon footprint reduction and consumed less than 54% fossil fuels. The amount of recycled plastic in the HP inkjet cartridge types varies between 50% and 75% of the total plastic used.

• Lenovo Monitors and Notebooks contain at least 10% PCR content and more (up to 36% or 42%).

• In

2012, Lexmark’s new product line announced three lines of printers having 5% 40% PCR content. The 2018 goal is to average 25% PCR plastic content across the entire toner cartridge product line.

• Oce´ has used recycled PC in a PC 1 ABS blend for a nonvisible component of the printer. The recycled PC is used approximately at 30% of the PC 1 ABS. The PC was sourced from water bottles.

• In 2015, Samsung Electronics applied a total of 34,322 tons of recycled plastics (6.3% of total plastic use to monitors, printers, washing machines, refrigerators, vacuum cleaners, and earphone cases). All 2015 monitors are designed with a 30% recycled plastic content and are PVC-free. Furthermore, Samsung uses 20% of recycled plastics in the cases of new smartphone chargers.

• For FY2014, Sony uses over 19,000 tons of recycled plastics (63% scrap from manufacturing process and 37% PCR plastic).

9.3.4 Auto: Closed- and Open-Loop Recycling Improving the recycling of plastics parts from 2% up to 7% of the used vehicle weight could save

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980,000 tonnes of CO2 in the EU. For example, Volvo Cars announced its ambition that from 2025, at least 25% of the plastics used in every newly launched Volvo car will be made from recycled material. To demonstrate the viability of their ambition, the company has unveiled a specially built version of its XC60 T8 plug-in hybrid SUV that looks identical to the existing model but has had several of its plastic components replaced with equivalents containing recycled materials. The special XC60’s interior has a tunnel console made from renewable fibers and plastics from discarded fishing nets and maritime ropes. On the floor, the carpet contains fibers made from PET plastic bottles and a recycled cotton mix from clothing manufacturers’ offcuts. The seats also use PET fibers from plastic bottles. Used car seats from old Volvo cars were used to create the sound-absorbing material under the car bonnet. Mercedes is another example. For the base version of the new E-Class launched in 2015, it is possible to produce a total of 72 components, with a total weight of 54.4 kg, with a proportion of highquality recycled plastics. Renault, another car manufacturer, increases the use of recycled plastics on its vehicles from generation to generation. For example, its Espace model includes 50 kg of recycled plastics. In 2013, recycled material used in wheel liners (Jeep Wrangler and the new Chrysler 200 sedan) rose from 52% to 64%. Average percentage of recycled polymers used is claimed 34.7% for Europe. Ford used more than 25,000 tonnes of PCR plastics on the exterior of Ford vehicles made in North America. BMW is reusing CFRP production scraps to manufacture the roofs for its i3 and i8 models as well as the rear seat structure in the i3. SGL Automotive Carbon Fibers reports that 10% of the CFRP used in the BMW i vehicles is recycled. Recycled carbon fiber could offer a 20% 40% cost savings compared to virgin fiber. Wastes of air intake manifolds: The recycling process, DuPont Composite Recycle Technology, can convert parts made of glass- or mineral-filled nylon 6 or 66 into first-use quality material in a way that is economically viable and environmentally responsible. Composite Recycle Technology dissolves used PA then filters away contaminants and fillers. The molecular weight of the recovered

PA is increased to whatever level is desired for the final application. DuPont Engineering Polymers and Denso announced a joint development program to test the viability of this technology by converting used radiators and tanks into new ones. The analysis of the recycling technique applied on air intake manifolds, made from virgin nylon 6 or from recycled nylon 6, shows that:

• Results of end-use testing for leaks, burst, and breaking strength are within specifications for parts made with recycled resin.

• Life cycle analysis of energy usage and CO2 emissions shows that the environmental footprint of Composite Recycle Technology is lower than virgin processes.

9.3.5 Recycling and Reprocessing of Building Products Recycled plastic products for construction are often, partially or totally, made from postconsumer and postindustrial plastic waste from one of three main plastic materials:

• PE sourced from plastic bottles, bags, and wrapping film.

• PS from sources such as CD cases, vending cups, and food packaging.

• PVC from windows and industrial products. Some products can be made from 100% recycled plastic or can include a core of recycled plastics and surface layers of the same virgin resin. Others, such as wood polymer composites use a blend of recycled plastic and (recycled) wood. The wide range of recycled plastic construction products, includes, but is not limited to:

• • • • • • • •

damp proof membranes water drainage pipes and ducting curbstones wall cladding, soffits and fascias roofing materials piling and ground stabilization scaffolding planks

9: RECYCLING PLASTICS: ADVANTAGES

• • • •

AND

LIMITATIONS

decking and flooring products fencing street furniture traffic management

According to calculations by Axion Recycling, manufacturing new building products from recycled PVC-U has about 6% of the global warming impact of using virgin polymer. In addition to environmental advantages, there are significant cost savings. Collecting and mechanically recycling 1 tonne of PVC, which can directly substitute virgin polymer in a new application, could create a 94% saving in CO2 emissions compared to production of 100% virgin PVC polymer. For example, VinylPlus (UK) has increased its target for recycling 800,000 tonnes by 2020 including ex-factory industrial waste as well as postconsumer waste.

9.3.6 Recycling of Thermosets From a practical point of view, the recycling of thermosets and composites is difficult for general causes as well as specific ones. Among others, it is constrained by:

• The irreversibility of the macromolecule crosslinking.

• The technical possibilities: the feasibility for handling mass quantities.

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• By

developing the Supercritical Fluid Recycling Technology, Vyncolit Sumitomo Bakelite Co (http://www.vyncolit.net/) claims to be able to recover the raw materials of thermoset composites such as monomers, oligomers and reinforcements (fiber) in their initial state before curing. The mechanical properties of the compound produced with monomer and fibers recycled by the Supercritical Fluid Technology are claimed equivalent to those of the virgin compound.

• Solvolysis Process refers to a thermochemical process leading to depolymerization of UP composites, using hot water as a reactant. This process uses a specific reactor that enables breaking the links of the thermostable resin and separating it from the fibers incorporated therein for reinforcement. The recycling process enables, on the one hand, recovery of the glass fiber with a claimed 65% of the mechanical properties of the virgin fiber and, on the other hand, the extraction of chemical products of potential value, such as benzoic acid, benzaldehyde, and benzene-acetaldehyde, among others.

• Thermolysis: gasification, pyrolysis, etc. to produce petrochemical feedstocks for steamcracking or alternative fuels.

• Cocombustion with MSWs.

9.3.7 Recycling of Composites

gin polymer cost ratio determine the success or failure of the method.

Because some fibers are deeply linked to the polymer matrix and easily broken, special methods are used for composites, for example:

• Environmental regulations: recycling must

• Sheet molding compound (SMC) and bulk

• Economics: the final cost and the recyclate/vir-

globally decrease the pollution balance versus tipping or landfill. The main recycling routes utilize some of the methods previously examined for the thermoplastics with some limitations, for example:

• Mechanical recycling: Unfortunately, reuse is possible only as a filler because of the crosslinking irreversibility.

• Chemolysis: This is, technically and economically, a difficult method that is industrialized in few cases.

molding compound can be recycled by mechanical shredding and grinding in three ways: • Micronized powders are added at the 5% 15% level in new adapted formulations to replace mineral fillers. The density is slightly inferior and the performances are in a similar range. • Short fiber (few millimeters or less) recyclates used to reinforce polymers or concrete. • Long fiber (10 mm and more) recyclates used to reinforce polymers.

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• The rear leaf springs of utility vans made of continuous glass fiber-reinforced epoxy are also recycled by mechanical shredding and grinding in two ways, to give either short fiber (few millimeters or less) or long fiber (10 mm and more) recyclates used to reinforce polymers.

• The high mineral content of glass fiber reinforced plastics makes them a poor fuel because of the low-organic content. However, they can be used in cement kilns where the glass goes into the raw materials and the matrix acts as fuel.

• UPs may be hydrolyzed by high-temperature (300°C 500°C) steam into phthalic acid, styrene, bituminous residue, and glass fibers. For a given part, the adopted recycling solutions can belong to several categories of processes. For example, for bumpers made out of SMC, six methods compete:

• Grinding and reuse with virgin SMC. • Shredding and reuse of the fibrous recyclate to reinforce other polymers.

• Shredding and reuse of the fibrous recyclate in the concrete industry.

• Use in cement kilns. • Pyrolysis with production of gas, oils, and tars. • Hydrolysis.

9.3.8 Recycling of Glass and Carbon Fibers, and HighPerformance Polymers The following three examples show the diversity of high-tech solutions. SGL Automotive Carbon Fibers (https://www. sglgroup.com/) has developed a recycling process which makes a recirculation of valuable carbon fibers into the production process possible and thus closes the material cycle. RECAFIL recycled carbon fibers are available as 50 k rovings or as socalled carbon fiber flocks. TENAX-E COMPOUND rPEEK CF30 (https:// www.teijin.com/news/2017/ebd170307_03.html) is a reinforced material combination of waste materials generated during processing of TENAX ThermoPlastics and recycled semicrystalline PEEK polymer, which contains 30% of carbon fiber by

weight and offers a high performance in strength and stiffness for injection molding applications. This compound has high tensile modulus and strength, fair viscosity, chemical resistance, abrasion, and a low moisture absorption. The price is claimed of 40% 60% compared to virgin carbon fiber-reinforced PEEK compounds. Minger (http://www.minger.ch/en/products/fluorplastics) supplies Fluoroplastics produced from clean and single-origin industrial wastes. The portfolio offers granules from:

• • • • • •

polyvinylidene fluoride ethylene chlorotrifluoroethylene ethylene tetrafluoroethylene polytetrafluorethylene perfluoroalkoxylalkane fluorinated ethylene and propylene

9.4 Recycling Advantages: CO2 Emission, Greenhouse Effect, and Carbon Footprint Solar infrared radiations bring heat to our Earth and the greenhouse effect of atmospheric gases controls the heat depletion. The balance of both phenomena maintain the average temperature at the Earth’s surface. This natural process is magnified by an overproduction of CO2 and other GHGs such as water vapor (H2O), methane (CH4), nitrous oxide (N2O), Freon’s (chlorofluorocarbons), hydrofluorocarbons, perfluorocarbons, and so on. Atmospheric concentrations of CO2, mainly due to fossil fuel combustion (hydrocarbon-based fuels formed by the decomposition of prehistoric flora and fauna, for example oil, natural gas, coal, tar sands, and peat) are now about 30% above preindustrial levels. The greenhouse effect of emitted gases leads to the global warming. To make the comparisons easier between several materials or routes, CO2 emission has been chosen as a standard to quantify the greenhouse effect of the manufacture, use, and discarding of any product. The carbon footprint can be defined, in a simplified manner, as the sum of all emissions of CO2 and other GHGs, expressed in equivalent CO2. The balance includes all the steps of the product life, namely manufacture, transport, use, and end of use

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treatments. Usually a carbon footprint is calculated for a defined time period. It can be noted that the carbon footprint of any plastic part depends on:

• The raw material origin: For example, the growing of plants leads to renewable raw materials absorbing CO2 and so their footprint is negative for this step (but positive for their transportation).

• • • •

The polymerization method. The processing methods. The real use including the actual lifetime. The energy sources used. For example, electricity from wind turbines has a negligible impact on the carbon footprint.

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• The production of 1 tonne PS emits 2.2 up to 6 tonnes CO2. Using recycled plastic could lead to near 40% 50% net carbon footprint gains.

• The production of 1 tonne ABS emits 3.1 up to 5 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 21% 37% (benefiting use).

• The production of 1 tonne PA emits 4.5 up to 9 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 63% 70% (benefiting use).

• The production of 1 tonne PC emits 4.1 up to 7.6 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 57% 66% (benefiting use).

• The recycling route of the postuse products,

• The production of 5000 plastic bags emits 1

mechanical or chemical recycling, burning, gasification, etc.

• The production of 2000 plastic bottles emits 1

tonne CO2. tonne CO2.

Consequently data can dramatically differ according to the sources. The following examples simply aim to illustrate ideas and other, different data can be found elsewhere:

• Burning 1 tonne PE, only made of carbon and

• An annual drive of 30,000 km distance emits 6

It is also possible to express the fossil energy requirements of materials in GJ/tonne as shown in Table 9.19.

tonnes of CO2 per year.

• The electricity production of 1000 kWh emits 0.8 up to more than 1 tonne for coal, 0.650 tonne for oil, 0.500 tonne for gas, 0.050 for photovoltaic, 0.005 for hydro, wind, or nuclear sources.

• The production of 1 tonne PVC emits 1.6 up to 2.6 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 2 10% (detrimental) to 69% (benefiting use).

• The production of 1 tonne PE emits 1.5 up to 4 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 2 23% (detrimental) to 63% (benefiting use).

• The production of 1 tonne PP emits 1.6 up to 4 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 14% 22% (benefiting use).

• The production of 1 tonne PET emits 1 up to 5 tonnes CO2. Using recycled plastic could lead to net carbon footprint gains as diverse as 14% 55% (benefiting use).

hydrogen, produces a weight of CO2 greater than 3 tonnes.

Table 9.19 Examples of Fossil Fuel Energy Requirements. Primary Energy (GJ/tonne) Starch-based plastics

25 up to 52

PLA

53

Polypropylene

74

Polyester thermoplastic

77

Polyester thermoset

96

HDPE

80

Polystyrene

87

Secondary Energy (GJ/tonne)

42

50

HDPE, High-density polyethylene; PLA, polylactic acid.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

9.4.1 Some Real Facts and Figures There are multiple cases from inhouse postprocessing wastes of well-sorted and stored, clean and in the best conservation state, up to mixed and dirty wastes containing high levels of food, industrial oils or acids such as fish boxes, waste from restaurants, or used car batteries. Obviously the economic and environmental balances are very different and, in some cases, recycling is not conceivable from an economic point of view. Before a study of some real cases we will consider some unprocessed data, for example:

• Plastics production approximately uses 8% of the world oil production, 4% as feedstock and 4% for manufacture.

• Andreas Kicherer, head of the Eco Efficiency Group at BASF, says that the US$4.6 bn cost for recycling 50% of plastics waste in the EU saves 9 million gigajoules of energy and 6 million tonnes of carbon dioxide.

• The 481,000 tonnes of waste PVC recycled across Europe in 2014 contributed to the creation of around 1000 direct jobs in recycling plants, according to VinylPlus, a sustainable development program of the European PVC industry. Per year, there are 2 kg saving of CO2 for each kilogram of PVC that is recycled. Energy demand for recycling PVC is typically around 90% lower than virgin PVC production.

%, Recycled

460

2004

2006

2008 Year

2010

2012

Figure 9.21 UK recycled bottles.

Table 9.20 Statistical Analysis of CO2 Savings. Mean

46

Median

42

Standard deviation

33

Range

94

Minimum

0

Maximum

94

• Various processes of manufacturing 1 tonne PET emit 0.7 5.3 tonnes of CO2. Various recycling routes emit 0.2 2.6 tonnes of CO2.

• A review of life cycle analyses has concluded that recycling plastics saves about 1.5 2 tonnes of CO2 per tonne of plastic recycled compared to alternatives of landfill and incineration with energy recovery.

• 684,000 tonnes of CO2 emissions were saved by recycling the UK’s plastics in 2006, the equivalent of taking more than 216,000 cars off the road.

• The 40,000 tonnes of end-of-life PVC recycled through Recovinyl in the United Kingdom during 2007 will have saved up to 71,000 tonnes of CO2 emissions because the majority of this material will have been used in applications that directly substitute virgin polymer.

• UK plastics bottle recycling is on fast-track growth as we can see in Fig. 9.21, UK recycled bottles. In 2003, just 5.5% of plastic bottles were recycled versus 35% in 2007, and near 80% in 2011 according to new research funded by WRAP and undertaken by Valpak in partnership with Recoup.

9.4.2 Statistical Analyses of Some Real Examples Statistical analyses (see Table 9.20) of a series of various cases differing by the nature of end-oflife parts, polymer family, reprocessing method, and recycled material level shows a mean value of near 50% for the CO2 saving with a broad standard deviation, approximately 33. Fig. 9.22, frequency versus CO2 saving, shows a symmetric distribution with extremum of 0% corresponding to very dirty wastes composed of difficult-to-sort polymers, a unique 94% corresponding to clean and sorted wastes (only one polymer family), and a 100% replacement of virgin resin.

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9.5 Recyclate Property Examples Most of the following examples relate to industrially recycled materials. Other examples can be seen in the Tables 2.20, 4.3, 7.26, 10.11, 11.2 6, 12.5, for example see Table 9.17 for soft PVC. Generally, performances of recycled materials are in the range of those of equivalent virgin plastics. As some properties are affected by recycling, the designer must be vigilant, notably concerning ultimate mechanical performances such as tensile and impact strengths, and also sensory properties such as color, odor, taste, fire behavior, fire retardancy, and smoke emission. Rheology changes, less known, can disturb processing and increase processing costs.

9.5.1 Polyamides Examples Table 9.21 displays examples of PA recycled in laboratories.

9.5.1.1 Industrially Recycled Polyamides Certain producers propose nylon grades containing a percentage of recycled material. For example, BASF markets NYPEL grades. Table 9.22 shows some property examples for an unfilled grade and a 30% glass fiber-reinforced grade. DuPont Engineering Polymers studies recycling of PA resin recovered from radiator end tanks collected from scrapped vehicles. After compounding with glass fibers and a viscosity modifier, mechanical properties and molding characteristics are claimed to be equivalent to those of virgin resins. Tests on radiator end tanks molded from the reprocessed material give results similar to those obtained with tanks made from virgin resin.

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The analysis of the recycling technique applied on air intake manifolds made from virgin nylon 6 or from recycled nylon 6 shows that:

• Results of end-use testing for leaks, burst and breaking strength show that parts made of recycled content are within specification.

• Life cycle analysis of energy usage and CO2 emissions shows that the environmental footprint of Composite Recycle Technology is lower than virgin processes. The technique could be also applied to wheel covers, fans and shrouds, and beauty covers. DuPont Composite Recycle Technology uses dissolution of PA and then the filtration of contaminants and fillers. DOMO Engineering Plastics (https://www. domochemicals.com/en/products/engineering-plastics/ econamid-pa6-pa66) offers PA6- and PA66-based reprocessed solutions for unfilled, mineral filled, glass fiber-reinforced, carbon fiber-reinforced, and flame retardant grades. For the automotive sector, Domo claims its special grades (named Econamid) perform better than traditional virgin versions with:

• 47% less water consumed • 80% less CO2 emitted • 60% less nonrenewable energy used

9.5.2 Polystyrene and Acrylonitrile Butadiene Styrene Examples Table 9.23 displays examples of industrially recycled PS and ABS marketed by recyclers, compounders, or plastics producers.

9.5.3 Polypropylene Examples %

Table 9.24 displays examples of industrially recycled PP marketed by recyclers, compounders or plastics producers.

0

20

40 60 % CO2 saving

80

Figure 9.22 Frequency versus CO2 saving.

100

9.5.4 Examples of Polycarbonate, PC/ABS, and PC/PBT Alloys Table 9.25 displays examples of industrially recycled PC, PC/ABS, and PC/PBT alloys

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Table 9.21 Performance Examples of Virgin and Recycled Polyamide (PA) 6. Virgin neat PA 6

Recycled neat PA 6

Variation (%)

Density

1.13

1.13

5

Shrinkage (%)

1.6

1.6

5

Water absorption saturation (%)

9.4

9.5

5

Rockwell R hardness

119

119

5

Tensile stress at yield (MPa)

85

80

26

Tensile strain at yield (MPa)

5

3.5

2 30

Tensile modulus (GPa)

3.3

3.2

5

Flexural modulus (GPa)

3

2.8

27

Notched izod, 2 30°C

5

4

2 20

Notched izod, 23°C

5.5

4.5

2 18

HDT B (°C)

184

175

25

HDT A (°C)

67

60

2 10

Coefficient of thermal expansion (1025/K)

7.5

7.5

5

33% GF PA 6

33% GF PA 6

Variation (%)

Virgin

Recycled

Density

1.39

1.38

5

Shrinkage (%)

0.2 0.9

0.2 1

5

Water absorption saturation (%)

6.7

6.6

5

Rockwell R hardness

121

121

5

Tensile stress at break (MPa)

200

165

2 17

Tensile strain at break (MPa)

3

3

5

Tensile modulus (GPa)

10.7

9.5

2 11

Flexural modulus (GPa)

9.4

9.3

5

Notched izod, 2 30°C

11

8

2 27

Notched izod, 23°C

15

12

2 20

HDT B (°C)

218

215

5

HDT A (°C)

203

208

5

GF, Glass fiber; HDT, heat deflection temperature.

marketed by recyclers, compounders, or plastics producers.

9.5.5 Examples of Polyetherimide SABIC-IP (https://www.sabic-ip.com/) proposes a postindustrial recycle-based, 20% glass fiber filled, high-flow polyetherimide blend. Table 9.26 displays some of its properties. Other grades are marketed.

Other examples of recycled plastics include, but are not limited to:

• SoRPlas by Sony is made from recycled DVDs and optical sheets from TVs. Sony claims “Combined together they make an extremely versatile recycled plastic containing sodium sulphate flame retardant. Only 1% of SoRPlas is made from non-recycled materials

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LIMITATIONS

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Table 9.22 Property Examples of Polyamides (PAs) Containing a Percentage of Recycled PA. With Recycled PA

Virgin PA

30% GF

Unfilled

30% GF

Unfilled

Specific gravity

1.36

1.06

1.36

1.1

Mold shrinkage (%)

0.3

0.3 0.5

(24 h)

1.1

0.8 1.1

(50% RH)

1.9

(Saturation)

6.7

Mechanical properties

Dry

Physical properties

Moisture (%)

Dry

Dry

Dry

40

120 155

. 50

15

3 8

Tensile strength, break (MPa) 2 40°C

220

23°C

155

80°C

80

121°C

65

Elongation, yield, 23°C (%)

3

. 100

Elongation, break (%) Flexural modulus, 23°C (GPa)

8.5

Rockwell hardness, R scale

121

Notched izod impact, 23°C (J/m)

. 200

1.1

5 8

1 2

85

210

130 160

. 50

220

220

215 220

215 220

Thermal properties Melting point (°C) Heat deflection at 1.8 MPa (°C)

205

230

3 4

,3

HB

HB

Mechanical w/o impact (°C)

140

140

Mechanical w/o impact (°C)

115

115

Electrical (°C)

140

140

Coefficient of linear thermal expansion, 10

25

(°C)

UL ratings, 1.5 mm Relative temperature index, 1.5 mm

GF, Glass fiber; RH, relative humidity or hygrometry; UL, Underwriters Laboratories.

cutting CO2 emissions by 77.3% over the manufacture of conventional plastic materials.”

• For production of bottles, by using 100% PCR resin, the cradle-to-gate energy consumption of the resin compared to virgin is reduced by 52% and the carbon footprint is lowered by 57%. In addition, an on-site production of PCR bottles keeps over 600

truckloads of bottles off the road each year and eliminates over 200 metric tons of carbon dioxide equivalent emissions, according to Amcor.

• For recycling of PET, the carbon cost of producing food grade rPET 78 pellet in 2010 was 254 kg/t, while the cost of producing virgin PET was 681 kg/t.

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Table 9.23 Examples of Industrially Recycled Polystyrene (PS) and Acrylonitrile Butadiene Styrene (ABS). Polystyrene Examples Impact Modified Virgin PS Property

Range

Specification

Typical Properties

5 8

6

1.03 1.06

1.03 1.06

1.03

20 45

15 25

22

MFI (5 kg @ 200°C) (g/10 min) Density Tensile strength (MPa) Impact strength (kJ/m

AXPOLY rPS01 3039 Black or White Impact Modified PS Produced from 100% Postconsumer Materials

2)

6 10

8

Moisture content (%)

0.05 0.30

, 0.25

0.17

Elongation at break (%)

20 65

25 50

35

Recycled, 40% PCR

Virgin, general range of properties

ABS examples

MFI (3.8 kg @ 230°C) (g/10 min)

7

Density

1.05

1 1.15

Tensile strength (MPa)

34

30 60

Flexural strength (MPa)

69

Impact strength (J/m)

187

100 350

HDT B (0.46 MPa) (°C)

100

100 125

HDT A (1.8 MPa) (°C)

95

85 120

HDT, Heat deflection temperature; MFI, melt flow index; PCR, postconsumer recycled.

Table 9.24 Examples of Industrially Recycled Polypropylene.

Property

Virgin Copolymer PP

AXPOLY r-PP51 Black Copolymer PP Recovered from Nonmetallic Waste Fraction from ELV

Virgin Copolymer PP Filled with 10% 40% Talc.

AXPOLY r-PP51 1071 Black PP Filled with 20% Talc

Axpoly PP19 1033 Black Homopolymer PP Filled with 40% Talc

Range

Spec.

Example

Range

Example

Example

6 12

6

9

5

MFI (2.16 kg @ 230°C) (g/ 10 min) Density

0.9 0.91

0.93 0.98

0.93

0.97 1.25

1.09

1.22

Tensile strength (MPa)

20 35

16 22

19.6

21 28

23

25

6 10

11.9

10

5

Impact strength (kJ/m2) Moisture (%)

0.01 0.1

Elongation at break (%)

200 500

0.01 0.03 25 60

33

20 30

0.19 25

Example of PP 20% mineral filled with up to 50% of postconsumer recycled PP. ELV, End-of-life vehicle; MFI, melt flow index; PP, polypropylene.

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Table 9.25 Examples of Industrially Recycled Polycarbonate (PC) and Alloys. rPC

rPC 10% GF

PC, Virgin

INFINO

Pryme

General Range of Properties

Density

g/cm3

Tensile strength

MPa

Tensile strength, yield

MPa

Tensile elongation

%

Flexural stress

MPa

78

83

Flexural modulus

MPa

2010

3240

2100 2500

Izod impact, notched at RT

J/m

785

64

650 950

143

130 145

135

130 140

rPC/ABS

PC/PBT

rPC/PBT

INFINO

Xenoy

Xenoy

1103

iQ1103

1.21

1.2

49

50

1771

1818

2

54

53

2

59

63

105

99

14

16

1.18

1.2 55 77

59

50 65 5

HDT at 0.45 MPa

°C

HDT at 1.8 MPa

°C

123

MVI @ 250°C and 10 kg

g/10 min

18

3

Density

g/cm

1.18

Tensile strength

MPa

68

Tensile strength, yield

MPa

59

Tensile elongation

%

107

Flexural stress

MPa

83

Flexural modulus

MPa

2010

Izod impact, notched at RT

J/m

Izod impact, notched at 23°C

1.25 59

100 150

588

kJ/m

Charpy impact, notched at 23°C

kJ/m

HDT at 0.45 MPa

°C

137

HDT at 1.8 MPa

°C

124

MVR at 250°C and 2.16 kg

cm3/10 min

MVI at 250°C and 10 kg

g/10 min

18

Infino by Samsung (http://www.samsungchemical.com); Pryme by Chase Plastics (http://chaseplastics.com/); Xenoy by Sabic (https://www.sabic-ip.com/). ABS, Acrylonitrile butadiene styrene; GF, glass fiber; HDT, heat deflection temperature; MVI, melt viscosity index; MVR, melt viscosity rate; PBT, polybutylene terephthalate.

Table 9.26 Examples of Industrially Recycled Polyetherimide. Density

g/cm3

1.44

Tensile strength

MPa

131

Tensile modulus

MPa

7000

Flexural strength

MPa

193

Flexural modulus

MPa

7230

Izod impact, notched at RT

J/m

53

HDT at 0.45 MPa

°C

198

MFI at 337°C and 6.6 kg

g/10 min

10

HDT, Heat deflection temperature; MFI, melt flow index.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Cost saving, %

50%

LFRT

40%

TPE

30%

ETP

20%

ETP ETP

10%

ETP 0% LDPE

PP

PS

HDPE

PET bottle

Figure 9.23 Recyclates save costs.

9.6 Recycled Materials Often Also Bring Cost Saving in Addition to Pollution Savings Fig. 9.23 displays the material cost saving percentage when totally replacing the virgin polymer with a recycled one. Often just a fraction of the polymer is replaced by recyclate. Very different cost savings may be found according to prices of crude oil and virgin polymers. For the quoted example, we can remark that, according to the polymer, costs savings evolve between 10% and 40% in round figures. If there is a high demand for recyclates the prices rise, and conversely.

9.7 Some Limitations to Recycled Material Use First of all, recycled plastics (as do virgin plastics) must obey national, regional, global directives, rules, regulations, and other requirements related to the aimed parts, subsets, and devices. Countries to be considered include those of production, transformation, use, and disposal. In addition, the use of recyclate must comply with specific requirements already mentioned for some. For example, remind the limitations of regrind (the least risky form of recycled plastic) recommended by UL and producers. Of course there are many other rules or regulations. Once again, it is the reader’s responsibility to search the paths and perils of his own case.

9.7.1 Underwriters Laboratories’s Recommendations on the Use of Regrind UL accepts:

• No regrind for thermosets, TPEs, and recycled materials.

TPE ETP

%

TPE 0

10

20

30

40

50

60

Figure 9.24 Examples of regrind levels for various thermoplastics.

• Regrind up to a maximum of 25% by weight with the same grade of virgin thermoplastic at the same molder facility without further testing.

• For regrind levels exceeding 25% in the same virgin thermoplastic, UL requires a special evaluation of relevant performance tests such as mechanical, flammability, and aging tests.

9.7.2 Producer Recommendations Fig. 9.24 displays some examples of maximum levels recommended by producers of long fiberreinforced thermoplastics (LFRT), ETP, and TPEs. Levels recommended for LFRT are very low because of the breakability of long glass fibers, which leads to a decrease of mechanical performances. For the other thermoplastics, levels depend on the sensitivity to hydrolysis and thermooxidation as well as the processing parameters. These indications relate to regrind of materials carefully processed and should not be used without severe previous testing.

References Almeras, X., et al., 2004. Prog. Rubber, Plast. Recycl. Technol. 20 (1), 25. Farahat, M.S., 2002. Polym. Int. 51 (2), 183 189. Guclu, G., et al., 1998. J. Appl. Polym. Sci. 69, 2311 2319. Halimatudahliana, et al., 2002. Polym. Test. 21, 163. Kallel, T., et al., 2003. Prog. Rubber, Plast. Recycl. Technol. 19 (2), 61.

9: RECYCLING PLASTICS: ADVANTAGES

AND

LIMITATIONS

La Mantia, F.P., et al., 2003. Prog. Rubber, Plast. Recycl. Technol. 19 (3), 135. Yarahmadi, N., et al., 2001. Polym. Degrad. Stab. 73 (1), 93.

Further Reading Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd.. Biron, M., 2016. Material Selection for Thermoplastic Parts. Elsevier Ltd.. Biron, M., 2014. Thermosets and Composites. Elsevier Ltd.. Plastics Additives & Compounding, Elsevier Ltd., ISSN: 1464-391X, , https://www.journals.elsevier. com/plastics-additives-and-compounding . . Modern Plastics Encyclopaedia, McGraw-Hill Publications. Modern Plastics International, Canon Communications LLC, Los Angeles, CA. PlasticsNews.com, Crain Communications. , https:// www.crain.com/brands/plastics-news . .

OF

USE

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Reinforced Plastics, Elsevier Ltd., ISSN: 00343617, , https://www.journals.elsevier.com/reinforced-plastics/ . . WEBSITES

BIR. , http://www.bir.org/industry/plastics/ . . British Plastics Federation. , http://www.bpf.co. uk/ . . Carbios. , http://www.carbios.fr/ . . Chase Plastics. , http://chaseplastics.com/ . . EPA (US Environmental Protection Agency). , www.epa.gov/ . . European Food Safety Agency (EFSA). , http:// www.efsa.europa.eu/fr/ . . Omnexus. , http://www.omnexus.com/ . . RAMPF. , http://www.rampf-gruppe.de/en/ . . Recoup. , www.recoup.org/ . . Sabic. , https://www.sabic-ip.com/ . . Samsung. , http://www.samsungchemical.com . . Vinyloop Ferrara SpA. , http://www.vinyloop. com/en/ . . Waste & Resources Action Programme (WRAP). , http://www.wrap.org.uk/ . . Wietek. , http://www.wietek.com/ . .

10 Transition of Plastics to Renewable Feedstock and Raw Materials: Bioplastics and Additives Derived From Natural Resources Biosourced polymers are directly or indirectly derived from renewable biomass sources such as vegetable oil, cornstarch, pea starch, sugar, wastes, and so forth, in opposition to fossil plastics which are derived from petroleum. Industry can use physical means, conventional or green chemistry or biosynthesis to convert biomass into feedstocks, building blocks, or usable end forms of plastics. Numerous examples are physical and chemical treatments such as distillation, chemolysis, hydrolysis, oxidation, cracking, hydrocracking, pyrolysis, and so forth, leading to bioblocks, often similar to those coming from oil sources. Bioplastics are not a single class of polymers but rather a broad family of products that can differ considerably one from the other. Let us point out that the needed energy to produce these polymers is mainly produced by conventional ways, including fossil fuels and nuclear energy. Certain bioplastics and fossil plastics are compatible and are used as alloys combining advantages (and some drawbacks) of both. Fig. 10.1 shows the main routes toward bioplastics. Research and development work and continuous financial support bring results leading to new biomonomers, thereby opening the way for the most consumed plastics such as polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), and engineering plastics like polyamide, thermoplastic polyurethane, thermosets, and others. Bioplastics are probably one of the smartest forms of plastics to satisfy sustainability concepts, to help the economic and industrial actors to think about ways able to improve or minimize the degradation of our planet, Earth. However please remember that natural products are not perfect from a sustainable point of view. For example, low cost of crude oil and technical level of fossil polymers make obstruction to their growing. That being so, today, bioplastics are not always the most sustainable way to solve a defined issue

and a good solution in one country may be not so good elsewhere. Let us remark that, contrary to certain preconceived ideas, all bioplastics are not biodegradable and, conversely, certain fossil plastics are biodegradable.

10.1 Brief Inventory of Renewable Polymers Biosourced plastics are recent and the following characteristics and features are those claimed by bioplastics producers. Classification of biosourced plastics is a difficult exercise because of the diversity of sources, treatments, formulations, and possible combinations with fossil polymers. Among resins more or less directly derived from natural raw materials, we can note, for example:

• Starch, produced by all green plants as energy storage, is a major source for food and industrial utilizations, therefore there are risks of competition. Starch-based plastics, modified with flexibilizers and plasticizers such as sorbitol and glycerin constitute an important part of the bioplastics market, mainly for packaging, but there are also various engineering applications.

• Polylactides and polylactic acid (PLA) plastics are the second family of bioplastics resembling conventional clear polystyrene (PS) with good esthetics (gloss and clarity), but are stiff and brittle, which requires formulation and plasticization for most practical applications. Generally they can be processed on existing standard equipment. Compared to a competitive oil-based polymer, dependency from fossil resources is reduced by 25% 55%, and exhaust gases influencing global warming are reduced by 10% 70%.

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00010-0 © 2020 Elsevier Ltd. All rights reserved.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Native biopolymers

Physical and light chemical treatments

Thermoplastic starch cellulose derivatives

Microbial production

Polymerization of bio-blocks

Fermentation

Conventional chemistry

purification

Hydroxyalkanoates

Bio-PE Bio-PA

Figure 10.1 Main ways toward bioplastics.

• Cellulose, the most widespread natural poly-

most abundant organic polymers on Earth, constituting from 25% up to 33% of the dry mass of wood. Lignin is unusual as a biopolymer because of its heterogeneity and imprecise composition. However, as a wood constituent, it is indirectly used in wood plastics composite (WPC), a fast-growing line of plastics.

mer, is usable after simple physical processing or conversion by chemical treatments. It is present in all wild or cultivated vegetal products such as wood, cotton, and other natural fibers (NFs). Chemical modifications lead to cellulosics, acetate, and other esters. Of course, new applications are in competition with existing ones, except if they use wastes. Let us remember that industrial cellulosics are esters of natural cellulose coming from wood. The most common are: • Cellulose acetobutyrate: CAB • Cellulose acetate: CA • Cellulose propionate: CP

• Natural rubber, a polymer of isoprene including

• Cellulosics are appreciated for their easy pro-

For more indirect routes, let us note for example:

cessability, esthetics, transparency, high gloss, pleasant touch, aptitude for coloring and decoration, low electrostatic build-up, balance of fair mechanical properties, and chemical resistance to oils, greases, and aliphatic hydrocarbons, fair electrical insulating properties, fair performance/cost ratio, food contact possibilities. However, cellulosics are handicapped by their density and sensitivity to heat, water, and several common chemicals.

• Polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), and other polyesters produced via microbial routes. According to the used raw materials and polymerization methods, their behavior can evolve from a rigid plastic up to an elastic material with melting points from about 40°C up to 180°C.

• Lignin, a complex chemical compound most commonly derived from wood, is one of the

exclusively carbon and hydrogen with the formula (C5H8)n, consists of a linear chain with a molecular weight of 100,000 up to 1,000,000. It must be noted that natural rubber has very few applications as a thermoplastic resin and must be vulcanized for most applications.

• Polyethylene and PP synthesized from alcohol obtained by fermentation of sugars leading to ethanol, itself leading to ethane.

• PS and PVC could be produced according to the ethanol route.

• Sorona (PTT, PolyTrimethyleneTerephthalate) and copolyester thermoplastic elastomers (Hytrel) can be synthesized from propanediol. SORONA by DuPont is derived from glucose in cornstarch. Fossil resource consumption for the production process is reduced by 50%.

• Polyamides: Rilsan Polyamide 11, Pebax, and Platamid are biobased, high-performance polymers produced from renewable resources. Polyamide 10.10 can have a very high level of biocarbon and PA6.10 can be based to the extent of about 60% on sebacic acid, a renewable raw material derived from castor oil.

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• Thermoplastic

and thermosetting polyurethanes (PUR) can include bio-polyols.

• Acrylics and styrenics: Vegetable Oil Polymer

RAW MATERIALS

471

• The suitable long-term behavior: aging (e.g., heat, sunlight, weathering, wet environment), creep, relaxation, fatigue, etc.

Network studies their production from renewable resources. A grade of Altuglas poly(methyl methacrylate) (PMMA) includes 20% of bioderived carbon.

• The cost. • Eventually, some more specific characteristics.

• Unsaturated polyesters (UPs) can include bio-

In addition to plasticizers and NFs, the oldest and most common additives based on renewable resources include:

polyols. Glycerol released in the production of biodiesel can be converted into propylene glycol for the production of UP resins.

• Phenol formaldehyde resins can include phenols from lignin.

• Epoxy

resins can include epoxidized vegetable oils and epichlorohydrin from glycerol that is released in the production of biodiesel.

• Aromatic polymers. A few material databases such as, for example, M-Base include a biopolymer database (https://biopolymer.materialdatacenter.com/bo/standard/main/ ds).

10.2 Renewable Additives As traditional plastics, biosourced plastics must be customized thanks to additives. Obviously, maintaining the environmental benefits of bioplastics requires the use of bioadditives but traditional additives may be used if necessary. In a general way, note that renewable additives may also include a certain level of synthetic components and that a same line of tradenames may include renewable products and synthetic ones. Like fossil-based plastics, bioplastics must be compounded with additives, blended with other bioplastics or petroleum-based resins to obtain the best balance of performance and cost necessary for most applications needing an optimized set of properties concerning:

• The initial characteristics: sensorial, mechani-

• Fatty acids, their salts, esters and amides used as lubricants, processing aids, PVC heat stabilizers, emulsifier, etc.

• Pine derivatives: pine tar, rosin, terpene used as tackifiers and processing aids.

• Vulcanized vegetable oils or factices used in rubber formulations.

• Phenol derivatives used as antioxidants. Table 10.1 displays some examples of natural additives, raw, or more or less modified, without claiming to be exhaustive. Many of those renewable additives (and plasticizers) have several functions, so a trade or chemical name can appear in several places. Arbitrarily we have sliced additives into several classes and other classifications can be used:

• Processing aids, rheology modifiers. • Surface friction modifiers: Lubricant, slipping, and antiblocking agents.

• Release agents. • Antistatic additives. • Optical property modifiers: antifogging, color, gloss modifiers.

• Impact modifiers. • Protective agents, stabilizers, thermal and aging additives, light stabilizers.

• Miscellaneous additives: nucleating agent, waxes, hardeners, etc.

cal, electrical, optical performances.

• The used processing method: rheology and heat stability must be adapted to molding, extrusion, or thermoforming.

Many of these renewable solutions are already known but some clarification can be useful for others.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.1 Natural and Seminatural Additive Examples. Fatty Acids

Carbon Atoms

Saturated Fatty Acids

Table 10.1 Natural and Seminatural Additive Examples.—Cont’d Fatty Acids

Carbon Atoms

Phenol Derivatives

Butyric or butanoic

4

Vitamin E

Caproic or hexanoic

6

Cardamom

Caprylic or octanoic

8

Cashew oil

Capric or decanoic

10

Liquid Depolymerized Natural Rubber

Lauric or dodecanoic

12

Epoxidized soya bean oil

Myristic or tetradecanoic

14

Oyster powder

Palmitic or hexadecanoic

16

Organic fillers

Stearic or octadecanoic

18

Natural colorants

Unsaturated Fatty Acids Myristoleic

14

10.2.1 Renewable Plasticizers

Palmitoleic

16

Oleic

18

Linoleic

18

Erucic

22

Often, plasticizers account for several percent of plastics parts, which makes the replacement of fossil plasticizers by renewable ones attractive. In specific cases, such as plastisols, high levels of renewable plasticizers allow obtaining a significant renewable content. According to the SPI Bioplastics Council, plasticizers have an estimated worldwide market of 6 million tons. Phthalate plasticizers are increasingly challenged and consequently a range of renewable plasticizers have come on the market. Note that fossil plasticizers can also be used to toughen bioplastics such as PLA. Be careful, trade names are generic and can include nonrenewable materials. Some materials can be synthetic, natural-sourced, or a blend of both. As with conventional plasticizers, renewable ones ease processing, soften rigid polymers, and improve cold temperature behavior. Among the numerous sources let us note, for example:

Metal Salts of Fatty Acids Ba, Ca, Cd, Zn stearates Ca, K, Na, Zn oleate Amides of Fatty Acids Erucamide Oleamide Stearamide Behenamid Oleyl palmitamide Stearyl erucamide Ethylene bis-stearamide Ethylene bis-oleamide Esters of Fatty Acids

• Vegetable oils and derivatives, castor oil,

Glycerol monostearate

epoxidized soybean oil (ESBO).

Pine Derivatives

• Esters. • Isosorbide diesters (Polysorb ID by Roquette), a

Rosin Pine tar Terpene Vulcanized Vegetable Oils White factices Brown factices (Continued )

nontoxic alternative to the phthalates, obtained from renewable resources and having plasticizing properties for PVC. The Polysorb ID line has been registered with the European Chemicals Agency to enable its industrial production. According to the producer, Polysorb ID additives are not suspected to be toxic and they

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473

Table 10.2 Examples of GRINDSTED SOFT-N-SAFE Properties in a Polyvinyl Chloride Formulation. DEHP

GRINDSTED SOFT-N-SAFE

Volatility loss

3.3

0.49

Extraction (water) @23°C

20.03

20.05

Extraction (saline) @23°C

0.01

20.03

Hardness

78

78

Specific gravity

1.24

1.24

Tensile strength (MPa)

20

20

Elongation (%)

383

419

Static stability @192°C

45

45

Delta E (BYK Gardner A65)

STD

2.35

Haze (BYK Gardner)

2.35

4.98

Table 10.3 Examples of reFlex Properties in a Polyvinyl Chloride Formulation. reFlex 100

DPHP/reFlex 50/50

DPHP

Shore A hardness

57

61

69

Tensile strength (MPa)

12

13

16

Elongation at break (%)

470

450

410

100% Modulus (MPa)

3.8

4.8

7.7

Brittle point (°C)

237

246

249

Oil extraction (%)

31

20

10

Volatility 24 h 100°C (%)

1

7

12

have comparable and sometimes better properties than conventional plasticizers. As for other esters, the choice of the acid allows to tune the plasticizing properties, processing characteristics, migration, and volatility.

• Numerous plasticizers based on isosorbide derivatives are quoted by patents (e.g., ATO BV) related to isosorbide esters, isosorbide polyesters, isosorbide ethers, isosorbide carbonates, isosorbide thioethers, isosorbide thioesters, isosorbide amides, isosorbide (thio)urethanes, isosorbide urea, isosorbide phosphates and isosorbide phosphonates, C3 to C11 alkanoates of isosorbide, etc.

• DuPont-Danisco’s

GRINDSTED SOFT-NSAFE based on a vegetable oil already used in foods is approved for food contact materials and will expectedly be used in toys and medical equipment. GRINDSTED SOFT-N-SAFE is claimed to offer (see Table 10.2): Equivalent processing capability to diethylhexylphthalate

(DEHP); no need for major adjustments to the standard formulation in terms of plasticizing efficiency or gel-fusion temperatures; good lowtemperature properties, clarity and color hold in clear formulations; good elongation at break after accelerated aging at 135°C for 7 days. • PolyOne has announced the commercial availability of reFlex 100 (see Table 10.3), a highsolvating, biobased plasticizer that has earned a USDA BioPreferred Label certifying to have 94% biobased content.

• Dow has launched DOW ECOLIBRIUM biobased plasticizers are a new family of phthalatefree plasticizers for use in wire insulation and jacketing that are made from nearly 100% renewable feedstocks. ECOLIBRIUM in PVC compounds reduces greenhouse gas emissions by up to 40%. According to Dow Wire & Cable, the field trials demonstrated that the new plasticizers exhibit the same performance and feel as

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.4 Original Properties of Hallgreen Plasticized Polyvinyl Chloride Formulations. Blank

Hallgreen Plasticized

Tensile strength ultimate (MPa)

45.8

27 41

Tensile strength at break (MPa)

45.8

26 38

Elongation @break (%)

3

3 47

Hardness Duro D (pts.)

77

71 77

Gardner impact resistance in lbf

1.3

2 14

incumbent PVC plasticizers while meeting all regulatory requirements for flame resistance. Hallstar markets Hallgreen environmentally renewable esters, plasticizers, and processing aids usable in all types of biopolymers, PLA, starch-based and traditional plastics. Table 10.4 displays ranges of properties obtained with a panel of Hallgreen plasticizers. • Jungbunzlauer claims its Citrofol products are compatible with a broad range of polymer types that include PVC, PUR, acrylics and also biopolymers such as cellulosics, PLA and PHA. Citrofol BII (Acetyltributyl citrate) is claimed a safe alternative for PVC plasticizers with a good compatibility. A 1:1 replacement is normally possible. Various trials have confirmed that the plasticizer migration of closures is clearly within the limits of the new regulation when Citrofol BII is used. Citrofol can be also used in cellulose derivatives.

• Citrate and blends of citrate and vegetable oil derivatives are quoted as plasticizers for sustainable cellulosic plastics. The European Commission’s scientific committee on toxicity, ecotoxicity, and the environment (CSTEE) is of the opinion that “the risk assessment has provided sufficient evidence to show that toys plasticized by acetyl tributyl citrate can be safely mouthed by children.”

• Unimoll AGF by Lanxess is a yellowish mixture of glycerin acetates developed mainly for plasticizing PVC. The material may also be used in applications requiring food contact approval and is in compliance with a range of food regulations throughout Europe and the United States.

• Triacetin TP LXS 51035 by Lanxess is a plasticizer for cellulose-based plastics such as CAs, CA butyrates, nitrocellulose, and cellulose-based paints.

• Lapol

bioplasticizer, predominantly plant derived resin, plasticizes PLA, and other polymers. It is compatible and miscible with PLA up to 20%.

• A block copolymer formed between PLA and polyethylene glycol plasticizes PLA.

• Glycerol can plasticize starch films and nanocomposites of starch and clay.

• Liquid depolymerized natural rubber is used as a crosslinkable polymeric plasticizer. Table 10.5 displays some renewable plasticizers and their producers without claiming to be exhaustive. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice. Please note that renewable content of renewable plasticizers (or other renewable additives) can be inferior to 100%, for example:

• • • • • • •

Near 100% for Polysorb ID 37 100% for Resiflex K50 100% for dicapryl sebacate 98% for Kalflex 14A 95% for Nexo E01 80% for Soft-N-Safe 66% for PLS Green 9

Of course, data sheets may evolve and other producers may market other grades.

10.2.2 Natural Reinforcements The following displays some examples but many other products are proposed by producers, compounders, or are made in-house.

Table 10.5 Examples of Renewable Plasticizers and Producers. Epoxidized SANSO CIZER

Epoxidized linseed oil

New Japan Chemical

http://www.nj-chem.co.jp/en/

MONSOL ESBO

Epoxidized soybean oil

Michael Ballance Plastics

http://www.ballance-plastics.co.uk/

Epoxidized soybean oil

Epoxidized soybean oil

Nanjing Capatue Chemica

http://www.capatue.com/english/

Baerostab H2000 IN

Epoxidised soybean oil

Baerlocher

http://www.baerlocher.com/

Epoxidized soybean oil

Epoxidized soybean oil

Novista

http://www.novistagroup.com/eindex.asp

Epoxidized soybean oil (ESBO)

Epoxidized soybean oil (ESBO)

Chang Chun Petrochemical

http://www.ccp.com.tw/

Epoxidized soybean oil (ESBO)

Epoxidized soybean oil (ESBO)

The Chemical Company

https://www.thechemco.com/chemical/

Kalflex Varflex

Epoxidized soybean oil and primary plasticizers mixture

Varteco Quimica Puntana

http://www.varteco.com.ar/en/home

Epoxidized soybean Oil (ESBO)

Epoxidized soybean oil

Zhejiang Jiaao Enprotech Stock

http://www.jiaaohuanbao.com/en/

PLS green

ESBO based (amyl, octyl or nonyl epoxy stearate)

Petrom

http://plsgreen.com.br/en/

Vikoflex

Epoxidized vegetable oil

Arkema

HY B, HY, S, Z

Epoxy fatty acid methyl ester, epoxidized soybean oil

Hebei Jingu Plasticizer

http://www.hbjingu.com/plasticizer/

Citroflex

Citrate esters

Vertellus specialties

http://www.vertellus.com/

OXBLUE ATBC

Acetyl tributyl citrate

Oxea

http://www.oxea-chemicals.com/

Citrofol

Acetyltributyl citrate; tributyl citrate; acetyltriethyl citrate; acetyl citrate

Jungbunzlauer

http://www.jungbunzlauer.com/

Dibutyl se´bacate (DBS)

Dibutyl se´bacate (DBS)

Arkema Casda biomaterials

http://casda-biomaterials.lookchem.com/

Esters

Dimethyl sebacate (DMS)

Dimethyl sebacate

Casda biomaterials

http://casda-biomaterials.lookchem.com/

Dioctyl sebacate (DOS)

Dioctyl sebacate (DOS)

Casda biomaterials

http://casda-biomaterials.lookchem.com/

Dicapryl sebacate (DCS)

Castor oil dicapryl sebacate

Jayant Agro-Organics

http://www.jayantagro.com/

OXBLUE DOSX

Dioctyl succinate [bis(2-ethylhexyl) succinate]

Oxea

http://www.oxea-chemicals.com/

Rhenosin

Fatty acid esters

Rhein Chemie Lanxess

http://lanxess.com/en/rhein-chemie/

(Continued )

Table 10.5 Examples of Renewable Plasticizers and Producers.—Cont’d NEO-C

Mixed alcohol ester

Aekyung Petrochemical

http://www.akp.co.kr/eng/

Unimoll AGF

Mixture of glycerine acetates

Rhein Chemie Additives (Lanxess)

http://www.rheinchemie.com/

Hallgreen

Plant-derived ester

Hallstar

http://www.hallstar.com/

Plasthall PR, ELO, ESBO

Renewable ester

Hallstar

http://www.hallstar.com/

GRINDSTED SOFT-N-SAFE

Castor oil derivative

Danisco (DuPont Group)

http://plasticadditives.dupont.com/ products/soft_n_safetm/

Castor oil

Triglyceride of fatty acid

Darwin Chemical Company

http://www.darwinchemical.com/

Blown castor oil

Oxidatively polymerized castor oil

Seatons

http://www.seatons-uk.co.uk/

JLD

Extracted from vegetable oil by modification

Zhejiang Jiaao Enprotech Stock

http://www.jiaaohuanbao.com/en/

Radia

Rapeseed oil-based

Oleon Sofiproteol

http://www.oleon.com/

Sylfat

Tall oil fatty acid

Arizona Chemical

MWV Rosin

Tall oil rosin

Meadwestvaco

Priplast

Mono- or polymeric

Croda

JLD 819

Chlorinated plasticizer extracted from vegetable oil

Zhejiang Jiaao Enprotech Stock

http://www.jiaaohuanbao.com/en/

Dow Ecolibrium

Biobased plasticizer

Dow Chemical

http://www.dow.com/

Polysorb

Isosorbid derivative

Roquette

EDENOLLOXIOL

Trimellitate, sebacate, azelaic, adipate esters; polymeric plasticizer based on adipic acid

Emery Oleochemicals

http://www.emeryoleo.com/

Drapex Alpha

Galata Chemicals

http://www.galatachemicals.com/

Lapol

Lapol

http://www.lapol.net/

Matrica

Matrica (Versalis and Novamont)

http://www.matrica.it/

Proviplast

Proviron

http://www.proviron.com/

ReFlex

PolyOne

http://www.polyone.com/en-us/

Resyflex

Resypar Industria e Comercio

http://www.resypar.com.br/eng/

http://lanxess.com/en/

Vegetable Oil Derivatives

http://www.mwv.com/en-us/

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10.2.2.1 Natural Fibers PP is probably the fossil polymer that is most often combined with NFs. Grades mentioned here are only a few examples taken at random without guarantee concerning their quality and suitability. These examples cannot cover all cases and the quoted company names, trademarks, and websites are provided “as they are” and do not constitute any professional advice. It should be noted that other grades can behave better (or worse). Composites evolution (http://www.compositesevolution.com/) markets, among other products, preconsolidated sheet based on NF and PLA or PP. Biotex Flax/PP sheets can be processed by stamp forming and compression molding allowing to manufacture semistructural and decorative components in applications such as sporting goods and consumer products. Table 10.6 displays some characteristic examples of PLA, biopolyethylene (PE), and fossil PP reinforced with flax fibers. Series of results are not comparable because the forms and levels of reinforcement are diverse. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Data sheets may evolve and other producers may market other grades. Composites evolution also proposes several reinforcements:

• Biotex Jute 550 g/m2 2 3 2 Twill, a low-cost fabric for fiberglass replacement, based on natural jute fiber and designed for fiberreinforced polymer composite applications.

• Biotex Flax 600 g/m2 6 45 Biaxial is a high performance noncrimp fabric for automotive, sporting goods, and decorative applications.

• Biotex Flax UD is a high-performance, unidirectional fabric for automotive, sporting goods, and decorative applications. The materials can be processed using standard composite manufacturing techniques and are suitable for semistructural and decorative applications in a range of sectors including automotive, sports and leisure, consumer goods, and construction. Table 10.7 displays some characteristics of NFreinforced fossil UP depending on the used fiber, jute, or flax. Data are only given to provide a general idea and cannot be used for designing any parts or goods.

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477

ARBOFILL grades by Tecnaro (http://www.tecnaro.de/english/) contain renewable resources and fossil plastics with ratios adjustable to individual client’s requirements, thereby enabling the production of different products with a broad range of properties. Table 10.8 displays some examples of Arbofill compound characteristics. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Under the brand name FIBROLON, FKuR has developed NF-reinforced compounds that can be injection molded or extruded into complex profiles, panels, and hollow profiles and/or into components for automotive interiors. Table 10.9 displays some examples of Fibrolon NF/PP grade characteristics. Data are only given to provide a general idea and cannot be used for designing any parts or goods. PolyFibra by FuturaMat (http://www.futuramat. com/) includes fossil plastics reinforced with wood fibers. Grades target extrusion for profiles or injected products as diverse as shims transport frames, boomerangs, broom sockets, and so forth, Table 10.10 displays some characteristic examples of Polyfibra based on acrylonitrile butadiene styrene (ABS) and PP. Data are only given to provide a general idea and cannot be used for designing any parts or goods. GreenGran (http://www.greengran.com/) markets NF/PP GG F023J special purpose flammability grade based on PP, NFs, and halogen-free additives, which combines high stiffness with 5VB flame retardant properties and V0 at thin wall. It is claimed suitable for production of complex articles with long flow paths and thin walls. Typical markets are within E&E and housing applications. Table 10.11 displays some examples of GreenGran NF/PP grade characteristics. Data are only given to provide a general idea and cannot be used for designing any parts or goods. RTP Company (http://www.rtpcompany.com/) markets cellulose fiber reinforced PP grades with 20% 30% of renewable content and eventually 40% 56% postconsumer recycled content (see Table 10.11). Fig. 10.2 outlines the versatility of NF/PP composites through some examples of compound characteristics. Of course, mechanical performances greatly depend on reinforcement form and rate but also of processing conditions. Tensile strength

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Table 10.6 Examples of Properties of Natural Fiber (NF)-Reinforced Polylactic Acid (PLA) (Fibrolon by FKuR), Biopolyethylene (PE), and Fossil Polypropylene (PP). NF-Reinforced PLA Density

g/cm3

1.1

Tensile modulus of elasticity

GPa

3.8

Tensile strength

MPa

34

Tensile strain at tensile strength

%

3.4

Tensile stress at break

MPa

34

Tensile strain at break

%

3.8

Flexural modulus

GPa

Notched impact strength (Charpy) RT Impact strength (Charpy) RT

3.7

kJ/m

2

4.8

kJ/m

2

11.7

Thermal properties Melt temperature

°C

Vicat A softening temperature

°C

150 160 72 3

Melt volume rate (190°C/5 kg)

cm /10 min

7 9

Melt flow rate (190°C/5 kg)

g/10 min

9 11

Examples of Properties of NF-Reinforced Bio-PE by FKuR 3

A

B

C

1.014

1.045

1.086

Density

g/cm

Tensile modulus of elasticity

GPa

1.3

1.9

2.6

Tensile strength

MPa

23

25

26

Tensile strain at tensile strength

%

9

6

4

Tensile stress at break

MPa

23

24

25

Tensile strain at break

%

10

7

4.5

Flexural modulus

GPa

1.3

2

2.6

Flexural strain at break

%

Flexural stress at 3.5% strain

MPa

7 2

22

29

34

Notched impact strength (Charpy) RT

kJ/m

3.1

3.6

3.5

Impact strength (Charpy) RT

kJ/m2

15

11

8

Melt temperature

°C

130 145

130 145

130 145

Melt flow rate (190°C/2.16 kg)

g/10 min

11 12

6 8

3 4

Thermal properties

Examples of Properties of Flax Fiber-Reinforced PP Preconsolidated Sheet 2 3 2 Twill

Weave style Typical mechanical properties of molded laminates Fiber volume fraction

%

40 3

1.04

Density

g/cm

Tensile modulus

GPa

8.1

Tensile strength

MPa

64

Elongation

%

1.9

Flexural modulus

GPa

5.2

Flexural strength

MPa

66

TRANSITION

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Table 10.7 Examples of Natural Fiber-Reinforced Fossil Unsaturated Polyester Composites Properties. Weave Style Fabric weight

g/m

Typical ply thickness

mm

2

2 3 2 Twill

45 Biaxial

UD

550

600

275

0.9 1

0.7 1.2

0.3 0.6

Jute

Flax

Flax

27

31

27

UP

UP

UP

1.28

1.28

1.28

Typical Mechanical Properties of Molded Laminates Fiber Fiber volume fraction

%

Resin 3

Density

g/cm

Tensile modulus

GPa

8.3

8.7

19

Tensile strength

MPa

55

85

174

Elongation

%

1

1.7

1.5

Flexural modulus

GPa

5.6

6.8

15

Flexural strength

MPa

66

135

196

UP, Unsaturated polyester.

Table 10.8 Renewable Resources and Fossil Plastic Composite: Property Example (Arbofill). Example of Injection Molding Grade Yield stress

MPa

28

Yield strain

%

3.6

Tensile modulus

GPa

2.7

Tensile stress at break

MPa

27

Tensile strain at break

%

4.5 2

Charpy impact strength

kJ/m

Smell

Strength

ranges from less than 10 up to 120 MPa and modulus from 2 up to 14 GPa. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Moreover, other data may be found elsewhere.

10.2.2.2 Balsa Balsa features include:

• relatively low density: 100 kg/m3 and above • attractive cost • fair mechanical properties: • compressive strength: 5 20 MPa in grain direction; 0.6 1.4 MPa in transverse direction (TD)

10.3 Very low

• compressive modulus: 2 8 GPa in grain direction; 0.1 0.4 GPa in TD strength: 6 17 MPa direction

• flexural

in

grain

• good impact behavior • fair thermal, acoustic, and electrical insulation • sensitivity to water and moisture needing a good waterproofing For example Gurit Balsaflex (http://www.balsaflex.com/en/) is a classic balsa wood core material with a high resistance-to-weight ratio for sandwich construction, wind energy, marine, transportation, industrial, and other composite applications. Composites can be produced using hand layup, pultrusion, infusion, press molding, and so forth.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.9 Examples of Properties of Natural Fiber-Reinforced Polypropylene (PP) (Fibrolon by FKuR). Polymer 3

PP

PP

1.03

1.05

Density

g/cm

Tensile modulus of elasticity

GPa

3.2

3.4

Tensile strength

MPa

22

26

Tensile strain at tensile strength

%

3

3

Tensile stress at break

MPa

22

24

Tensile strain at break

%

3

4.5

Flexural modulus

GPa

3.6

3.5

Flexural strain at break

%

4

6

Flexural stress at 3.5% strain

MPa

32

41

Notched impact strength (Charpy) at RT

kJ/m

2

3.3

3.6

Impact strength (Charpy) at RT

kJ/m2

7.9

11

Melt temperature

°C

150 180

160 180

Vicat A softening temperature

°C

139

155

Melt flow rate (190°C/5 kg)

g/10 min

Melt flow rate (230°C/5 kg)

g/10 min

Thermal Properties

2 3 13 15

Table 10.10 Examples of Properties of Polyfibra Compounds Based on Acrylonitrile Butadiene Styrene (ABS) or Polypropylene (PP). ABS

PP

PP

Biocontent

%

20

30

50

Hardness

Shore D

70 84

65 77

67 80

Density

g/cm3

1.04 1.16

0.96 1.06

1.03 1.13

Flexural modulus

GPa

2.3 3.5

2.1 3.3

3.2 5.1

Tensile elongation at yield

%

1.6 2.8

2.2 3.8

2 3.4

Tensile modulus

GPa

2.1 2.8

2 2.7

2.6 3.6

Tensile strength at yield

MPa

23 39

22 36

27 45

Tensile strength at break

MPa

23 39

21 35

27 45

8 14

12 20

10 18

2.7 8.3

0.5 1.7

50 58

79 87

2

Unnotched impact strength

kJ/m

Melt mass-flow rate 190°C/2.16 kg

g/10 min

Melt mass-flow rate 220°C/10 kg

g/10 min

17 32

HDT at 264 psi (1.80 MPa)

°C

35 43

HDT, Heat deflection temperature.

Examples of producers:

Bcomp—http://www.bcomp.ch/

3A Composites, Banova—http://www.airexbaltekbanova.com/banova.html

Diab Group, ProBalsa—http://www.diabgroup. com/Products-and-services/Core-Material/ ProBalsa

TRANSITION

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481

Table 10.11 Examples of Properties of Renewable Fiber-Reinforced Polypropylene (PP). HFFR Grades Based on NF-Reinforced PP (GreenGran) Undefined NF 3

HFFR NF/PP

HFFR NF/PP

1.25

1.2

Density

g/cm

Flexural strength

MPa

.70

.70

Flexural modulus

GPa

5.3 5.5

5.3 5.5

V0

5VB

UL94 Fire rating (4 mm) UL94 Fire rating (1.75 mm)

V0

Examples of Properties of Cellulose Reinforced PP (RTP Company) Renewable content

30

30

Additional postconsumer recycled content

56 3

1.02

1.02

MPa

69

69

Tensile modulus

GPa

2.7 2.8

2.5 2.8

Notched izod impact

J/m

53

48

HDT 0.46 MPa

°C

142

119

HDT 1.8 MPa

°C

78

63

Density

g/cm

Flexural strength

HDT, Heat deflection temperature; HFFR, halogen free fire retardant; NF, natural fiber.

16

Modulus (Gpa)

14 12 10 8

6 4 2

0 0

20

40

60

80

100

120

140

Strength (MPa)

Figure 10.2 PP/NF examples: tensile modulus (GPa) versus tensile strength (MPa). NF, Natural fiber; PP, polypropylene.

Gurit, Balsaflex—http://www.balsaflex.com/en/ I-Core Composites, EG Balsa—http://www.icorecomposites.com/

10.2.2.3 Other Organic Natural Fillers Organic natural fillers bring together a very wide range of disparate materials often locally used because of local or sectorial opportunities or combination of special features. Short fibers and flours may be classified in that family.

Arbitrarily, without claiming to be exhaustive some examples include:

• BioLogiQ has invented a process for making homogeneous blends of NuPlastiQ BioPolymers (starch derivative) with polyolefins. The resulting thermoplastic blend, called BioBlend (https:// www.biologiq.com/bioblend), can be used to make plastic items that could exhibit beneficial properties.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

482

• Wood flour and chips used for WPC and chipboards

• Flour of hulls, shells, seeds, stones or grits and so on of almond, apricot, coconut, nut, peanut, pecan, pine-nut, pistachio-nut, corn, cottonseed, hazelnut, olive, rice, soybean, walnut

• Tree-bark flour, cork, etc. Cork is an example of combination of special features including mechanical behavior and acoustical and damping properties. For example, Amorim cork composites (https:// amorimcorkcomposites.com/en-us/) proposes solutions for acoustical and vibration issues concerning wall bearing material, underlay, underscreed, floating screed, corkwall (final coating to protect houses), core materials for lightweight sandwich composites for thermal, acoustical, or fire performance used in residential and industrial constructions. Amorim cork composites also develops for the European Space Agency a project of thermal protection by ablative shielding that will simultaneously perform structural and thermal functions, allowing the reentry process of space capsules into Earth’s atmosphere. The studied solution is based on a composite material with a high percentage of cork. Lifocork (by Hexpol Tpe) commercializes thermoplastics filled with cork for bowls, trays, boxes, and plant pots.

10.2.2.4 Other Inorganic Renewable Natural Fillers Generally speaking, mineral fillers are not renewable but some special cases may be considered as renewable such as, for example flours of clam shells and oyster shells that are built from CO2 from oceans.

10.2.3 Processing Aids Processing aids is a broad class of additives used to improve processability of plastics mainly by increasing the flowability. Internal lubricants improve the melt flow of material by lowering the viscosity and heat dissipation. Some other additives can ease processing such as lubricants, plasticizers (see section 10.2.1), melt strength improvers and so on, enabling plastics

processors to achieve greater output rates and increased efficiency. Table 10.12 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks and websites are provided “as they are” and do not constitute any legal, or professional advice.

10.2.4 Surface Friction Modifiers: Lubricant, Slipping, and Antiblocking Agents Internal lubricants improve the melt flow during processing and act also as processing aids. Slipping agents reduce the surface coefficient of friction of polymers and ease processing and end applications. Antiblocking agents reduce the adhesion between two adjacent surfaces of a film. Table 10.13 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks and websites are provided “as they are” and do not constitute any legal, or professional advice.

10.2.5 Release Agents Release agents, also known as demolding agents, are added into plastics compounds to ease the separation of the molded part from the mold, enabling plastics processors to achieve greater output rates and increased quality. Table 10.14 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks and websites are provided “as they are” and do not constitute any legal, or professional advice.

10.2.6 Antistatic Additives Antistatic additives prevent the buildup of static dielectric charges when processing insulating plastics. Static dielectric discharges disturb processing and can be an issue for safety, hygiene, and esthetics. Table 10.15 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks and websites are provided “as they are” and do not constitute any legal, or professional advice.

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Table 10.12 Examples of Processing Aids. Castorwax

Processing aid glycerol tri-(12hydroxystearate)

Vertellus Specialties

http://www.vertellus.com/

Finaid

Processing aid

Fine Organics

http://www.fineorganics. com/

FINALUX, Finastat

Processing aid

Fine Organics

http://www.fineorganics. com/

Maxomer Lube

Vegetable-based processing aids

PCC Chemax

http://www.pcc-chemax. com/

Hallgreen R

Processing aid (plant-derived ester)

Hallstar

http://www.hallstar.com/

Jemini 100

Processing aid

JJI Technologies

http://www.jji-technologies. com/

Struktol

Polymeric processing aid (fatty acid derivatives)

Struktol

http://www.struktol.com/

Struktol WS 280 PASTE

Processing aid (blend of fatty acid derivatives and silicone)

Struktol

http://www.struktol.com/

Ultra-Plast

Processing aid (fatty acid derivatives)

http://www.performanceadditives.com/

Waradur

Processing aid (derived from lignitea)

Performance additives ¨ LPKER VO

Soyanol

Coalescing agent (soy-based alkyd resin)

Soy Technologies

http://www.soytek.com/

GEL ALL

Rheology modifier

New Japan Chemical

http://www.nj-chem.co.jp/en/

Lapol

Rheology modifier

Lapol

http://www.lapol.net/

EDENOLLOXIOL

Rheology modifier

Emery Oleochemicals

http://www.emeryoleo.com/

http://voelpker.com/en/

a

Lignite isn’t really renewable at the human time scale.

10.2.7 Optical Property Modifiers: Antifogging, Color, Gloss Modifiers In wet environment, antifogging additives help to avoid the condensation of water vapor on cold plastic surfaces, which results in the formation of water droplets. Colors have aesthetic, safety, and marketing roles enhancing the product value added. Gloss relates to the shiny, bright, luster, or matt appearance and more generally the reflective feature of a plastic material.

10.2.7.1 Renewable Colorants Renewable colorants can be fully renewable (colorants and carriers) or partly renewable. Color concentrates can be based on carriers of currently commercially available biopolymers such as modified starch compounds, biodegradable copolyesters, PHAs and PLA, and so forth. Colorants can be traditional or biobased. For the latter, possible colorants are among, orange curcuma (root of turmeric spice plant), yellow urucum (tropical flower), green (chlorophyll, other plant sources), carmine red (cochineal insect).

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.13 Examples of Surface Friction Modifiers. Oleamide

Slip agent

Croda SIPO

http://www.sipo.com.cn/ch/en

ADD-VANCE SA

Slip agent (masterbatch formulated with oleamide)

AddComp

http://www.addcomp.nl/

IncroMax

Slip agent

Croda

http://www. crodapolymeradditives.com/

EDENOL LOXIOL

Antiblocking agent

Emery Oleochemicals

http://www.emeryoleo.com/

ULTRA-PLAST

Slip agent

PerformanceAdditives

http://www.performanceadditives.com/

Rikemal Rikemaster

Antiblocking agent

Riken

http://www.rikenvitamin.com/ chemicals/plastics.html

Crodamide

Antiblocking agent

Croda

http://www. crodapolymeradditives.com/

Ethylene bis stearamide

Antiblocking agent

Erucamide derivatives

Antiblocking agent

Stearates

Antiblocking agent

Butylstearate

Lubricant

NAYAKEM ORGANICS

http://www.nayakem.com/

CALCIUM STEARATE Zinc stearate Stearine Waxso

Lubricant

SO.G.I.S. Industria Chimica

www.sogis.com/

DOMPLAST BIO

Fatty acid ester lubricant

Domus Chemicals

http://www.domuschemicals.it/

EDENOL LOXIOL

Lubricant

Emery Oleochemicals

http://www.emeryoleo.com/

FINALUX, Finastat

Lubricant

Fine Organics

http://www.fineorganics.com/

Hydrogenated Castor Oil

Lubricant (hydrogenated castor oil)

Frank B Ross

http://www.frankbross.com/

KALCOL

Lubricant fatty alcohol

Pilipinas Kao

http://chemical.kao.com/

Keratech

Lubricant (hydrogenated castor oil—hydroxy stearic acid)

Kerax

http://www.kerax.co.uk/

Ligalub

Lubricant

Peter Greven FettChemie

http://www.peter-greven.de/en/

Ligastab

Lubricant (metal salt of stearic acid)

Peter Greven FettChemie

http://www.peter-greven.de/en/

Loxiol G

Lubricant

Emery Oleochemicals

http://www.emeryoleo.com/ (Continued )

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Table 10.13 Examples of Surface Friction Modifiers.—Cont’d Rheolub RL

Lubricant (blend of in situ calcium stearate and fatty acid esters)

Honeywell

http://www.honeywelladditives.com/

Rice bran wax

Lubricant

HUZHOU SHENGTAO BIOTECH

http://www.shengtao.com/ products/main_en.html

RIKAFLOW EP

Lubricant

New Japan Chemical

http://www.nj-chem.co.jp/en/

Struktol

Lubricant, (fatty acid derivatives)

Struktol

http://www.struktol.com/

Waradur

Lubricant (derived from lignite)

¨ LPKER VO

http://voelpker.com/en/

Oleamide

Slip agent

Croda SIPO

http://www.sipo.com.cn/ch/

ADD-VANCE SA

Slip agent (masterbatch formulated with oleamide)

AddComp

http://www.addcomp.nl/

EDENOL LOXIOL

Antiblocking agent

Emery Oleochemicals

http://www.emeryoleo.com/

Rikemal Rikemaster

Antiblocking agent

Riken

http://www.rikenvitamin.com/ chemicals/plastics.html

Erucamide

Antisticking (nitrogen derivatives of erucic acid)

Darwin Chemical Company

http://www.darwinchemical. com/

Aluminum stearate

Antitack agent

Blachford

http://www.blachford.ca/

Table 10.14 Examples of Release Agents. CALCIUM STEARATE Zinc stearate Stearine Waxso

Release agent

SO.G.I.S. Industria Chimica

www.sogis.com/

Dimodan HP

Release agent

Danisco (DuPont Group)

www.danisco.com/

DOMPLAST BIO

Fatty acid ester release agent

Domus Chemicals

http://www.domuschemicals.it/

EDENOL LOXIOL

Release agent

Emery Oleochemicals

http://www.emeryoleo.com/

Erucamide

Release agent (nitrogen derivatives of erucic acid)

Darwin Chemical Company

http://www.darwinchemical. com/

Finalux

Release agent

Fine Organics

http://www.fineorganics.com/

Rikemal Rikemaster

Release agents

Riken

http://www.rikenvitamin.com/ chemicals/plastics.html

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Table 10.15 Examples of Antistatic Agents. OnColor BIO

PolyOne

http://www.polyone.com/

ACCUREL SF268

75% Antistatic masterbatch based on PP

Membrana

http://www.membrana.com/

Atmer

Antistatic agent

Croda

http://www.crodapolymeradditives. com/

Behenamide

Antistatic agent

Croda SIPO

http://www.sipo.com.cn/ch/

Dimodan HP

Antistatic agent

Danisco (DuPont Group)

www.danisco.com/

EDENOL LOXIOL

Antistatic agent

Emery Oleochemicals

http://www.emeryoleo.com/

Erucamide

Antistatic agent (nitrogen derivatives of erucic acid)

Darwin Chemical Company

http://www.darwinchemical.com/

Finalux

Antistatic agent

Fine Organics

http://www.fineorganics.com/

GRINDSTED AR, PGE, PS

Antistatic agents

Danisco (DuPont Group)

http://www.dupont.com/productsand-services/food-ingredients/ brands/danisco-food-ingredients. html

PE STA1905, SLA, LTA

Antistatic agents of vegetable origin in PE carrier resin

MLPlastics Additive Masterbatches

www.mlplastics.co.za/

Polywhite

Masterbatch containing antistatic additive, titanium dioxide in polyethylene

A Schulman

www.aschulman.com/

Rikemal Rikemaster

Antistatic agent

Riken

http://www.rikenvitamin.com/ chemicals/plastics.html

PE, Polyethylene; PP, polypropylene; PS, polystyrene.

A same provider can propose several solutions such as for example clariant proposing:

• RENOL-natur and CESA-natur, specially formulated for use in biopolymer applications, derived exclusively from renewable resources.

• RENOL-compostable color masterbatches and CESA-compostable additive masterbatches based on conventional additives and pigments that are pretested following EN 13432 and certified. PolyOne has developed a range of color concentrate products specific for use with biodegradable resins. OnColor BIO Colorants are based on biodegradable resins commercially available, including starch, PLA, PHA, PHB-co-hydroxyvalerate (PHBV), polybutylene succinate (PBS), PBAT, and blends of these different polymer families.

Table 10.16 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks and websites are provided “as they are” and do not constitute any legal, or professional advice.

10.2.8 Renewable Impact Modifiers and Tougheners Impact modifiers or tougheners enable plastic products to absorb shocks and resist impact without damage. Hallstar (http://www.hallstar.com/hallgreen.php) proposes two renewable impact modifiers:

• Hallgreen R-3020—100% biobased, transparent impact modifier with limited US Food and Drug Administration (FDA) acceptability.

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Table 10.16 Examples of Optical Property Modifiers. CALCIUM STEARATE Zinc stearate Stearine Waxso

Antifogging agents

SO.G.I.S. Industria Chimica

www.sogis.com/

EDENOL LOXIOL

Antifogging agents

Emery Oleochemicals

http://www.emeryoleo.com/

Finafog

Antifogging agents

Fine Organics

http://www.fineorganics. com/

Rikemal Rikemaster

Antifogging agents

Riken

http://www.rikenvitamin. com/chemicals/plastics.html

Atmer

Antifogging agents

Croda

http://www. crodapolymeradditives.com/

RENOL-natur color masterbatches

Color

Clariant

http://www.clariant.com/

APL 308

Gloss imparting, grinding agent (zinc stearate)

Tianyi Chemical Engineering Material

http://en.tianyi-chemical. com/

• Hallgreen IM-8330—38% bio-based, transparent impact modifier acceptability.

with

limited

FDA

Hallgreen R-3020 are plant-derived and biodegradable esters compatible with many biopolymers, such as PLA, starch and environmentally friendly polyesters. It is also compatible with PVC. Suggested uses include film and sheeting for use in low temperatures, food packaging, food trays, gaskets, and seals. Hallgreen IM-8830 is a partially renewable ester designed to improve the impact resistance of bioplastics such as PLA, starch, PHA, and environmentfriendly polyesters. IM-8830 claimed features include low volatility, high-plasticizing efficiency, excellent resistance to polar fluids, and low-temperature flexibility as well as increased impact resistance. Suggested uses include film and sheeting for use in low temperatures, food packaging, food trays, general-purpose film, packaging, and printable film. Table 10.17 displays some examples of renewable Hallgreen impact modifiers. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Aliphatic polyesters: A variety of aliphatic, lowglass temperature (Tg) polyesters have been combined with PLA and have shown significant improvement in ductility and impact properties.

Polyhydroxyalkonates, such as Nodax, are being developed by several companies (Danimer Scientific, Metabolix, Procter & Gamble) and are one of the few renewable resource-based elastomers that both toughen PLA and help retain the biodegradability characteristics. These elastomers have been blended into PLA at levels up to 60%, with 10% 20% being the preferred range. Bionolle is another aliphatic polyester that also toughens PLA and biodegrades, although it is not based on 100% renewable resources. Yield10 Bioscience (https://www.yield10bio.com/) is developing biopolymers (Mirel) as PVC performance additives. Those resins are miscible with a broad range of biobased and petroleum-based materials, and could improve a range of performance attributes such as impact strength, heat resistance, barrier properties, processability, and plasticization. Epoxidized natural rubber (ENR) with 25% 50% of the unsaturation functionalized with epoxy groups, is more compatible with PLA and has been shown to raise the impact strength from 0.2 to 1.0 ft lb/in. of notch at a 20% level. Higher levels of epoxy functionality (50%) are more effective at increasing toughness than the lower levels (25%). Two ENR grades are available commercially from Muang Mai Guthrie Public Limited Company of Thailand (http://www. mmguthrie.com/), Epoxyprene 25 and Epoxyprene 50.

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Table 10.17 Examples of Impact Modifiers. Hallgreen

R-3020

R-3020

IM 8830

Polymer

PLA

PVC

PLA

Plasticizer (phr)

10

67

10

Tensile strength (MPa)

27

12

35

Ultimate elongation (%)

47

345

125

Shore A hardness

69

Shore D hardness

77

75

Tg (°C)

50

51 228

Brittle point (°C) Gardner impact (lbf)

34

8.3

Air Oven Aging 20.10

70 h @50°C, Weight change (%)

21.7

70 h @121°C, Weight change (%) PLA, Polylactic acid; PVC, polyvinyl chloride.

Table 10.18 Injection Molded Properties of Polylactic Acid (PLA) Parts Containing Various Impact Modifiers. Additive

% Additive

Notched Izod (ft lb/in.)

Tensile Yield (psi)

Elongation (%)

PLA

0

0.5

63

10

Bionolle 3001

15

0.9

60

230

Hytrel 3078

30

3.7

35

430

Core shell type impact modifiers offer good impact performance at moderate loading in PLA for opaque applications. Some fossil Hytrel are compatible with PLA and increase the toughness in blends at levels of 5% 30%. Even at low levels of rubber, very high elongation at break and good impact properties are reached. Renewable Hytrel being chemically similar might be compatible with PLA. Table 10.18 displays properties of injection molded parts containing various impact modifiers. Data sheets may evolve and other producers may market other grades. Masterbatches based on renewable carrier polymer include, for example without claiming to be exhaustive:

• Terraloy 9000 Series masterbatches are formulated with Biostrength impact modifier from Arkema, Inc. and carrier polymers consisting of Ingeo PLA from NatureWorks LLC. Teknor Apex recommends adding the masterbatch to

PLA resins at 5% 10% levels. The Terraloy 9000 Series is in compliance with the FDA requirements for food-contact applications at loadings up to 20%. In one series of standard tests with 2-mil thick cast film tape, Terraloy 9000 Series masterbatch at 5% and 10% loadings increased Gardner impact strength 9-fold and 16-fold, respectively, in comparison with neat PLA. At the same time, haze levels increased from 4.1% to only 4.5% and 6.5%, respectively.

• Polyvel (http://www.polyvel.com/content/products/products.asp) proposes HD-L01 and HDL02 PLA masterbatches developed to improve the impact toughness of PLA. HD-L01 is recommended for use in opaque applications where transparency is not an issue. Typical use levels range from 5% to 10% weight. HD-L02 maintains clarity.

• Biostrength 280 impact modifier (Arkema) can be supplied as a masterbatch in PLA.

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• PolyOne supplies ready-to-use masterbatches

• A renewable polymer collected as a gum from

with Dow Plastics Additives’ Paraloid BPM520.

Moringa oleifera improves the aging resistance of styrene-butadiene rubber (SBR) with a slightly lower effectiveness than a conventional antioxidant such as IPPD.

• SUKANO (https://www.sukano.com/en/applications) proposes biobased transparent Impact Modifiers.

• Viba (http://www.vibagroup.com/en/) has developed Vibatan PLA Modifier 03925, a masterbatch containing an active substance which can improve resilience on a PLA support.

10.2.9 Protective Agents, Stabilizers, Thermal, and Antiaging Additives, Light Stabilizers Antioxidants prevent and delay oxidation of the polymer reacting with oxygen of air. Oxidation can cause loss of impact strength and elongation, surface cracks, and discoloration. Heat stabilizers prevent and delay decomposition of the polymer during processing. Light stabilizers inhibit and delay the reactions in plastics which cause undesirable chemical degradation, discoloration, cracking and loss of performance from exposure to UV light. As synthetic phenols and amines, suitable natural phenol, and amine derivatives have antioxidant properties. For example:

• In a thermal behavior study, the oxidation induction time is 7 minutes for PP, 11 minutes for PP protected thanks to a standard antioxidant (Irganox), and 8 12 minutes for PP containing various lignins.

• For PP fibers, Chemtura’s (today Addivant— www.addivant.com/) patented amine oxide GENOX EP. Derived from renewable resources, it exhibits excellent performance, especially for gas-fading protection.

• Cashew nut shell liquid (CNSL) is a mixture of meta-alkylphenols with a variable degree of unsaturation attached to the benzene ring. The kinetic studies of the thermal degradation at 140°C of polyisoprene films, in the presence of technical CNSL and some derivatives show an increase of the induction period and a decrease of the apparent rate constants of thermal oxidation.

• Vitamin E, a natural antioxidant, is expected to improve the longevity of the polyethylene implant bearings used in total joint replacements. CESA-natur antioxidants (Clariant) use such natural antioxidants.

• CESA-natur light masterbatches (Clariant) provide light stabilization in both conventional and biopolymers. They can also function as a UV filter to protect the contents of packaging made of bioplastics such as PLA. Like synthetic additives, they are based on aromatic molecules coming from naturally occurring ingredients. The newest CESA-natur light masterbatches are formulated from lightcolored substances that are substantially more heat stable and offer UV protection comparable to conventional synthetic UV absorbers.

• Abad et al. (2002) for natural rubber, study the replacement of conventional synthetic antioxidants with a natural mixture of α, β, γ, δ tocopherols or with natural keratin extracted from chicken feathers. After optimization of the preparation processes, results are promising. These natural products perform better than certain synthetic antioxidants and compete well with some others.

• Abad et al. (2002) found that nonwater soluble amino acids such as cystine, tyrosine, asparagine phenyl alanine, and alanine have antioxidant properties on rubber latex films. Keratin from chicken feathers has anti- or prooxidant effects according to the extraction method and posttreatments.

• Cerruti et al. (2009) study and prove the efficiency of tomato extracts and grape seeds as stabilizers for PP films.

• Polymer scientists have been awarded a USD 304000 grant to develop a range of antioxidants from the active natural ingredients present in rosemary. Rosemary Antioxidant Extract (http://www.flavex.com/flavex_home_cms_2_13_13.html) produced by supercritical fluid extraction has antioxidative, antimicrobial and antiinflammatory properties.

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Table 10.19 Examples of Protective Agents. Akcrostab LT

Heat and light stabilizer (mixed metal, epoxidized soybean oil blend)

Akcros Chemicals

http://www.akcros.com/

CESA-natur antioxidants

Antioxidant (vitamin E)

Clariant

https://www.clariant.com/ masterbatches

CESA-natur light masterbatches

Light stabilizer

Clariant

https://www.clariant.com/ masterbatches

Baerostab LSA, LSU, NT

Heat and light stability (epoxidized soybean oil)

Baerlocher

https://www.baerlocher.com/ products/

Caplig

HALS (bis-tetramethylsebacate)

Nanjing Capatue Chemica

http://www.capatue.com/english/

GENOX EP

Heat stabilizer

Addivant

https://www.addivant.com/ content/genox%C2%AE-epstabilizer

LIGA Calcium Behenate

Heat stabilizer (calcium salt of behenic acid)

Peter Greven FettChemie

http://www.peter-greven.de/en/

Lignin

Heat stabilizer

CNSL

Heat stabilizer

https://www.cardolite.com/cnsl http://muskaangroup.com/CNSLExtraction-Plants.html http://www.sridevigroup.com/

Catechin and epicatechin

Heat stabilizer (green tea extract)

CNSL, Cashew nut shell liquid; HALS, hindered amine light stabilizer.

It is already used in fatty oils, carotenoids, essential oils, food industry, and cosmetics.

• The aqueous extract of natural Diospyros peregrina was found to improve aging of natural rubber latex films.

• The performance of green tea extract, or its individual components catechin and epicatechin, was compared in PP samples stabilized with a mixture of the synthetic antioxidants Irganox 1076 and Irgafos 168. Each sample was extruded and consecutively reextruded up to four times. The obtained results showed the interest of these natural materials as a potential source of antioxidants for plastics. (Dopico Garcı´a and Coll, 2011, p.3553)

• In˜iguez-Franco et al. study (2012). They conclude “the films produced in this study could

be an attractive alternative to control oxidation problems in the pharmaceutical, medical, food, or cosmetic areas.” Table 10.19 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks and websites are provided “as they are” and do not constitute any legal, or professional advice.

10.2.10 Miscellaneous Additives: Fire Retardants, Tackifiers, Nucleating Agent, Waxes, Hardeners, Foaming Agents, etc Antimicrobials help prevent deterioration of plastic materials by microbiological attack. Such

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attacks can cause staining, discoloration, odor, and loss of esthetics but also change of electrical properties, hygiene issues, and loss of mechanical properties in the material. Fillers or extenders are substances used to change properties and lower the cost of the material. Flame retardants prevent or retard ignition or spread of flame in plastic materials. Plastics have substantial use in construction and electrical and transport applications subjected to harsh fire safety requirements. Tackifiers increase tack or sticky behavior of polymers. Wax can be from natural or synthetic origin. Renewable waxes are animal-based (beeswax) or vegetable-based (carnauba for example). Montan wax or lignite wax is not really renewable at human-time scale. The functions depend on the chemical structure, origin, melting point, and chemical modifications of the raw wax. Functions can be as diverse as flow improver, mold-release agent, protective additive, surface enhancer, and dispersing agent for fillers and additives. Hardener, crosslinker or curing agent: A threedimensional (3D) network of thermosets is built thanks to chemical reactions linking several polymer chains generally in presence of hardeners, crosslinkers, or curing agents. Crosslinking can be achieved by heating, moisture exposition, UV, or electron beam irradiation, among others. CNSL is mainly composed of four phenol derivatives and can be used as curing agents for epoxy resins curing at relatively low temperatures. Table 10.20 displays some examples of renewable additives and related producers without claiming to be exhaustive. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice.

10.2.11 Renewable Masterbatches Based on Renewable Matrix or Renewable Additive In addition to previously quoted masterbatches without claiming to be exhaustive, Table 10.21 displays some examples of renewable masterbatches containing renewable additives or renewable carrier polymers. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice.

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10.3 Ready-to-Use Thermoplastic Blends Derived From Starch, a Natural Polymer The following information, claimed by producers, relates to some examples but many other producers propose other grades, blends, and derivatives, some of which may have somewhat different features. The reader must be cautious concerning the exact sense of expressions and figures concerning renewable content, biobased carbon level, renewable carbon, compostable, biodegradable, and so forth.

10.3.1 Overview The oldest industrial product is probably MaterBi (by Novamont), a thermoplastic starch (TPS) (today fourth generation) that can be processed by injection, extrusion, thermoforming, and foaming. It can be colored using Mater-Bi-based biodegradable masterbatches (Clariant and other manufacturers). According to Novamont, properties of ready-to-use grades are in the range of those of polyolefins, not basically different from commodity petroleum-based resins, particularly low-density polyethylene (LDPE) (see Table 10.22). These data are not a rule and other characteristics can be found elsewhere. They cannot be used for designing any parts or goods. Bioplastic resins may contain various levels of biologically sourced polymers such as potato starch, PLA, aliphatic copolyesters, patented proprietary compatibilizers, and so forth.

10.3.2 Processing Generally speaking: Injection grades can be molded using standard injection presses. The maximum injection temperature must be inferior to 200°C and the residence time must be as short as possible. Parts have the advantage of being antistatic, eliminating the accumulation of electrical charges. About 10% of the scraps can be reused. Many parts can be injection molded such as, for example, pencil sharpeners, rulers, cartridges, toys, combs, plant pots, and “bones” and other toys for pets. Extrusion grades can be processed into film using traditional LDPE extruders but at lower extrusion temperatures. Productivity and scrap level are similar and scraps can be recycled using the

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Table 10.20 Examples of Miscellaneous Renewable Additives. Alve-One

Foaming agent

Solvay

https://www.solvay.com/en/ products/brands/alve-one

Charmor PM40 Care

Flame retardant (pentaerythritol derivative)

Perstorp

https://www.perstorp.com/

Kronitex CDP, TCP

Flame retardant (naturally derived cresyl diphenyl phosphate; naturally derived cresol based tricresyl phosphate)

Great Lakes Chemtura

http://www.greatlakes.com/

Polycard XFN

Flame retardant (renewable aromatic multifunctional polyol— cashew shell oil-based)

Composite Technical Services

http://ctsusa.us/

Sylvatac RE SYLVAPACK RE Sylvalite RE

Tackifier (pentaerythritol ester of rosin) (stabilized tall oil rosin ester and crude sulfate turpentine) (polyol ester of rosin)

Arizona Chemical

http://www.arizonachemical. com/

Piccolyte

Tackifier (polyterpene resin)

Pinova

http://www.pinovasolutions. com/

MWV Rosin

Tackifier (tall oil rosin)

Meadwestvaco

http://www.mwv.com/en-us/

Terpene Resin

Tackifier (terpene resin)

Rosin Chemical Wuping

http://www.rosin-wuping. com/en-index.html

Staybelite Pexalyn

Tackifier (rosin derivative)

Pinova

http://www.pinovasolutions. com/

Montan Wax

Wax (derived from lignite)

Frank B Ross

http://www.frankbross.com/

NatureWax

Wax

Elevance Renewable Sciences

http://www.elevance.com/

Rice bran wax

Wax

http://www.shengtao.com/ products/main_en.html

Waradur

Wax (derived from lignite)

HUZHOU SHENGTAO BIOTECH ¨ LPKER VO

GEL ALL

Nucleating agent

New Japan Chemical

http://www.nj-chem.co.jp/en/

GLIDOX

Polymerization initiator (terpene hydroperoxide)

Symrise (previously Renessenz)

https://www.symrise.com/ search/

Micropel 2 ESO

Antimicrobial (2% solution of OBPA in epoxidized soybean oil plasticizer)

Troy Corporation

http://www.troycorp.com/

Novocard

Biobased epoxy hardeners systems

Composite Technical Services

http://ctsusa.us/

http://voelpker.com/en/

(Continued )

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Table 10.20 Examples of Miscellaneous Renewable Additives.—Cont’d CNSL

https://www.cardolite.com/ cnsl

Curing agent for epoxies

http://muskaangroup.com/ CNSL-Extraction-Plants. html http://www.sridevigroup. com/ Walnut Shell Fillers

Filler

Composition Materials Co

http://compomat.com/

NeroPlast

Filler

New Polymer Systems

http://www. newpolymersystems.com/

BioTred

Filler (starch)

Novamont

www.novamont.com

Laurel BioComposite

https://www. laurelbiocomposite.com/

BioRes Sacrificial binder

Sacrificial binder (PPC)

Novomer

http://www.novomer.com/

Oleris 2Octanol Fatty alcohol based

Solvent and antifoaming agent

Arkema

http://www.arkema.com/

CNSL, Cashew nut shell liquid; PPC, polypropylene carbonate.

Table 10.21 Examples of Masterbatches Based on Renewable Polymers. Bylox Compound

Bioadditive masterbatch

Genarex

http://www.genarex.com/

CM, CN, CP

Bioadditives masterbatches based on PLA

Polyvel

http://www.polyvel.com/

Terraloy 9000

Renewable carrier: PLA

Teknor Apex

VIBATAN

Renewable carrier: PLA

Viba Group

http://www.vibagroup. com/en/

PLA/PHA masterbatch

Renewable carrier: PLA

Metabolix

http://www.metabolix. com/

PHA Cellulose Starch PLA Bio-PE PA11 PA6 PA10

Renewable carrier: PHA Cellulose Starch PLA Bio-PE PA11 PA6 PA10

CP, Cellulose propionate; PE, polyethylene; PHA, polyhydroxyalkanoate; PLA, polylactic acid.

same techniques as those used for PE. Different film grades are available for specific applications, for example, bags, shopping bags, mulching films, packaging, and hygiene products. Films can be

printed on using water- or solvent-based inks, with any type of printing technique and without the need for surface treatment. Sealing is similar to that of PE with a competitive speed.

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Table 10.22 Starch-Based and Petroleum-Based Resin Property Examples. MATER-BI

PP

PS

LDPE

Injection

Film

MFI (g/10 min)

6 30

2 4

6 30

19 24

0.1 6

Tensile strength (MPa)

15 35

20 50

20 40

20 60

10 30

Elongation at break (%)

20 150

200 600

100 500

1 5

150 600

Young’s modulus (GPa)

0.6 5

0.1 0.6

0.6 1.6

2.5 3.5

0.15 0.3

LDPE, Low-density polyethylene; MFI, melt flow index; PP, polypropylene; PS, polystyrene.

Thermoforming: Starch-based films and sheets can be used to manufacture nontransparent, rigid, thermoformed trays, which are used for fresh-food packaging. This packaging can be disposed of in a composting plant with the food scraps. Foaming: The Mater-Bi Wave foam sheet is an alternative to PS, polyurethane, and polyethylene foams commonly used in protection packaging. Starch is expanded using water, extruded into sheets and then assembled into blocks that can be cut into any shape. Mater-Bi Wave has a robust and resilient closed-cell structure. Sheets and blocks are available in different sizes, with densities from 30 to 400 kg/m3. Sealability: Biofilms are often sealable by hot, radio frequency, and ultrasonic processes. Recycling: Wastes of bioplastics may be pollutants of traditional fossil plastics wastes.

10.3.3 Environmental Features Be cautious of environmental properties. For example, the renewable raw material content and the biobased carbon share may be far lower than 100%, for example 30% and 23%, respectively, for a given grade. Generally, main environmental indicators are of interest:

• Starch derivatives have a renewable content higher than 50%.

• For 15 grades the average embedded energy is 35 MJ/kg polymer for a range of 19 55 MJ/kg polymer.

• For 14 grades the average net carbon footprint is 1.4 CO2 equivalent per kg for a range of 0.9 3.6 CO2 equivalent per kilogram. Biodegradability and compostability depend on the end product thickness and the used method.

From an environmental point of view, some materials are certified “biodegradable and compostable” under the EN13432 and EN14995 standards for Europe and under the ASTM D-6400 standard for the United States, and some materials have received similar compostability certifications (AS 4736 in Australia, GreenPla system in Japan). The certifying bodies operating in the biodegradable and compostable plastics sector include CICCertiquality (Italy), DIN CERTCO (Germany), and VINC ¸ OTTE (Belgium). Materials that are awarded compostability certificates are entitled to use specific logos that can be printed on the packaging for granular Mater-Bi and on accompanying advertising and technical documentation. In general these are proprietary logos of the certifying bodies and are subject to strict regulations for use and reproduction on products. Logos (such as “Compostabile CIC”, “Ok Compost,” or “OK Compost Home”) awarded to specific resins may not be used on finished products if these products have not in turn undergone the same certification procedures.

10.3.4 Application Sectors Quoted applications can be commercialized, in development, potential or related to very specific uses. The designer must check the possibility to use the quoted plastics family for his or her own problem and test the right grade under real service life conditions. Applications include, but are not limited to:

• Single-use and multiuse bags, carrier bags, loop-handle bags, refuse bags, bin liners, dustbin bags, green-waste bags, animal-waste bags, compost bags, garbage bags, laundry bags.

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• Disposable apron, retail shopping bags. • Mono layer and coextrusion bags, films for seaweed and mud therapy (spa treatments), heavy-duty sacks.

• Industrial films (single layer or coextrusion), packing and laminating films, stretch films and hoods, protective sheaths and covers, netting, safety tapes.

• Agricultural films, mulch films, horticultural, and garden uses.

• Short-life packaging, food packaging, food trays, electronic wrapping material, spare parts wrapping material.

• Injection-molded and thermoformed products, cutlery, medical devices, clips, cups for hot and cold drinks, shatterproof articles.

• Rigid applications like flower pots, tomato clips, cultivation tubes, promotional items, toys, CD- and DVD-trays, protection corners for packaging, cup holders, plant stakes, golf tees, cotton buds.

• Tubes. • Consumer goods, caps, closures. • Automobile parts.

10.3.5 Examples of Producers and Trademarks The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice. Only some examples are quoted and many other producers market many other grades. AMITROPLAST by Agrana (https://services. agrana.com/en/) Biolice by Limagrain (http://www.carbiolice. com/en/) BIOPAR by BIOP Biopolymer Technologies AG (https://unitedbiopolymers.com/biopar-technology/) Bioplast by Biotec (https://en.biotec.de/) Cardia Biohybrid by Cardia Bioplastics (http:// www.cardiabioplastics.com/products/biohybrid) Cornpole by Japan Corn Starch (http://www. nihon-cornstarch.com/product/bio_plastic/tabid/160/ Default.aspx) ENVIPLAST by Enviplast (http://www.enviplast.co.id/company_profile.html) Mater-Bi by Novamont (http://materbi.com/en/)

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Plantic by Plantic (http://www.plantic.com.au/) Solanyl Optimum, FlourPlast, and Optimum Optinyl by Rodenburg Biopolymers (biopolymers. nl) and Solanyl Biopolymers Inc (http://solanylbiopolymers.com/) Wuhan Huali Environment Protection—PSM (https://psm.en.alibaba.com/)

10.3.6 Property Tables Table 10.23 displays some examples of properties of molded or extruded TPS. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Other grades are marketed.

10.4 Polylactic Acid Polymerized From a Natural Monomer PLA is one of the most consumed bioplastics.

10.4.1 Overview Several forms of PLA lead to somewhat different properties:

• poly-L-lactide [P-L(levogyre)-LA] the most used. Poly-L-lactide (PLLA) has a crystallinity of around 37%, a glass transition temperature between 50°C and 80°C, a heat deflection temperature (HDT) of about 100°C and a melting temperature around 175°C.

• poly-D-lactide [P-D(dextrogyre)-LA]. Poly-Dlactide (PDLA) is amorphous with an HDT of about 60°C and is optically transparent.

• blends of PLLA and PDLA • copolymers block-PLAs (bPLAs) resulting from block copolymerization of PLLA and PDLA leading to neo-PLA having properties almost comparable to those of poly(butylene terephthalate) (PBT) used as an engineering plastic.

• stereocomplex PLA (scPLA): BIOFRONT by Teijin having a special crystal structure in which the poly-L-lactic (PLLA) acid and polyD-lactic (PDLA) acid are arranged alternately. Of course, the formulation with usual or specific additives even more broadens the range of properties.

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Table 10.23 Property Examples of Thermoplastic Starch. Density (g/cm3)

1.1 1.3

1.25

1.28

3.7

4.6

,1

, 0.3

, 0.3

#2

$7

25

29

$ 16

24

27

MFR (190°C, 5 kg) (g/10 min) Moisture content (% weight)

1.2 1.4

Mechanical Properties Tensile strength MD (MPa) Tensile strength TD (MPa) Tensile modulus (GPa)

0.8 1.7

1.3

Elongation at break MD (%)

470

250

Elongation at break TD (%)

550

470

Flexural strength (MPa)

12 18

Flexural modulus (GPa)

0.8 1.8

25

Oxygen permeability (80 μm) [cm3/(m2 day bar)]

750

Water vapor permeability (80 μm) [g/(m day)]

120

2

High Modulus Compounds Density (g/cm3)

1.3

1.3

1.3

1.35

MFR (190°C, 2.165 kg)

8

Moisture content (% weight)

, 0.2

Mechanical Properties Tensile strength (MPa)

29

30.5

29.5

31

Tensile modulus (GPa)

1.85

2.05

2.85

2.3

Elongation at break (%)

16.5

7

1

4

Flexural strength (MPa)

53

Flexural modulus (GPa) HDT 0.45 MPa (°C)

1.8

1.8

2.7

50

55

47

2

Charpy impact strength unnotched (kJ/m )

2.4 75

2

Charpy impact strength notched (kJ/m )

5

HDT, Heat deflection temperature; MD, machine direction; TD, transverse direction.

For each family, PLLA/PDLA rates can broadly vary, allowing to control final properties. For formulated blends of PLLA and PDLA, the most used, the melting temperature can evolve in the range 175°C 220°C and the HDT can be substantially enhanced when the PDLA rate increases. The optimized ratio is about 50:50 but concentrations as low as 3% 10% of PDLA can be efficient. PLA has a low crystallization rate, so that after processing it remains mostly amorphous, which limits its use for commercial applications. For the scPLA, for instance BIOFRONT developed by Teijin Limited or Compound SC by TotalCorbion, melting points are about 210°C/215°C. In addition, by developing a new additive (cyclic

carbodiimide) that controls the hydrolysis of the polymer, it is possible to improve the hydrolysis durability allowing the production of durable engineering plastics widening the application scope of PLA in uses such as automobile, electronic equipment, and apparel. The stereocomplex series aims applications such as medical care, packages, civil engineering and construction, and oil fields (the drilling phase in shale gas extraction, etc.). According to the ratio PLLA/PDLA, bPLA can reach melting temperatures of 215°C, tensile strengths in the order of 65 MPa, and modulus of about 2 GPa. Findings of a European Union-funded project looking at the potential to use biobased PLA polymers in

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packaging applications were published at a recent K show, revealing both opportunities and challenges. The German DKI institute found considerable variation in commercially available PLA grades. It tested PLA and modified PLA materials to determine the proportion of D-lactic and L-lactic acid monomer, highlighting extreme differences in commercially available PLA. Some grades can be processed at 300°C without signs of degradation, others discolored “under normal conditions,” according to the institute.

10.4.2 Processing Processing equipment and conditions are more or less comparable to those of commodity resins. However it is necessary to take into account:

• The sensitivity to water and humidity as far as the temperature is higher. Drying is essential for the stability of the material in the molten state. A moisture content of less than 0.025% (250 ppm) is recommended to prevent viscosity degradation. It is necessary to keep sealed the foil-lined boxes or bags initially dried avoiding exposition to atmospheric conditions after drying. Pellets that have been exposed to the atmosphere for extended time periods will require additional drying time.

• The incompatibility with other resins. All the processing machinery and lines must be properly cleaned before feeding and purged to prevent any cross contamination.

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Extrusion: PLA can be processed on conventional extrusion equipment with a suitable generalpurpose screw. As well as for molding, the material is stable in the molten state, provided that the drying procedures are carefully followed and the temperature and residence times are suitable. Rheology is highly dependent on melt temperature. Thermoforming: PLA extruded sheets must be stored in a dry and temperate environment, below 40°C and 50%RH, which avoids drying before thermoforming, haze parts, blocking and unwinding issues, molecular weight breakdown, and loss of physical strength. PLA is highly polar and has an electrostatic build-up needing the use of antielectrostatic bars. Generally, PLA can be processed using forming ovens, molds, and trim tools designed for PET or PS, high impact polystyrene (HIPS) and oriented polystyrene (OPS). Corona or flame surface treatment can be used to ensure high-quality printed graphics. Foam: Synbra Group (https://www.synbratechnology.com/biofoam/) uses a new polymerization technology for the production of BioFoam (Synterra BF 1505—Foam Grade) based on PLA developed by Sulzer Chemtech and Purac Biochem. BioFoam will be positioned complementary to the wide range of PS foam products offered today. Synbra has received the cradle-to-cradle certification for the production of BioFoam. The process of molding is adapted to suit expansion of the raw beads (called BioBeads) in existing expanded polystyrene (EPS) shape molding equipment. Reduction of CO2 emission compared to expanded PS could be as high as 60% 70%.

• PLA regrind is not compatible with other regrind products. It is necessary to carefully clean the grinding equipment and transfer lines or to have dedicated systems for PLA. Some grinding systems can require additional cooling to efficiently grind PLA. Amorphous regrind must be crystallized prior to drying at low temperature (e.g., below 50°C) to assure efficient and effective drying.

• The thermal stability: processing temperatures must be as low as possible and the residence times must be as short as possible. Injection: Suitable PLA grades can be processed on conventional injection molding equipment. The material is stable in the molten state, provided that the drying procedures are carefully followed and the temperature and residence times are suitable. Rheology is highly dependent on melt temperature.

10.4.3 Environmental Features Be cautious of environmental properties. For example, the renewable raw material content and the biobased carbon share of commercialized products may be far lower than 100%. Generally, main environmental indicators are of interest:

• PLA compounds often have a renewable content higher than 70%.

• For 24 grades the average embedded energy is 47 MJ/kg polymer for a range of 17 70 MJ/kg polymer.

• For 24 grades the average net carbon footprint is 1.4 CO2 equivalent per kilogram for a range of 22 to 3.8 CO2 equivalent per kilogram (negative values come from farming of raw materials).

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Suitable end products made with PLA, depending on the formulation and application, may compost in municipal and/or industrial facilities according to ISO, ASTM, and EN regulations, and PLA resin may be certified appropriately. Biodegradability and compostability depend on the end product thickness and the used method. NatureWorks committed to use:

10.4.5 Examples of Producers and Trademarks The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice. Only some examples are quoted and many other producers market many other grades.

• By 2019, 60% of the feedstock certified as sustainably and responsibly managed via International Sustainability and Carbon Certification plus (ISCC 1 ).

• By 2020, 100% of feedstock certified as sustainably and ISCC 1 .

responsibly

managed

via

Website

Arctic Biomaterials Oy—ABM Composites

https:// abmcomposite. com/

ArcBiox

Corbion Purac

http://www. corbion.com/

Luminy

ISCC 1 is an independent, third-party, sustainability certification system.

https://www.totalcorbion.com/ Futerro

http://www. futerro.com/index. html

Futerro

NatureWorks

http://www. natureworksllc. com/

Ingeo

RTP Cy

http://web. rtpcompany.com/ info/data/ bioplastics/

Biobased PLA

Showa Denko

http://www. showa-denko. com/

Bionolle Starcla

Synbra

http://www. biofoam.nl/index. php

Biofoam

10.4.4 Application Sectors PLA targets molded parts, profiles, films, foam, and fiber. Quoted applications can be commercialized, in development, potential, or related to very specific uses. The designer must check the possibility to use the quoted plastics family for his or her own problem and test the right grade under real service life conditions. Applications include, but are not limited to:

• cutlery, cups, plates and saucers, dairy containers, food serviceware, transparent food containers, blister packaging, cold drink cups, outdoor novelties, trash bags

• food and nonfood packaging, blister packag-

https://www. synbratechnology. com/biofoam/ synterra-pla/ datasheets/

ing, coffee capsules, cards, cartons, and nonfood packaging, paper laminating

• rooting substrate, twine, tomato clips and pegs, drains, plastic pots

• consumer goods, electronics, cosmetics, housewares, toys, phone cases

• • • •

building and construction 3D printing filaments biaxially oriented films, mulch film textiles, nonwovens, fabrics

Brand Name

Company

Teijin

https://www.teijin. com/

Biofront

Total Corbion PLA

https://www.totalcorbion.com/

Luminy PLA

Zhejiang Hisun Biomaterials

http://en. hisunplas.com/

Hisun

PLA, Polylactic acid.

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10.4.6 Property Tables Properties of PLAs are tailored by usual formulation means using, among others, the broad choice of additives examined at the beginning of this chapter but two specific issues merit a brief and superficial overview.

10.4.6.1 Melt Strength Enhancement Arkema markets Biostrength 700 product that can double the melt strength of PLA. Biostrength B280 transparent impact modifier is said to be particularly well-suited to toughening sheet for reduced scrap and increased line speeds. Rohm and Haas (Dow) markets PARALOID BPMS-250; 255 and 265, acrylic melt strength enhancers improving film and sheet extrusion, blown film extrusion or calendering. Polyvel markets CT-L02 and CT-L03 masterbatches containing 30% active compounds that increases the melt strength of PLA. Additionally, CT-L02 will raise the impact strength of the final product. Joncryl ADR 4368 and 4370 by BASF maximize melt viscosity through branching where high melt strength is needed for steady parisons, nonsagging profiles, and closed-cell, low-density foams. Joncryl ADR 4300 and 4385 increase melt viscosity through moderate branching for higher elasticity in deep-draw thermoforming and orientation processes. Joncryl ADR 4380 raises melt viscosity through linear extension for resistance to shear-rate variations in injection molding.

10.4.6.2 Heat Stabilization Vibatan Blue Antiox 97838 by Viba Group increases thermal stability of PLAs during processing and controls yellowing that can occur thanks to a blue agent. Lapol HDT-P increases HDTs in PLA to greater than 150°C and improves toughness of PLA products. The team from the US Government’s Agricultural Research Service and private company Lapol said they have created a modifying system that could see PLA used in hot-filled applications across the food and beverage industry. The modifier is said to be more than 90% corn-based and fully biodegradable. Preliminary tests indicate that, when blended with PLA, the modifier can raise the bioplastic heat-deflection temperature by at least

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10°C, said the group. Thanks to the modifier, PLA could be used for food and beverage containers that are hot-filled. Sukano Polymers Corp. markets some additive masterbatches for heat and impact resistance improvements. Sukano’s PLA uv S547 masterbatch is said to protect light-sensitive goods in clear PLA packages. Table 10.24 displays some examples of properties of molded or extruded compounds based on PLA, neat, modified, or reinforced with synthetic or natural additives. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Other grades are marketed.

10.5 Natural Linear Polyesters Produced by Bacterial Fermentation— Polyhydroxyalkanoates Natural aliphatic polyesters are synthesized through the fermentation of sugar and lipids (glucose, sucrose, vegetable oils, even glycerin from the production of biodiesel) by a wide variety of bacteria. They can combine many monomers, which leads to a wide range of characteristics and applications. Some specific examples of PHAs include PHB, PHBV, hydroxybutyrate, 3-hydroxyhexanoate (PHBH), and many others. the GO!PHA (https://www.gopha.org/pha), Global Organization for PHA is a member-driven, nonprofit initiative to accelerate the development of the PHA-platform industry.

10.5.1 Overview PHAs are a family of polyesters produced by bacterial fermentation with the potential to replace some conventional hydrocarbon-based polymers. PHAs occur naturally in a variety of organisms using various renewable waste feedstocks. A generic process to produce PHA by bacterial fermentation involves fermentation, separation from the growth medium, and purification. PHA versatility allows obtaining a broad range of properties. Poly-3-hydroxybutyrate, the first bacterial PHA identified can be tailored to obtain thermal and mechanical properties in the range of

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Table 10.24 Property Examples of Polylactic Acid (PLA) Compounds. Unreinforced Injection Grades

General Purpose

General Purpose

Durable Goods

Durable Goods

Amorphous

Semicrystalline

Neat PLA Resins Specific Gravity

1.24 1.25

1.24

1.24

1.24

Melt index (g/10 min) (210°C/2.16 kg)

10 85

14 22

65

65

Melt index (g/10 min) (190°C/2.16 kg)

10 40

Clarity

Transparent

Transparent

Opaque

Tensile strength (MPa)

48

63

63

Tensile modulus (GPa)

3.8

3.6

3.6

3.6

Flexural strength (MPa)

108

108

108

Flexural modulus (GPa)

3.6

3.6

4.3

Tensile elongation (%)

2.5

3.5

3.5

1.3

Notched izod impact (J/m)

16

16

16

16

55 56

55 56

151

HDT 0.45 MPa (°C) Unreinforced Extrusion Grades

Thermoforming

Bioriented BOPLA

Specific gravity

1.24

1.24

Melt index (g/10 min) (210°C/2.16 kg)

5 7

2.1

Clarity

Transparent

Haze

2.1

Gloss (20°)

90

Tensile strength (MPa)

53

103 110 (MD) 144 (TD)

Modulus (GPa)

3.5

3.3 3.4 (MD) 3.8 3.9 (TD)

Tensile elongation (%)

6

160 (MD) 100 (TD)

Notched izod impact (J/m)

13

Examples of Natural Fiber-Reinforced PLA Density (g/cm3)

1.1

1.15

Tensile modulus of elasticity (GPa)

3.8

3.3

Tensile strength (MPa)

34

46

Tensile strain at tensile strength (%)

3.4

4.8

Tensile stress at break (MPa)

34

42

Tensile strain at break (%)

3.8

5.5

Flexural modulus (GPa)

3.7

3.9 (Continued )

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Table 10.24 Property Examples of Polylactic Acid (PLA) Compounds.—Cont’d Unreinforced Extrusion Grades

Thermoforming

Bioriented BOPLA

4.8

4.2

Impact strength (Charpy), RT (kJ/m )

11.7

19

Melt temperature (°C)

150 160

. 155

72

72

Melt volume rate (190°C/5 kg) (cm /10 min)

7 9

7 9

Melt flow rate (190°C/5 kg) (g/10 min)

9 11

9 11

2

Notched impact strength (Charpy), RT (kJ/m ) 2

Vicat A softening temperature (°C) 3

Property Examples of Glass Fiber-Reinforced PLA Resins Glass fiber (%)

10

20

30

40

Specific gravity

1.32

1.39

1.48

1.57

Izod impact strength, notched (J/m)

43

48

53

48

Izod impact strength, unnotched (J/m)

320

320

320

320

Tensile strength (MPa)

79

97

110

110

Tensile elongation (%)

1.5

1.5

1.5

1.0

Tensile modulus (GPa)

6.9

8.3

10.2

13.8

Flexural strength (MPa)

93

117

145

145

Flexural modulus (GPa)

6.6

8.6

11.2

13.8

HDT @1.8 MPa (°C)

106

148

149

149

HDT @0.46 MPa (°C)

143

152

160

160

Property Examples of Mineral-Filled PLA Resins for Injection Molding 10% Talc

10% CaCO3

30% CaCO3

Biocontent (%)

68 78

73

53

Specific gravity

1.25 1.28

1.26

1.4

Tensile strength (MPa)

36 48

39

32

Tensile elongation (%)

8 . 10

5 10

3

Flexural strength (MPa)

66 76

69

45

Flexural modulus (GPa)

3.4 4.1

3.1

4.1

Notched izod impact (J/m)

80 182

320

80

Unnotched izod impact (J/m)

800 No break

No break

800

Melt temperature (°C)

171 193

HDT 0.45 MPa (°C)

66 82 SC0

SC1

SC2

Glass fiber content

0

20

40

Biobased content (%)

98

78

58

Biobased carbon content

98

98

98

Tensile strength (MPa)

54

135

150

Property Examples of Stereocomplex

(Continued )

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.24 Property Examples of Polylactic Acid (PLA) Compounds.—Cont’d Property Examples of Stereocomplex SC0

SC1

SC2

Tensile modulus (GPa)

2.8

8

13.5

Tensile elongation (%)

2

2

1

Flexural modulus (GPa)

3

6

13.5

2

4

10

10

2

Unnotched izod impact (kJ/m )

44

44

44

Melt temperature (°C)

215

220

220

HDT 1.80 MPa (°C)

64

195

198

HDT 0.45 MPa (°C)

140

211

209

Notched charpy impact (kJ/m )

HDT, Heat deflection temperature; MD, machine direction; TD, transverse direction.

commodities such as PS or PP. In addition, various copolymers broaden end properties and processing windows.

10.5.2 Processing PHA polymers can be processed with standard equipment for conventional plastics after suitable adaptations. The possible incompatibility with other resins, humidity, and thermal stability of the resin must be considered. Injection: Suitable PHA grades can be processed on conventional injection-molding equipment. The material is stable in the molten state, provided that the drying procedures are carefully followed and the temperature and residence times are suitable. Extrusion: PHA could be processed on conventional extrusion equipment provided that the drying procedures are carefully followed and the temperature and residence times are suitable. Thermoforming: PHA extruded sheets must be stored in a dry and temperate environment.

10.5.3 Environmental Features Be cautious of environmental properties. For example, the renewable raw material content and the biobased carbon share may be far lower than 100%. Generally, main environmental indicators are of interest:

• PHAs have a renewable content higher than xx %.

• For 18 grades of PHA the average embedded energy is 49 MJ/kg polymer for a range of 223 up to 107 MJ/kg polymer. For 3 grades of PHB the average embedded energy is 57 MJ/kg polymer for a range of 45 80 MJ/kg polymer.

• For 17 grades of PHA the average net carbon footprint is 0.8 CO2 equivalent per kilogram for a range of 23.1 up to 4.6 CO2 equivalent per kilogram. For 3 grades of PHB the average net carbon footprint is 0.6 CO2 equivalent per kilogram for a range of 23 up to 2.6 CO2 equivalent per kilogram. By nature PHAs offer a vast diversity. Some are claimed to be biobased and biodegradable in natural soil and water environments, home composting systems, and/or industrial composting facilities. The rate and extent of biodegradability depend on the size and shape of the articles made from it. Some are not designed to biodegrade in conventional landfills. For example, PaperMate has used PHAs for its line of biodegradable pens. They can be composted in an ambient home compost environment, completely biodegrading within a year.

10.5.4 Application Sectors PHA targets molded parts, profiles, films, foams, and filaments. The designer must check the possibility to use the quoted plastics family for his or her own problem and test the right grade under real service life conditions.

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Quoted applications can be commercialized, in development, potential, or related to very specific uses including, but not limited to:

• films and other flexible packaging uses • rigid grades developed for disposable cutlery, disposable razors, etc.

• thermoformed blisters • injection molded food service and packaging applications including caps and closures, and disposable items such as forks, spoons, knives, tubs, trays, jars, etc.

• consumer product applications, golf tees, etc. • packaging barrier for moisture and odors (PHB), biodegradable containers (of which shampoo bottles are the most high-profile example)

• fibers produced through conventional melt spinning processes that can be processed using conventional textile processes such as braiding, knitting, and weaving

• monofilament suture

10.5.5 Examples of Producers and Trademarks The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice. Only some examples are quoted and other producers market other grades.

Company

Website

Bio-on

http://www. minerv.it/ indexEng.php

Bioplastech

http://www. bioplastech.eu/

Danimer

https:// danimerscientific. com/

Kaneka

http://www. kaneka.co.jp/ kaneka-e/

Lux-on (Bio-on and Gruppo Hera)

https://www.luxon.com/

Brand Name Minerv

Kaneka PHBH

(Continued )

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—Cont’d Brand Name

Company

Website

(Meredian) Today Danimer

http:// meredianinc.com/

PHB Industrial

http://www. biocycle.com.br/ imprensa_ing_01. htm

Biocycle

TEPHA

http://www.tepha. com/technology/ overview/

TephaFLEX

TianAn Biopolymer

http://www. tianan-enmat. com/

Enmat

Tianjin Green Biosciences

http://www. tjgreenbio.com/ en/

GreenBio

SIRIM (Malaysia)

http://www.sirimqas.com.my/

Yield10 Bioscience

https://www. yield10bio.com/

Mirel

PHB, Polyhydroxybutyrate.

10.5.6 Property Tables According to the used polymerization methods, raw materials, and formulation, PHA behavior can evolve from a soft plastic up to a rigid material with melting points from about 40°C up to 180°C. Table 10.25 displays some examples of properties of molded or extruded compounds based on PHA, neat, modified, or reinforced with synthetic or natural additives. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Other grades are marketed. There is a prevalence of stiff sample and high elongations at break samples are rare.

10.6 Cellulose Derivatives Based on Natural Cellulose Cellulose, the most common natural polymer, is usable after simple physical processing or modification by chemical treatments. It is present in all wild or cultivated vegetal products such as wood, cotton, and other NFs. Chemical modifications lead to

Table 10.25 Examples of Natural Linear Polyesters. PHA: Property Examples Statistical Analysis of 20 Samples Mean

Median

Standard Deviation

Minimum

Maximum

Tensile strength (MPa)

25

22

7.6

15

43

Elongation at break (%)

183

20

2

850

1.25

1.25

1.2

1.25 1.6

1.25

1.25

Moisture absorption equilibrium (%)

0.75

0.4

Linear mold shrinkage (%)

1.3

1.3 1.6

57

67 31 36

40

Detailed Examples Density

1.3

Mechanical Properties Hardness, Shore D Tensile strength, yield (MPa)

23 40

Tensile strength, break (MPa)

22 30

Tensile modulus (GPa)

0.1 0.7

0.5

Elongation at break (%)

250 500

35

25 30 15 20

20 27

39

0.6 1.2

0.9 1.2

1.7 3

2.8 3.5

3.5

5 15

11 18

4 9

2

5

18

29 40

Flexural strength (MPa) Flexural modulus (GPa)

1.3 2

Izod impact, unnotched (J/m)

200

3.5 4.2

100

35 60

Izod impact, notched (J/m)

26 37 2

Charpy impact, unnotched (kJ/m ) 2

Charpy impact, notched (kJ/m )

21

30

2.1

2.7

22

Electrical Properties Electrical resistivity (Ω cm)

1E 1 16

1E 1 16

1E 1 16

Dielectric constant (1 MHz)

3.0

3.0

3.0

Thermal Properties Maximum service temperature, air (°C)

95

120

120

Minimum service temperature, air (°C)

2 30

230

2 30

95

(Continued )

Table 10.25 Examples of Natural Linear Polyesters.—Cont’d PHA: Property Examples Statistical Analysis of 20 Samples Mean Melting temperature (°C)

Median

Standard Deviation

Minimum

170

Maximum 170 176

Specific heat (J/g °C)

1.4

1.4

Thermal conductivity (W/m K)

0.15

0.15

PHB Examples (Based on Biocycle Data) Density

1.2

1.3

1.3

Tensile strength (MPa)

32

24 30

36 38

Elongation at break (%)

3.5

2 2.2

2

Flexural modulus (GPa)

2.25

2.4 2.6

3.8

Izod impact, notched (J/m)

26

19 23

34 36

HDT 0.45 MPa (°C)

115 117

121

123 125

HDT 1.8 MPa (°C)

65

65 70

74 75

Melting point (°C)

170 175

165 170

165 170

PHBH by Kaneka Semirigid PHBH

Rigid PHBH

Density

1.19

1.2

Tensile strength (MPa)

25

28

Tensile modulus (GPa)

0.665

1.24

Elongation at break (%)

331

26

Flexural modulus (GPa)

0.9

1.53

Izod impact, notched (J/m)

39

33

HDT 0.45 MPa (°C)

87

100

Melting point (°C)

136

142

Glass transition temperature, Tg (°C)

0

2

HDT, Heat deflection temperature; PHB, polyhydroxybutyrate.

506

cellulosics, acetate, and other esters. Industrial cellulosics are esters of natural cellulose coming from wood. The most common are: Cellulose acetobutyrate: CAB Cellulose acetate: CA Cellulose propionate: CP

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

10.6.2 Processing Cellulosics, among the oldest industrialized plastics, are easy to process by conventional moltenstate methods such as extrusion, injection, compression, transfer, rotomolding, and thermoforming; They can also be processed in the solvent phase and by welding and machining.

Cellulose acetate propionate: CAP Other cellulose-based engineering thermoplastic (e.g., Tre¨va by Eastman)

10.6.1 Overview The properties can be modified via the broad possibilities offered by plasticization. Relatively hard, rigid, and strong original polymers can be plasticized to produce tough, more-flexible, but weaker materials. CA is chosen for its transparency but is sensitive to water and weathering. CAB is less sensitive to weathering, water, and chemicals but has a stronger smell. CP has better mechanical properties, is odorless, and sterilizable. Eastman TREVA are new cellulose-based engineering bioplastics that offer both high performance and reduced environmental impact. The USDA’s BioPreferred program has certified Eastman TREVA Engineering Bioplastic GC6011 with a biobased content of 45%.

10.6.1.1 Advantages Cellulosics are appreciated for their: easy processability; esthetics; transparency; high gloss; pleasant feel; aptitude for coloring and decoration; low electrostatic build up; balance of fair mechanical properties and chemical resistance to oils, greases and aliphatic hydrocarbons; possibilities of plasticization allowing very low moduli to be obtained; fair electrical insulating properties; fair performance/cost ratios; food contact possibilities.

10.6.1.2 Drawbacks Cellulosics are handicapped by their sensitivity to heat, several common chemicals, and water; the price (justified by the performances); density; the small number of sources and grades.

10.6.3 Environmental Features Be cautious of environmental properties. For example, the renewable raw material content may be far lower than 100%, for example 40% or 60%. Generally, CA and CAB may have a renewable content up to 60%. Other common environmental indicators are less attractive than those previously quoted for renewable plastics:

• For 5 grades the average embedded energy is 83 MJ/kg polymer for a range of 65 106 MJ/ kg polymer.

• For 5 grades the average net carbon footprint is 0.9 CO2 equivalent per kilogram for a range of 20.3 up to 3.8 CO2 equivalent per kilogram.

10.6.4 Application Sectors Cellulosics are mainly used for aesthetic applications related to color, gloss, and feel. Quoted applications can be commercialized, in development, potential, or related to very specific uses:

• Automotive: furniture trims, sun visors, face shields, etc.

• Packaging: films, transparent wrappers, containers, bottles, boxes, tubing, etc.

• Blister packaging, healthcare, cosmetics, perfumery, personal care supplies.

• Containers, furniture trims, combs, etc. • Medical: ophthalmic, optical safety frames, spectacles, sunglasses, etc.

• Lighting, signs, diffusers, lighting devices and accessories, displays, profiles.

• Films, extruded sheets and plates, thin-gauge extruded tubes, etc.

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• Household, appliances items, toothbrushes, door handles, curtain rings, hairdressing items, stoppers on scent vials, etc.

• Knitting needle cases, dice, knife handles, etc. • Industry: hand tools, screwdriver handles, but-

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10.6.6 Property Tables Table 10.26 relates to examples only and cannot be generalized. Data are only given to provide a general idea and cannot be used for designing any parts or goods.

tons, handles, hammer heads, etc.

• Metallized parts, vacuum metallized parts, reflectors, etc.

• Pen/stationary supplies: pen barrels, writing instruments, squares, etc.

• Miscellaneous: recreational parts, costume jewelry, toys, sporting goods, etc.

10.6.5 Examples of Producers and Trademarks The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal, or professional advice. Only some examples are quoted and other producers market other grades. Trade name examples: Bioceta, Biograde, Cellidor, Eastman CA, CAB, CAP, EnviroPlastic, Ocalio, Setilithe, Tenite, Tre¨va. Producer examples: Albis

http://www.albis.com/ en/

Celanese Acetate Products

http://www. celaneseacetate.com/

Daicel

http://www.daicel.com/

Eastman

http://www.eastman. com/

FKuR

https://fkur.com/en

Innovia films

http://www.innoviafilms. com/

Mazzucchelli1849

http://www. mazzucchelli1849.it/

Planet Plastics Cy

http://www. planetplastics.com/

Rhodia

http://www.rhodia.com/

Rotuba

http://www. naturacellnow.com/

Sateri

http://www.sateri.com/

Solvay Acetow

http://www.solvay.com/ en/

10.7 Biopolyethylene and Biosourced Ethylene Vinyl Acetate 10.7.1 Overview Today, several different ways are used for the production of biopolyethylene:

• dehydration of ethanol coming from sugar cane on the one hand (Braskem for example) and

• treatment of waste or byproducts such as postconsumer recycled PE, used fats and oils, methane captured in palm oil mills, used cooking oils, and so forth, that are not in direct competition with the food chain (e.g., Sabic, LyondellBasel, Neste). Braskem inaugurated one of the largest ethylenefrom-ethanol plants that will enable the production of 200,000 t of green polyethylene per year (I’m green Polyethylene). The process used to produce each ton of polyethylene from the primary raw material removes 2.5 t of carbon dioxide from the atmosphere through sugarcane photosynthesis. The final product is claimed having the same properties and characteristics as conventional polyethylene and can be processed by clients’ equipment without the need for any major adjustments. Braskem has stepped up its research into the development of other polymers, especially green PP. Sabic investigates or uses two ways for its renewable feedstocks: methane capture in palm oil mills and recycling of waste fats. LyondellBasell and Neste have jointly announced the first production at a commercial scale of biobased, LDPE using renewable hydrocarbons derived from waste and residue oils. Several thousand tons of biobased plastics approved for the production of food packaging are marketed under Circulen and Circulen Plus tradenames dedicated to circular economy products. Ethylene vinyl acetate (EVA) derives from sugarcane.

Table 10.26 Cellulosics: Examples of Properties. CA Minimum

CAB

CP

Maximum

Minimum

Maximum

Minimum

Maximum

Miscellaneous Properties Density (g/cm3)

1.22

1.34

1.15

1.22

1.17

1.24

Shrinkage (%)

0.3

1.0

0.2

0.9

0.1

0.9

Absorption of water (%)

1.9

7.0

0.9

2.2

1.2

3.0

Mechanical Properties Shore hardness (D)

.50

,95

60

90

.40

90

Rockwell hardness (R)

,125

,125

,125

,125

,125

,125

Rockwell hardness (M)

,80

,90

,70

,70

,75

75

Stress at yield (MPa)

23

23

34

34

32

32

Tensile strength (MPa)

13

67

18

48

14

50

Elongation at break (%)

6

70

40

90

30

100

Tensile modulus (GPa)

0.6

2.8

0.4

1.7

0.45

1.4

Flexural modulus (GPa)

0.6

2.8

0.6

2.1

0.45

1.4

Notched impact strength ASTM D256 (J/ m)

50

400

50

500

25

NB

HDT B (0.46 MPa) (°C)

50

100

54

108

60

120

HDT A (1.8 MPa) (°C)

44

90

45

94

44

110

Continuous use temperature (°C)

45

95

60

105

60

105

Glass transition temperature (°C)

100

130

80

120

80

120

Brittle point (°C)

230

230

0.30

0.40

0.30

0.40

0.40

0.40

8

18

10

17

10

17

Volume resistivity (Ω cm)

1013

2 3 1013

1011

2 3 1015

2 3 1015

3 3 1015

Dielectric constant

3

8

3

7

3

4

Loss factor (1024)

100

1000

100

400

60

300

Dielectric strength (kV/mm)

8

15

10

17

12

18

Arc resistance (s)

50

300

175

190

Oxygen index (%)

17

17

17

17

17

17

UL94 fire rating

HB

HB

HB

HB

HB

HB

Thermal Properties

Specific heat (cal/g/°C) 25

Coefficient of thermal expansion (10 /°C)

Electrical Properties

Fire Behavior

(Continued )

Table 10.26 Cellulosics: Examples of Properties.—Cont’d CA Minimum

CAB Maximum

CP

Minimum

Maximum

Minimum

Maximum

General chemical properties are subject to the compatibility of the fillers and reinforcements with the ambient conditions. If the fillers are well-adapted, the chemical properties are the same for filled and neat polymers Light

UV stabilization is needed

Weak acids

Limited behavior

Strong acids

Unsatisfactory

Weak bases

Limited behavior

Strong bases

Unsatisfactory

Solvents

Cellulosics generally resist oils, greases, and aliphatic hydrocarbons Aromatic or chlorinated hydrocarbons, detergents have a limited effect They are attacked or dissolved by esters, ketones, phenols, concentrated acids and bases, alcohols

Food contact

Possible for special grades

¯ TREVA Engineering Bioplastic GC6011 Clear Biobased content (%)

GC6021 Clear

OP6026 Clear

42

Miscellaneous Properties Density (g/cm3)

1.23

1.22

1.22

Shrinkage (%)

0.7

0.8

0.7

Absorption of water (%)

2.3

2.2

2.3

Rockwell hardness (R)

108

102

100

Tensile strength (MPa)

51 55

48 50

48 49

Elongation at break (%)

21

22

18

Flexural modulus (GPa)

2.160

1.946

1.940 216

Mechanical Properties

Notched impact strength ASTM D256 (J/m) (23°C)

82

195

Notched impact strength ASTM D256 (J/m) (240°C)

66

80

Notched impact strength ASTM D256 (J/m) (230°C)

100

Thermal Properties HDT B (0.46 MPa) (°C)

116

114

114

HDT A (1.8 MPa) (°C)

102

100

99

CA, Cellulose acetate; CAB, cellulose acetobutyrate; CP, cellulose propionate; HDT, heat deflection temperature; PHA, polyhydroxyalkanoate.

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10.7.1.1 Reminder of Advantages of Traditional Polyethylene General advantages are low price, attractive price/property ratios, easy transformation, chemical inertness, impact resistance, low absorption of water, low density [high-density polyethylene (HDPE) included], good electrical insulator, low coefficient of friction, suitability for food contact (special grades), ease of welding, and good machinability for rigid grades; good resistance against high-energy radiation, physiological inertness, and versatility of processing methods except for UHMWPE.

• LDPE: good mechanical properties, flexibility, and impact resistance at ambient temperature; good insulating material even in a wet medium; chemically inert.

• HDPE: same properties as LDPE but more rigid; better thermal and creep behavior; lower coefficient of friction and higher pressure strength, allowing antifriction applications with higher PV (pressure 3 velocity) factor; more transparent.

• UHMWPE:

better mechanical properties, lower coefficient of friction and higher pressure strength allowing antifriction applications with higher PV factor.

• Linear PE: same properties as the equivalent branched PE with an improvement in the mechanical properties, thermal and creep behavior, and resistance to stress cracking.

• Metallocene: enhanced toughness, impact and puncture strengths, better low-temperature behavior, and optical properties.

• Crosslinked PE: more resistant to temperature, creep, and cracking.

10.7.1.2 Reminder of Drawbacks of Traditional Polyethylene General drawbacks are the innate sensitivity to heat, UV, light, weathering (but stabilized grades are marketed), stress cracking, and creep; low rigidity, significant shrinkage, limited transparency. Due to the surface tension, gluing, painting and printing are difficult without surface treatments. Composed only of carbon and hydrogen, PEs are naturally flammable but flame-retardant (FR) grades are marketed.

Processing is difficult for UHMWPE due to the high-molecular weight. PE is sensitive to prooxidant metals such as copper, manganese, or cobalt, which must be avoided as inserts.

10.7.2 Processing Theoretically, all molten-state processing methods are usable: extrusion, injection, compression, blown film, blow molding, rotational molding, thermoforming, foam, coating, powdering, coextrusion, fluidized bed, machining for high hardness grades, welding. Special grades can be crosslinked after shaping.

10.7.3 Polyethylene Environmental Features Be cautious of environmental properties. For example, the renewable raw material content and the biobased carbon share may be far lower than 100%. Generally, main environmental indicators are of interest:

• Renewable PE compounds often have a renewable content higher than 80% (84% 96% for Braskem PE).

• For 2 grades the average embedded energy is 34 MJ/kg polymer for a range of 18 50 MJ/kg polymer.

• For 8 grades the average net carbon footprint is 21.4 CO2 equivalent per kilogram for a range of 23.9 to 2.2 CO2 equivalent per kilogram (negative values come from farming of raw materials that absorb more CO2 from the atmosphere than it emits throughout its production cycle, from the cultivation of sugarcane to final PE resins).

Generally polyethylene is not biodegradable.

10.7.4 Polyethylene Application Sectors Table 10.27 displays some examples of quoted renewable polyethylene potential applications without claiming to be exhaustive, fossil polyethylene being replaceable by renewable polyethylene in most cases.

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Table 10.27 Renewable Polyethylene: Examples of Claimed Usages. Users and Usages

Packaging Food

Tetra Pak

Nonpackaging Nonfood

Food containers

Ecover LIQUID DETERGENT

Detergent bottles

L’Occitane LIQUID SOAP

Soap bottles

Sphere GARBAGGE BAGS

Waste bags

Papier-Mettler SHOPPING BAGS

Shopping bags

Amsterdam ArenA STADIUM SEATS

Stadium seats

Plastic Omnium

Trash can and bin bags

Tetra Pak LIDS FOR CARTONS

Lids

McCain FROZEN POTATOES

Food pouches

Procter & Gamble PANTENE NATURE FUSION

Cosmetic containers

Coca-Cola ODWALLA

Food bottles

Danone STONYFIELD

Food bottles

Kimberly Clark NEVE

Packaging films

Danone DANONINHO & ACTIVIA

Food pots

Nomacorc wine bottle closures

Food bottle closures

Prysmian AFUMEX GREEN

Industrial packaging

Adimax MAGNUS ECO

Pet food packaging

Tigre ECOLOGICAL GRID FOR DRAIN

Grid for drains

MSA V-GARD HELMET

Helmets

Fitesa sheath of nonwoven (core in PLA)

Sheath of nonwoven

Natura CONDITIONERS AND REFILLS

Liquid soap containers

Faber Castell PENCIL CASE

Pencil cases

Ecomotion ROTOMOLDED KAYAKS

Kayaks

BASF AGROCHEMICAL CONTAINERS

Agrochemical containers

J&J SUNDOWN

Sunscreen lotion containers

Yuhan Kimberly DIAPERS PACKAGING

Packaging films

Calpis DRINK PACKAGING Shiseido COSMETICS

Drink bottles Cosmetic containers (Continued )

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Table 10.27 Renewable Polyethylene: Examples of Claimed Usages.—Cont’d Users and Usages

Packaging Food

Nonpackaging Nonfood

Ajinomoto LIDS

Bottle lids

Kao STAND-UP POUCH

Pouches

Aeon BASKETS AND BAGS

Baskets

Mitsubishi AUTOMOTIVE CARPETS

Carpets

Nepia PACKAGING FOR TISSUES

Film wrap

Nature Organics CLEANING PRODUCTS

Cleaning product containers

BubblePack BUBBLE PLASTIC

Bubble wrap

PLA, Polylactic acid.

At more or less long term, renewable PE could replace fossil PE in all the actual applications of fossil polyethylene such as:

• films and sheets for packaging (food, nonfood, shrink, stretch, other applications), agricultural and industrial films; extrusion coating

• injection molding, blow molding, pipes, and conduits

• household chemical bottles, industrial drums, liquid food bottles, food and beverage containers; drugs, cosmetics and toiletries containers, crates and totes

• housewares • rotomolded products • fuel tanks for the automotive industry, molded basins, bottles, stoppers, toys, hollow parts, small electric equipment, pallets, street furniture, seats

• large-sized objects: cisterns, tanks, septic tanks, hulls of boats, canoes, buoys, sailboards, barrels, drums, etc.

• gas, water or sewer pipes, sheaths • crosslinked foams, extruded, and molded parts • UHMWPE: gears, bearings, antifriction parts for light loads, prostheses

• foams: densities from 25 up to 330 kg/m3, semirigid to flexible, with insulating and damping properties for packaging, building insulation, panels and sandwich structures, multilayer composites for damping (e.g., helmets).

10.7.5 Examples of Producers and Trademarks • Braskem markets I’m green Polyethylene. • SABIC launches renewable polyolefins and begins commercialization of certified circular polymers. Volumes of pyrolysis oil from plastic waste are introduced in the feedstock polyethylene (PE) and PP. The pyrolysis oil is produced by Plastic Energy Ltd from the recycling of low quality, mixed plastic waste otherwise destined for incineration or landfill. The polymers are certified through the ISCC 1 scheme that certifies: • Circular content, and • Standards across the value chain from source to end product. The ISCC 1 certification (https://www.iscc-system.org/) works on a “mass balance system,” meaning in brief that for each ton of circular feedstock fed into the cracker and substituting fossil-based feedstock, a ton of the output can be classified as circular.

• Axens, Total and IFPEN launch Atol, an innovative technology for the production of bioethylene that can be integrated in existing downstream polymerization installations without the need of modifications.

• LyondellBasell and Neste market Circulen and Circulen Plus including biobased LDPE using renewable hydrocarbons derived from waste and residue oils.

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• The Dow Chemical Company is working with various societies to manufacture polyethylene from sugar cane.

• Total (rPE 6407), Borealis, and others market grades that contain recycled HDPE coming from postconsumer material intended for nonfood contact applications.

• Neste produces renewable feedstock primarily from waste and residue fats and oils. In 2017, waste and residues accounted for 76% of renewable raw material usage. Neste has started exploring ways to introduce plastics waste as raw material in fossil oil refining and petrochemical industries. Neste has been selected for inclusion in the Dow Jones Sustainability Indices for the 12th consecutive year.

10.7.6 Polyethylene Property Tables Renewable polyethylene has properties and characteristics of the same order as traditional fossil polyethylene and can be processed by clients’ equipment without the need for any drastic adjustments. The following information deals with general properties of renewable or fossil polyethylenes and, of course, some properties of renewable polyethylenes can be different. Most polyethylene resins are thermoplastic but some grades are crosslinkable. Table 10.28 displays some properties of renewable polyethylene and fossil polyethylene for comparison. These results relate to examples only and cannot be generalized nor used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions.

10.7.7 Biobased Ethylene Vinyl Acetate Copolymer Derived from sugarcane this biosourced EVA copolymer (by Braskem) with characteristics such as flexibility, lightness, and resistance targets applications in footwear, automotive, and flexible packaging industries. The resin helps to reduce greenhouse gases (GHG) in the air by capturing and storing CO2 during its production process.

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10.8 Renewable PET, PBT, PEF, PTT Alternatives to Fossil Thermoplastic Polyesters PET and PBT Today some solutions are only partially renewable polymers. Development of renewable PET results from a marketing determination developed by steps:

• In a first step, fossil components are partially replaced by bio-monomers.

• In a second step, fossil components are totally replaced by bio-monomers

• In a third step, PET could be replaced by PEF (polyethylene-furanoate). Another way uses recycled PET (rPET).

10.8.1 Replacement of the Fossil Alcohol by Natural Alcohol First Step: Plant-Based Mono Ethylene Glycol Coca-Cola launches innovative PlantBottle packaging technology based on recyclable PET beverage bottles made from up to 30% plant. Up to 2015, Coca-Cola has sold more than 44 billion PlantBottle packages around the world. Since the package launched in 2009, its use has eliminated the equivalent of almost 428,000 MT of carbon dioxide emissions. In this first step, the renewable PET resin is made with bio-based monoethylene glycol (MEG). To further push plant-based PET in end-use markets, Coca-Cola put together a partnership with Ford Motor, HJ Heinz, Nike and Procter & Gamble, the target being to spur the development and use of plant-based PET material in packaging and fibers. Toyota Tsusho Corp., among others, is also a global supplier of bio-PET resin named GLOBIO. GLOBIO consists of biobased MEG made by plantderived bioethanol, and refers to all bio-PET plastics produced and sold by Toyota Tsusho. Up to 30% is plant derived. Toyota Motor Corporation has announced it plans to make vehicle liner material and other interior surfaces from an ecological PET consisting of

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Table 10.28 Examples of Properties of Renewable and Conventional Polyethylenes. Renewable Polyethylene, Extrusion Grades Biobased material (%)

Mini

HDPE

LLDPE

LDPE

97/96

84/87

95

1

0.8 2.7

0.25 8.1

0.948 0.952

0.916 0.92

0.922 0.924

Physical Properties MFR 190°C, 2.16 kg Density

g/10 min g/cm

3

Mechanical Properties Tensile strength MD

MPa

85

50

17 25

Tensile strength TD

MPa

45

30

17 30

Elongation at break

%

59 740

950/1500

200/1040

Tensile modulus

GPa

0.78 0.87

0.17 0.24

0.26

Dart drop impact

g/F50

245

100 170

60 170

Elmendorf tear strength, MD/TD

gF

58/51

140/520

Optical Properties Haze

%

5 10

Gloss 60°

72 120 HDPE

LLDPE

Injection Grades

Lamination Grades

6 7

2.4 3

0.959

0.919

Physical Properties MFR 190°C, 2.16 kg Density

g/10 min g/cm

3

Mechanical Properties Tensile strength

MPa

25

14 15

Elongation at break

%

.450

475 480

Tensile modulus

GPa

1.035

0.2

Flexural modulus

GPa

0.945

0.180

Charpy notched impact strength

kJ/m

Melt temperature

°C

2

5.2 130 145

130 145

Fossil-Based Polyethylene for Comparison HDPE

LLDPE

LDPE

Physical Properties Density

g/cm3

0.94 0.97

0.915 0.950

0.917 0.940

Shrinkage

%

1.5 4

2 2.5

2 4

Absorption of water

%

0.005 0.01

0.005 0.01

0.005 0.015

Hardness

Shore D

60 70

55 56

40 50

Stress at yield

MPa

25 30

10 30

10 15

Mechanical Properties

(Continued )

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Table 10.28 Examples of Properties of Renewable and Conventional Polyethylenes.—Cont’d Fossil-Based Polyethylene for Comparison HDPE

LLDPE

LDPE

Strain at yield (%)

%

10 15

3 16

Tensile strength

MPa

30 40

25 45

10 20

Elongation at break

%

500 700

300 900

200 600

Tensile modulus (GPa)

GPa

0.500 1.100

0.266 0.525

0.130 0.300

Flexural modulus (GPa)

GPa

0.750 1.575

0.280 0.735

0.245 0.235

Notched impact strength ASTM D256

J/m

20 220

54 NB

No break

HDT B (0.46 MPa)

°C

60 90

40 50

HDT A (1.8 MPa)

°C

44 60

30 40

Vicat softening point A

°C

Continuous use temperature

°C

Glass transition temperature

Thermal Properties

96 118

76 109

80 120

90 110

80 100

°C

2110

2110

2110

Melting temperature

°C

130

122 124

110 120

Minimum service temperature

°C

270 to 2100

270

270

Thermal conductivity

W/m K

0.40 0.50

0.35 0.45

0.32 0.35

Specific heat

cal/g/°C

0.55

0.55

0.55

Coefficient of thermal expansion

25

10

/°C

6 15

10 20

Electrical Properties Volume resistivity

Ω cm

Dielectric constant 24

Loss factor

10

Dielectric strength

kV/mm

Arc resistance

s

1016 1018

1016 1018

1016 1018

2.3

2.3

2.3

2 20

3 4

17 45

16 28 130 160

Fire Behavior Oxygen index

%

UL94 fire rating

,20

,20

,20

HB

HB

HB

HDPE, High-density polyethylene; HDT, heat deflection temperature; LDPE, low-density polyethylene; LLDPE, linear low density polyethylene; MD, machine direction; TD, transverse direction.

70% terephthalic acid and 30% MEG, by weight; bio-PET is made by replacing MEG with a biological raw material derived from sugar cane. Several companies (Toray, Lanxess, Genomatica, BASF) announced they produce partially biobased PBT starting from biobased 1,4-butanediol (BDO). The properties, the quality, and applications of the resulting biobased thermoplastic polyesters are claimed similar to those of conventional petrobased PBT with regard to all tested parameters.

10.8.2 Second Step: Paraxylene for 100% Biopolyester The plastics industry currently uses paraxylene from petroleum as a precursor of phthalic acid. Virent Cy has successfully made paraxylene, named BioFormPX, from 100% renewable plant sugars. When combined with existing PET technology using bio-MEG, it allows companies to offer customers 100% natural, renewable, plant-based

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PET. BP has formed a partnership (in April 2019) with Virent and Johnson Matthey to commercialize this process. University of Massachusetts Amherst has discovered a new, high-yield method of producing paraxylene from the biomass feedstock with an efficient yield of 75%. Gevo, Inc. has announced that it has successfully produced fully renewable and recyclable PET with its potential customer, Toray Industries. Toray employed its existing technology and new technology jointly developed with Gevo, and used Gevo’s paraxylene and commercially available renewable MEG to produce fully renewable PET (all of the carbon in this PET is renewable). Main applications could be those of traditional PET and characteristics should be similar.

10.8.3 The Third Way: Polyethylene-Furanoate Dutch research and technology company Avantium has developed a patented technology YXY to produce 100% biobased PEF bottles. The company has announced an agreement with The Coca-Cola Company to further codevelop Avantium’s YXY technology for producing PEF bottles. Avantium has demonstrated that PEF has some superior properties over PET, including barrier properties (oxygen, carbon dioxide, and water) and ability to withstand heat. The YXY technology makes it possible to produce a 100% biobased and 100% recyclable polyester. Avantium is actively working on the development of PEF bottles for water, soft drinks, fruit juices, alcoholic drinks, food, cosmetic products, soaps, and detergents. Avantium’s researchers claim that PEF bottles outperform PET bottles in some areas, particularly:

• barrier properties • PEF oxygen barrier could be 10 times better than PET.

• PEF carbon dioxide barrier could be 4 (or more) times better than PET.

• PEF water barrier could be 2 times better than PET. That results in longer-lasting carbonated drinks and extended shelf life.

• heat behavior • The Tg of PEF is 86°C compared to 61° C 79°C for PET.

• the melting temperature is about 235°C compared to 240°C 265°C for PET. PEF could replace PET in typical applications like films, fibers and in particular bottles for the packaging of soft drinks, water, alcoholic beverages, fruit juices, sauces, dressings, baby foods and edible oils, personal and homecare applications, cosmetics, detergents, food, and nonfood products. Avantium Renewable Polymers [previously Synvina (https://www.synvina.com/), initially a joint venture BASF/Avantium] was launched for the production of PEF based on furandicarboxylic acid (FDCA) and MEG. Synvina (Avantium Renewable Polymers) claims:

• FDCA is a 100% bio-based monomer and the essential chemical building block for the production of the polymer PEF.

• PEF oxygen barrier could be 10 times better than PET.

• PEF carbon dioxide barrier is 6 10 times better than PET.

• PEF water barrier is twice as good as PET. • The glass transition temperature (Tg) of PEF is 86°C compared to the Tg of PET of 74°C.

• The melting temperature (Tm) of PEF is 235°C compared to the Tm of PET of 265°C.

10.8.4 Recycled Polyethylene Terephthalate Pepsico (https://www.pepsico.com/) drives a policy of PET recycling adapted to local conditions, technical possibilities and food contact regulations (see also Chapter 9: Recycling of Plastics, Advantages and Limitation of Use). For example, Pepsico claims:

• They were the first and only major consumer packaged goods company to incorporate up to 10% postconsumer recycled content into its PET plastic, beginning in 2004. rPET comes from plastic that has already been used for packaging, such as plastic bottles. Prior to being transformed into a new plastic bottle, the plastic is sorted, cleaned, and tested in accordance with food safety standards.

TRANSITION

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• In France, Pepsico incorporated 2268000 kg of rPET, achieving up to 50% recycled content in individual product lines.

• In Germany, Pepsico achieved its 2015 goal of utilizing 25% rPET in approved bottles. In 2013 5000 t of rPET were used.

• In Canada, 7UP bottles were the first 100% postconsumer content bottles for a carbonated soft drink.

• Pepsico Brazil’s is now utilizing 2 L PET bottles with 100% rPET for Teem carbonated soft drinks.

10.8.5 PolyTrimethylene Terephthalate Sorona (by DuPont), a thermoplastic PTT, contains up to 37% renewable material from nonfood biomass thanks to a key intermediate called Susterra, a renewably sourced propanediol made from corn sugar. DuPont claims PTT has performance (see Table 10.30) similar to conventional PBT plastics delivering molding characteristics, strength, stiffness, dimensional stability, and finishing qualities comparable to PBT. RTP markets glass fiber reinforced, FR, and lubricated grades (e.g., 26% biocontent). Aimed applications include automotive parts, furniture, mobile phone housings, and industrial and consumer products.

10.8.6 Partially Renewable Thermoplastic Elastomer Ester Among others, DuPont Engineering Polymers and DSM have launched Hytrel RS and Arnitel ECO thermoplastic elastomers providing characteristics (see Table 10.31) similar to those of fossil thermoplastic elastomer esters, while offering a more environmentfriendly solution than products that are entirely petroleum-based. Hytrel RS has been developed using a renewably sourced polyol derived from corn sugar or others derived from nonfood biomass. It contains between 20% and 60% renewably sourced material. One of the first uses worldwide of DuPont Hytrel RS thermoplastic elastomer in sporting goods applications is the collar of the Salomon “Ghost” freerider alpine ski-boot. DSM intends to use biobased BDO made with Genomatica’s process in Arnitel products as soon

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517

as it is readily available commercially. The introduction of biobased BDO could increase the biobased content up to 73% for best cases.

10.8.7 Polybutylene Succinate PBS is an aliphatic polyester produced by polymerization of succinic acid and BDO. Monomers can be derived from petroleum-based systems or starting from renewable raw materials. PBS may become degradable in compost, wet soil, fresh water, seawater, and activated sludge where microorganisms are present. It will decompose completely into water and carbon dioxide. See property Table 10.32. Polybutylene succinate-adipate (PBSA), PBS-coadipate, is a copolymer. Trade name examples: Bionolle, Biosuccinium, Enpol G4560. Examples of biopolyesters and precursors producers: Arctic Biomaterials Oy

https://abmcomposite. com/wp-content/ uploads/Technical-DataSheet-ArcBiox-BGF20G.pdf

BioAmber

http://www.bio-amber. com/bioamber/en/

DSM

http://www.dsm.com/

Hexing Chemical

http://www.hexinggroup. com/en/

IRE Chemical

http://irechem.en. ecplaza.net/

Mitsubishi Chemical Corp. MCC

http://www. mitsubishichem-hd.co. jp/english/group/charter/

Reverdia (JV DSM and Roquette)

http://www.reverdia. com/

Showa Denko Group

http://www.showadenko.com/

SK Chemicals

http://www.skchemicals. com/en/

Succinity (BASFCorbion JV)

http://www.succinity. com/

Synvina (previously BASF/Avantium JV)

https://www.synvina. com/

Toray

https://www.toray.com/ products/

518

10.8.8 Property Examples of PET, PBT, PTT, TPEE, PBS

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

most polyamide producers including, without claiming to be exhaustive:

Table 10.29 displays some examples of properties of thermoplastic polyesters based on renewable (or not) feedstock, neat, modified with undefined additives. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Other grades are marketed.

• Arkema markets Rilsan PA11, 100% bio-

As previously said, renewable polyesters have properties and characteristics of the same order as homologous fossil polyesters and can be processed by clients’ equipment without the need for any drastic adjustments. The previous information deals with general properties of fossil polyesters and, of course, some properties of renewable grades can be different.

• BASF proposes the “MB” (mass balance)

Table 10.30 displays examples of characteristics of PTT. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions. Table 10.31 displays examples of characteristics of three renewable sourced Hytrel RS. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions. Table 10.32 displays examples of characteristics of renewable or fossil PBS and PBSA (PBS-adipate). These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions. PBS, PBSA, and their blends target applications in agriculture, fishery, forestry, construction, and other industrial fields such as mulch film, foam and food or nonfood packaging, utensils, disposable cups, and flushable hygiene products. PBS is also proposed as a nonmigrant plasticizer for PVC.

10.9 Renewable Polyamides “Renewable”, “green”, “bio”, or “eco” polyamides are high-performance polymers developed by

sourced polymers and Rilsan S a PA610 partially sourced from castor oil. Arkema also develops Rilsan T PA10.10 a new biosourced polyamide 10.10 processed from castor oil and Rilsan HT a polyphthalamide (PPA) biopolymer. materials partially or totally derived from biobased feedstock and thus helping to save fossil raw materials and reduce greenhouse gas emissions. For example, 100% of the fossil raw materials needed to make Ultramid B3EG6 MB are replaced with renewable raw materials at the beginning of the production process. The MB plastic is claimed to be identical to its fossil counterpart in terms of formulation and quality. (The method is also used for polyurethane.)

• BASF develops its Ultramid S3K Balance PA610 containing more than 60% of renewable materials based on sebacic acid derived from castor oil.

• Cathay markets Terryl (www.cathaybiotech. com/en/products/terryl) PA56, 510, 511, 512, 513, 514 containing 26% 100% renewable content.

• EMS-GRIVORY has launched the GreenLine series of polyamides including PPAs, amorphous transparent PA, PA1010, and PA610 that provide a wide spectrum of special properties from very flexible to extremely rigid, from high heat or hydrolysis resistant to transparent. The biobased content of GreenLine products varies from about 50% up to 99% depending on the type of polymer, when determined according to ASTM D 6866-12 and expressed in percentage of total carbon.

• Evonik proposes its VESTAMID Terra line including: • VESTAMID TERRA HS (PA610) is 62% based on biorenewables and has a carbon footprint of 4.6 kg CO2 eq./kg • VESTAMID TERRA DS (PA1010) is 100% based on biorenewables and has a carbon footprint of 4.0 kg CO2 eq./kg

Table 10.29 Fossil Polyesters: Examples of Properties. Amorphous PET

PET

PBT

Minimum

Maximum

Minimum

Maximum

Minimum

Maximum

Density (g/cm3)

1.3

1.4

1.3

1.4

1.3

1.4

Shrinkage (%)

0.2

1.0

0.2

3.0

0.5

2.2

Absorption of water (%)

0.1

0.2

0.1

0.2

0.1

0.2

Shore hardness (D)

85

95

90

95

Rockwell hardness (M)

50

100

70

80

Miscellaneous Properties

Mechanical Properties

Tensile strength (MPa)

40

40

45

70

40

50

Elongation at break (%)

250

300

30

70

50

200

Tensile modulus (GPa)

2.2

2.2

2.8

3.5

2

3

Flexural modulus (GPa)

2.2

2.2

2.8

3.5

2

3

Notched impact strength ASTM D256 (J/m)

10

35

15

40

35

55

HDT B (0.46 MPa) (°C)

72

72

75

115

115

150

HDT A (1.8 MPa) (°C)

70

70

65

80

50

85

Continuous use temperature (°C)

80

140

80

140

80

140

220

265

220

265

Thermal Properties

Melting temperature (°C) Brittle point (°C)

240

240

240

240

240

240

Thermal conductivity (W/m K)

0.24

0.24

0.29

0.29

0.21

0.21

Specific heat (cal/g/°C)

0.31

0.31

0.31

0.31

0.32

0.32

Coefficient of thermal expansion (10 5/°C)

8

8

6

8

6

10

1016

1016

1016

1016

Electrical Properties Volume resistivity (Ω cm) Dielectric constant Loss factor (10

24

)

3

4

3

4

3

3

20

300

20

200

10

200 (Continued )

Table 10.29 Fossil Polyesters: Examples of Properties.—Cont’d Amorphous PET

PET

PBT

Minimum

Maximum

Minimum

Maximum

Minimum

Maximum

Dielectric strength (kV/mm)

45

45

60

60

45

60

Arc resistance (s)

75

125

75

125 21

24

HB

HB

Fire Behavior Oxygen index (%) UL94 fire rating

HB

HB

PET 30% GF

HB

HB

PET 30% GF Impact Modified

PBT 30% GF

Miscellaneous Properties Density (g/cm3)

1.5

1.6

1.5

1.5

1.5

1.6

Shrinkage (%)

0.2

1

0.2

0.9

0.2

1

Absorption of water (%)

0.1

0.1

0.1

0.3

0.1

0.1

Shore hardness (D)

95

.95

90

90

95

.95

Rockwell hardness (M)

90

100

62

62

90

95

Stress at yield (MPa)

140

160

100

110

135

140

Strain at yield (%)

2

7

6

6

2

3

Tensile strength (MPa)

140

160

100

110

135

140

Elongation at break (%)

2

7

6

6

2

3

Tensile modulus (GPa)

9

12

7

9

9

11.5

Flexural modulus (GPa)

9

12

7

9

9

11.5

Notched impact strength ASTM D256 (J/m)

80

110

150

230

50

90

HDT B (0.46 MPa) (°C)

225

250

245

245

215

250

HDT A (1.8 MPa) (°C)

220

240

220

220

195

225

Continuous use temperature (°C)

100

140

100

140

100

140

Mechanical Properties

Thermal Properties

(Continued )

Table 10.29 Fossil Polyesters: Examples of Properties.—Cont’d PET 30% GF

PET 30% GF Impact Modified

PBT 30% GF

245

220

265

Melting temperature (°C)

245

265

Thermal conductivity (W/m K)

0.33

0.33

0.24

0.24

Specific heat (cal/g/°C)

0.24

0.24

0.28

0.28

Coefficient of thermal expansion (1025/°C)

2

5

2

5

1016

1016

1.5

255

2

Electrical Properties Volume resistivity (Ω cm) Dielectric constant Loss factor (10

24

)

Dielectric strength (kV/mm)

3

4

3

4

20

160

20

120

55

55

50

50

19

20

HB

HB

Fire Behavior Oxygen index (%) UL94 fire rating

HB

HB

HB

HB

General chemical properties are subject to the compatibility of the fillers and reinforcements with the ambient conditions. If the fillers are well adapted, the chemical properties are the same for filled and neat polymers Light

UV stabilizers are needed

Weak acids

Good to limited behavior

Strong acids

Unsatisfactory

Weak bases

Good to limited behavior

Strong bases

Limited to unsatisfactory behavior

Solvents

Chemical resistance is generally good to limited at room temperature versus dilute bases and weak acids, oils, greases, aliphatic hydrocarbons, certain alcohols Limited to unsatisfactory resistance to aromatic and halogenated hydrocarbons. Polyesters are attacked by organic and mineral acids, oxidizing agents, concentrated bases, phenols

Food contact

Possible for special grades

GF, Glass fiber; HDT, heat deflection temperature; PBT, poly(butylene terephthalate); PET, polyethylene terephthalate.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.30 Examples of Characteristics of PolyTrimethyleneTerephthalate DuPont Glass fiber

%

Renewable material

% 3

Sorona

Sorona 3030GV BK001

None

30

29 35

25 1.56

Density

g/cm

1.05 1.32

Molding shrinkage

%

1.3 1.7

Mechanical Properties Yield or break stress

MPa

35 60

142

Yield strain

%

5 5.5

2

Strain at break

%

15

2

Tensile modulus

GPa

1.6 2.4

10.6

Flexural modulus

GPa

1.6 2.4 2

kJ/m

4 22

7

Deflection temperature (0.45 MPa)

°C

75 125

226

Deflection temperature (1.80 MPa)

°C

53 60

205

Melting temperature

°C

228

227

HB

HB

Notched charpy impact strength

Thermal Properties

Fire Behavior UL94 fire rating (0.8 mm) Oxygen index

%

21

Ωm

.E13

Electrical Properties Volume resistivity Relative permittivity Dielectric strength Dissipation factor

4.1 4.3 kV/mm

32

24

15 155

10

RTP Company Glass fiber

%

Renewable material

%

32

3

PTFE Lubricated GF

Nonhalogen FR GF Reinforced

Yes

Yes

20

19

Density

g/cm

1.69

1.59

Molding shrinkage

%

0.3

0.3

Tensile stress

MPa

124

103

Elongation at break

%

2

1 2

Flexural modulus

GPa

9.65

11.7

Notched izod impact strength

J/m

80

374

Deflection temperature (0.45 MPa)

°C

218

218

Deflection temperature (1.80 MPa)

°C

204

204

HB

V0

Mechanical Properties

Thermal Properties

Fire Behavior UL94 fire rating (0.8 mm) FR, Flame-retardant; GF, glass fiber; PTFE, polytetrafluoroethylene.

Table 10.31 Examples of Characteristics of Renewably Sourced Hytrel RS. Physical Properties

Hytrel RS 40F3 NC010

Hytrel RS 40F5 NC010

Hytrel RS R4275 BK316

Renewable ingredients (%)

.50

.50

Unknown

Density (g/cm )

1.11

1.11

1.17

Linear mold shrinkage, flow (%)

0.8 0.9

0.9 1

1.4

Linear mold shrinkage, transverse (%)

0.6 0.7

0.7 0.8

1.9

Melt flow (g/10 min, 2.16 kg, 220°C)

20

9

Hardness, Shore D

33 37

33 37

50

Tensile strength at break (MPa)

26

25

35

Tensile stress (MPa) at strain 5.00%

2.1

2.1

6.4

Tensile stress (MPa) at strain 10.00%

3.3

3.5

10

Tensile stress (MPa) at strain 50%

6.56

6.7

18

Elongation at break (%)

$ 300%

$ 300%

$ 300%

Tensile modulus (GPa)

0.045

0.045

0.15

Flexural modulus (GPa)

0.05

0.05

Charpy impact unnotched (20°C)

NB

NB

NB

Charpy impact unnotched (230°C)

NB

NB

NB

Charpy impact, notched (J/cm2 at 20°C)

NB

NB

NB

Charpy impact, notched (J/cm at 230°C)

NB

NB

16

Charpy impact, notched (J/cm at 240°C)

NB

NB

4.5

Tear strength (kN/m)

97

101

140

CTE, linear, parallel to flow (μm/m °C)

210

210

180

CTE, linear, transverse to flow (μm/m °C)

200

200

190

Melting point (°C)

190

190

190

Brittleness temperature (°C)

290

295

270

3

Mechanical Properties

2 2

Thermal Properties

230

Glass transition temperature, Tg (°C) Flammability, UL94, thickness (1.50 mm)

HB

HB

Oxygen index (%)

20

20

HB

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.32 Examples of Characteristics of Polybutylene Succinate (PBS) and Polybutylene SuccinateAdipate (PBSA). PBS

PBSA

Density

1.26

1.23

Glass transition temperature (°C)

232 to 218

245 to 234

Melting point (°C)

112 114

92 96

Heat distortion temperature (°C)

97

69

Tensile strength (MPa)

34

19

Elongation at break (%)

560

800

Izod impact strength (J/m)

300

.400

Degree of crystallinity (%)

35 45

20 35

• VESTAMID TERRA DD (PA1012) is 45% 100% based on bi-renewables and has a carbon footprint of 5.2 kg CO2 eq./kg

• Royal DSM N.V. introduced EcoPaXX and some ForTii grades, biobased polyamides 30% 60% derived from renewable resources. DSM uses castor beans as the basis for the C10 chemistry. The grades have a biocontent ranging from 10% to 25% by weight on a compound basis.

• Solvay biosourced materials TECHNYL eXten PA6.10 polyamides; Kalix 2000 Series based on biosourced PA610.

• Suzhou HiPro Polymers develops its Hiprolon containing 40% 100% biorenewable resource. Biobased high performance polyamides include PA610, PA612, PA1010, PA1012, PA11. In addition to a lower consumption of nonrenewable resources, the carbon footprint is generally reduced but prices are higher. Lastly note renewable muconic acid and its derivatives could replace nonsustainable chemicals used in the production of nylons. The muconic acid is a C6 dicarboxylic acid with two double bonds that can be catalytically converted into adipic acid, the precursor to nylon synthesis.

10.9.1 Polyamides With Long Hydrocarbon Segments: PA11, 1010, 1012 Compared to PA6 and PA66, PA11 the oldest and best-known polyamides, PA10.10 and

PA10.12 are generally more flexible, have better behavior at low temperature, and are adapted to extreme climates, are less sensitive to water and moisture, but are more expensive. Their market share is only a few percent of the total polyamide consumption. PA11 and other PA with long hydrocarbon segments generally have good stress-cracking resistance, a low density, and a high-abrasion resistance. The heat behavior can be increased through formulation and sometimes by radiation crosslinking. Technically speaking, PA1010 occupies a position between the long-chain polyamides such as PA11 and the standard polyamides PA6 and PA66, which have a shorter chain length. PA1010 is semicrystalline, which is the reason for its high mechanical resistance and chemical stability. It absorbs only little water. As a result, its mechanical properties vary little when exposed to changing environmental humidity, and the material features a high dimensional stability. Despite its crystallinity, PA1010 can be used to manufacture films with good transparency. Compounds based on VESTAMID Terra DS have high melting points. In turn, HDTs are high, which can be advantageous for some applications. Table 10.33 displays examples of characteristics of long chain renewable polyamides. Humidity is not defined what is important for some characteristics. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions.

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Table 10.33 Examples of Properties of Neat Long Chain Polyamides. PA11 Minimum

PA10.12 Maximum

PA1010

Minimum

Maximum

Biobased content ASTM 6866 (% of C)

45

100

100

Global warming potential (kg CO2 eq/kg)

3

5.8

2.8

4

1.05

1.05

1.07

Miscellaneous Properties Density (g/cm3)

1.01

1.06

1.03

Absorption of water (%)

0.2

0.4

1.6

1.8

50

65

40

54

5

5

Mechanical Properties Stress at yield (MPa) Strain at yield (%) Tensile strength (MPa)

50

65

Elongation at break (%)

250

400

.50

.50

Tensile modulus (GPa)

0.9

1.2

1.3

1.7

Flexural modulus (GPa)

0.9

1.2

Notched impact strength ASTM D256 (J/m)

70

NB

HDT B (0.46 MPa) (°C)

130

155

HDT A (1.8 MPa) (°C)

50

60

Continuous use temperature (°C)

80

150

Melting temperature (°C)

175

190

190

200

Brittle point (°C)

2120

270

Volume resistivity (Ω cm)

1014

1014

Dielectric constant

3

9

200

2000

25

30

HB

HB

Thermal Properties

Electrical Properties

Loss factor (10

24

)

Dielectric strength (kV/ mm) Fire Behavior UL94 fire rating Food contact: possible for special grades HDT, Heat deflection temperature.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

526

10.9.2 Polyamides Alternating Long and Short Hydrocarbon Segments: PA610, 510, 512, 514, 410 PA610 and other PA alternating long and short hydrocarbon segments have intermediate properties between PA66 and PA11. Generally speaking, concerning sensitivity to water and moisture they are nearer to PA11, and for rigidity and mechanical performances they are nearer to PA66. The number of producers and grades are limited. The continuous-use temperatures in an unstressed state are generally estimated from 80°C up to 150°C if softening temperatures are higher. The UL temperature indices of specific grades can be 65°C 120°C for electrical and mechanical properties including impact. Service temperatures can be lower under loading because of modulus decay, strain, creep, relaxation, among others. For example, HDTs under 1.8 MPa for neat PA610 or other PA alternating long and short hydrocarbon segments are in a range from about 60°C up to 90°C. Compared to PA6 or 66, polyamides 610 and other PA alternating long and short hydrocarbon segments absorb less water and are less sensitive to it. Special grades are marketed for their hydrolysis resistance. Chemical resistance is generally good to limited at room temperature versus dilute bases and weak acids, oils, greases, hydrocarbons, certain chlorinated solvents, cosmetics, aldehydes, some alcohols, ketones, esters, and glycols. Polyamides are attacked by organic and mineral acids, oxidizing agents, concentrated bases, and phenols. Trade name examples: Suitable grades of EcoPaXX, Grilamid, Grivory, Ultramid Balance, Vestamid Terra, Zytel, and so forth. Table 10.34 displays examples of characteristics of renewable polyamides alternating short and long hydrocarbon segments. Humidity is not defined what is important for some characteristics. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions

10.9.3 Polyamides With Short Hydrocarbon Segments: PA56 PA56 properties are more or less similar to those of PA66 or PA6. There is only one producer and the number of grades is limited. The mechanical properties are generally good with high elongations at break but much more limited strains at yield. Moduli and hardnesses are fair to high according to the moisture content. Polyamides 56 absorb water and are sensitive to it to a greater or lesser degree. Producer example: Cathay Industrial Biotech (http://www.cathaybiotech.com/en/products/terryl). Table 10.35 displays examples of characteristics of renewable polyamides with short hydrocarbon segments. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions.

10.9.4 Amorphous Transparent Renewable Polyamides Amorphous transparent renewable polyamides combine transparency and general properties of polyamides, possibly including:

• • • • • •

transparency and natural color good chemical resistance gloss and scratch resistance low moisture absorption for a PA good mechanical behavior high heat distortion temperature

Table 10.36 displays examples of characteristics of renewable transparent polyamides. Humidity is not defined what is important for some characteristics. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions

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Table 10.34 Examples of Properties of Polyamides Alternating Long and Short Hydrocarbon Segments. 610

410

510 514

56 70

26 100

Property

Unit

Neat

Biobased content ASTM 6866 (% of C)

%

63

Global warming potential

kg CO2 eq/ kg

2 4.6

%

0.4 3.3

1.07 2

0.3 0.5

1.06 1.1

1.05 1.09

1.06

35 85

42 60

Physical Properties Water absorption at RT Density

g/cm

3

Mechanical Properties Shore hardness

D

70 85

Tensile stress at yield

MPa

50 70

Tensile strength

MPa

45 90

Tensile strain at yield

%

5

5 20

Tensile strain at break

%

.50

16 . 50

$ 100

Tensile modulus

GPa

1 2.1

0.9 3.1

1.5 2

Notched impact strength ASTM D256

J/m

Charpy impact strength (23°C) Charpy impact strength (230°C) Charpy notched (23°C) Charpy impact strength (230°C)

30 80

kJ/m

2

NB

kJ/m

2

NB

kJ/m

2

6 7

kJ/m

2

6

NB 5 75

7 8

Thermal Properties HDT B (0.46 MPa)

°C

160 175

140 175

HDT A (1.8 MPa)

°C

75 85

75 77

6 14

7 14 250

25

/°C

Coefficient of thermal expansion

10

Melting temperature

°C

210 223

Glass transition temperature

°C

48

VICAT softening temperature, Method B (50 N)

°C

196

Ω cm

1012 1015

50 60 206 218

Electrical Properties Volume resistivity Dielectric constant

3 6 24

70 900

Loss factor

10

Dielectric strength

kV/mm

16 26

%

23 27

Fire Behavior Oxygen index UL94 fire rating HDT, Heat deflection temperature; NB, no break.

HB-V2

1013

528

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.35 Examples of Properties of PA56 (Cathay). Physical Properties

Dry

Cond. 50%RH

Renewable

26 100

26 100

Specific gravity

1.14

1.14

Tensile strength, yield (MPa)

81

45

Elongation at yield (%)

5

$ 50

Tensile modulus (GPa)

3

1.2

Flexural strength (MPa)

108

35

2.6

0.8

Izod impact, notched (kJ/m )

8.5

NB

Izod impact, unnotched (kJ/m2 )

NB

NB

Charpy impact, notched (J/cm2 )

0.8

NB

Mechanical Properties

Flexural modulus (GPa) 2

Thermal Properties Melting point (°C)

254

HDT at 0.46 MPa (°C)

205

HDT at 1.8 MPa (°C)

67.5

Fire Behavior Oxygen index (%)

34 35

Flammability, UL94

V2

HDT, Heat deflection temperature.

10.9.5 Polyphthalamide The biobased content of renewable products varies from about 50% up to 99% depending on the type of polymer. Some renewable PPAs have main features of PPA, such as:

• heat resistance and high peak temperature • good mechanical behavior • resistance to chemicals and hydrolysis. Certain grades are claimed to perform as well as polyphenylene sulfide at operating temperatures up to 120°C and others are suitable for lead-free soldering. Table 10.37 displays examples of characteristics of renewable or fossil PPA. Humidity is not defined what is important for some characteristics. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions.

10.9.6 Renewable Polyether Block Amides Polyether block amides (PEBAs) are block copolymers of a polyether for the soft segments and a polyamide for the rigid segments. The properties, including hardness, which is often used for the denomination of the grades, very strongly as functions of the nature and length of the flexible and rigid segment, molecular weight, ratio of rigid-to-flexible segments. PEBAs are appreciated for their high-mechanical performances; tenacity; good abrasion resistance; good flex fatigue resistance; broad range of hardnesses including Shore D scale and upper Shore A scale values; good low-temperature behavior; low density; fair thermal resistance for suitable grades; ease of waste recycling; broad possibilities of coloring; electric insulation; and US Pharmacopoeia class VI clearance for suitable grades. PEBAs are handicapped by a lower elasticity than conventional rubbers, the more so the greater the hardness; certain risks of creep, relaxation, and permanent set, the more so the higher the

Table 10.36 Examples of Characteristics of Renewable Transparent Polyamides. Minimum

Maximum

Density (g/cm )

1.00

1.12

Shrinkage (%)

0.4

1

Absorption of water (%)

0.4

1.4

Shore hardness (D)

80

85

Rockwell hardness (M)

30

50

Stress at yield (MPa)

60

75

Strain at yield (%)

7

10

Tensile strength (MPa)

50

105

Elongation at break (%)

50

300

Tensile modulus (GPa)

1.4

2.3

Flexural modulus (GPa)

1.6

2.2

Notched impact strength ASTM D256 (J/m)

60

150

HDT B (0.46 MPa) (°C)

95

165

HDT A (1.8 MPa) (°C)

75

135

CUT (°C)

80

100

Melting temperature (°C)

250

250

Glass transition temperature (°C)

97

155

Thermal conductivity (W/m K)

0.21

0.23

0.33

0.34

7

9

3

Specific heat (cal/g/°C) Coefficient of thermal expansion (10

25

/°C)

13

1015

Volume resistivity (Ω cm)

10

Dielectric constant

3

4

50

325

Dielectric strength (kV/mm)

25

50

Oxygen index (%)

26

26

UL94 fire rating

V2

V2

Loss factor (10

24

)

CUT, Continuous use temperature; HDT, heat deflection temperature.

Table 10.37 Examples of Characteristics of Polyphthalamide. Minimum

Maximum

Density (g/cm )

1.11

1.15

Shrinkage (%)

1.3

2

Absorption of water (%)

0.5

0.8

Tensile strength (MPa)

62

76

Elongation at break (%)

28

30

Tensile modulus (GPa)

1.9

2.6

Flexural modulus (GPa)

2.2

2.6

Notched impact strength ASTM D256 (J/m)

15

1070

HDT A (1.8 MPa) (°C)

85

120

9

9.5

3

Coefficient of thermal expansion (10 HDT, Heat deflection temperature.

25

/°C)

530

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

Table 10.38 Renewable Polyether Block Amide: Examples of Properties. Shore Hardness (D)

22

25

40

65

1.01

1.02

1.03

1.03

Shrinkage (%)

0.6

0.7

1.5

Absorption of water (%)

1.3

1 1.4

0.7

3

Density (g/cm )

Mechanical Properties Tensile strength (MPa)

34

28

Elongation at break (%)

$ 50

$ 50

$ 50

$ 50

Tensile modulus (GPa)

0.015

0.04

0.075

0.56

Flexural modulus (GPa)

0.04

Notched impact strength ASTM D256 (J/m) at 20°C

NB

NB

NB

NB

Notched impact strength (J/m) at 20°C

NB

NB

NB

NB

Melting point (°C)

136

135

148

186

VST 50°C/h 50 N (°C)

62

81

121

175

Thermal Properties

NB, No break.

temperature; high cost; risks of hydrolysis; risks of UV degradation, but special grades are marketed; lack of soft grades; inherent flammability, but FR grades are marketed; and sensitivity to certain chemicals. Some producers such as Arkema have developed, via proprietary technologies, new ranges of sustainable PEBA made from raw materials derived from renewable sources resulting in innovative Rnew, Bio, or Eco PEBA families with properties close to those of standard PEBA product families. PEBAs target technical applications in various sectors such as medical, automotive, E&E, industry, consumer goods, and packaging for various molded and extruded technical goods, soft-touch overmolding, grips, and so forth. The UL temperature indices of specific grades can be about:

• 110°C for the electrical properties alone • 85°C up to 95°C for the electrical and mechanical properties, excluding impact strength

• 85°C up to 95°C for the electrical and mechan-

because of modulus decay, strain, creep, relaxation, and so forth. Chemical resistance varies widely with hardness and, generally, for homologous series, increases with it. PEBAs inherently burn easily but FR grades are proposed. Trade name examples: Pebax RNew.

10.9.6.1 Property Tables Table 10.38 displays examples of characteristics of renewable PEBA. Humidity is not defined what is important for some characteristics. These results relate to examples only and cannot be generalized. Data cannot be used for design purposes. These general indications should be verified by consultation with the producer of the selected grades and by tests under operating conditions.

10.10 Renewable Polyurethanes Renewable thermoplastic and thermosetting PUR generally include bio-polyols and synthetic isocyanates but renewable isocyanates are emerging.

ical properties, including impact strength The continuous use temperatures in an unstressed state are sometimes estimated up to 130° C. Service temperatures are lower under loading

10.10.1 Natural and Renewable Oil Polyols Natural oil polyols (NOPs) or bio-polyols are derived from diverse vegetable oils by several

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different techniques, which lead to various properties. Most NOPs are based on natural castor oil, soybean oil, and linseed oil. Market studies (Grand View Research, Transparency market, etc.) anticipate a global market in the order of near 3 million tons and US$7 8 billion by 2020. For example some companies, trademarks and websites include without claiming to be exhaustive:

• BASF: Lupranol: BALANCE: https://www. basf.com/us/en/company/sustainability/management-and-instruments/quantifying-sustainability/eco-efficiency-analysis/examples/lupranol-balance-50.html

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performance_products/Applications/itemrenderer?p_rendertitle 5 no&p_renderdate 5 yes&p_renderteaser 5 yes&p_item_id 5 230138646&p_item_caid 5 1143

• IFS Chemicals (subsidiary of Huntsman Corp): Enviropol polyols: https://ifs-group.com/aboutus/envirofoam-sustain/

• Perstorp offers three essential base polyols— Penta, TMP, Neo—in renewable grades, under the names Voxtar (Penta), Evyron (TMP), and Neeture (Neo). All are claimed certified by third-party ISCC and come with a proof of https://www.perstorp.com/en/ sustainability: products/proenvironment_polyols/

• BASF: Sovermol: https://www.basf.com/tw/en/

• Polygreen: Polygreen polyols: https://www.

products-and-industries/paint-coating-industry/ sovermol.html

• Vertellus: Polycin polyols: http://www.vertel-

• Biobased Technologies: Agrol polyols: http:// www.biobased.net/our-products.html#agrolpolyols

• Cardolite, CNSL-based polyols: https://www. cardolite.com/products/polyols_diols/

• Cargill: BiOH polyols: https://www.cargill. com/bioindustrial/what-are-bioh-polyols

• Croda: Priplast and Pripol polyols: https://www. crodacoatingsandpolymers.com/en-gb/productsand-applications/elastomers-and-foams

polygreen.com.my/advantages lus.com/products/case/polycin-polyols

• Vithal Castor Polyols Pvt. Ltd: bio-polyols: https://www.jayantagro.com/product-category/ polymers-and-plastics/9/ Often, biosourced polyols partly replace petroleum-based components. The used level can vary from less than 20% to more than 60% and even 100% of the fossil polyols according to the targeted properties and the environmental requirements.

• Dow: Renuva polyols: http://msdssearch.dow. com/PublishedLiteratureDOWCOM/dh_009d/ 0901b8038009d9da.pdf?filepath 5 renuva/pdf

• DuPont: Cerenol renewable polyols: http:// www.duponttateandlyle.com/news_060407

• Elastogran (BASF): Lupranol BALANCE: https://www.basf.com/us/en/company/sustainability/management-and-instruments/quantifying-sustainability/eco-efficiency-analysis/ examples/lupranol-balance-50.html

• Emery: EMEROX Renewable Polyols and INFIGREEN Recycle Content Polyols (made from recycled polyurethane scrap foam): http://www.emeryoleo.com/ Eco_Friendly_Polyols.php

• Exaphen: Exaphen-polyols: http://elmira.co.uk/ exaphen-polyols-1/

• Huntsman:

JEFFADD Bio-Based http://www.huntsman.com/

Polyol:

10.10.2 CO2-Containing Polyols One way to enhancing sustainability is the sequestration of CO2 by using it as building blocks in polymers. Some examples are quoted without claiming to be exhaustive: Covestro (http://www.covestro.com/en/), formerly Bayer MaterialScience, offers a range of cardyon branded polyols based on CO2 technology including CO2 capture, treatment and adaptation to use in all kinds of PUR and CAS applications. This turns a waste greenhouse gas, CO2, into a useful raw material that serves as a building block. The use of CO2 in polyurethane production benefits the environment by reducing the overall carbon footprint and establishing an alternative carbon source beyond fossil hydrocarbons and biobased raw materials. Covestro claims those polyols have at least the same high level of quality as conventionally manufactured materials and a more sustainable impact.

532

Covestro also launched a new series of thermoplastic PUR (TPUs) containing polyether carbonate. For example, Desmopan 37385A has a hardness of 85 Shore A. Its mechanical properties are at least at the level of conventional TPU grades of similar hardness, and even exceed some of them. The tensile strength is about 36 MPa with an elongation at break reaching 660%. This plastic is designed for extrusion, but is also suitable for injection molding. Repsol (https://www.repsol.com/en/energy-andinnovation/a-better-world/transforming-co2/index. cshtml) has launched the NEOSPOL PROJECT for the development of polymers such as polycarbonate (PC) polyols that incorporate high levels of CO2 in their chemical structure. Novomer’s PC polyol technology platform (https://www.novomer.com/novomer-announcessuccessful-commercial-scale-trials-converge% C2%AE-polyols-rigid-foams) uses a proprietary catalyst to combine waste CO2 with commodity epoxides to produce polyols which are up to 50% CO2 by weight. Novomer claims these polyols enhance the sustainability and economics of polyurethane products in a wide range of end-use applications. Succinity (http://www.succinity.com/), a 50 50 joint-venture of BASF and Corbion produces biobased succinic acid suitable for polyurethane production. The new process combines high efficiency with the use of renewable raw materials and the fixation of the greenhouse gas carbon dioxide (CO2) in the production of succinic acid. Hauenstein et al. (2016) describe completely biobased poly(limonene carbonate), which can be synthesized by copolymerization of limonene oxide (derived from limonene, which is found in orange peel) and CO2. Depending on the conditions, this may lead to hard thermoplastic polymer or soft rubberlike product.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

food production. Applications are developing in coatings, adhesives and others. Bayhydur eco 7190 is a ionically modified (sulfonic acid) crosslinker for 2K WB coatings containing 68% renewable carbon. Mitsui Chemicals, Inc. has launched STABiO, 1,5-PDI 70% biobased. Claimed properties include:

• High reactivity compared to 1,6-hexamethylene diisocyanate

• Improved gloss and improved chemical and abrasion resistance of paints and adhesives

• Nonyellowing • 70% biobased. • Uses in automotive paints, plastic paints, adhesives, etc. Novomer is developing Biocyanate isocyanates. These plant-based or renewable isocyanates are produced through a novel route that does not require environmentally dangerous phosgene.

10.10.4 Applications Global biobased PUR market was about 1500 1600 t in 2013/2014, that it to say in the order of 1/10,000 of the PUR total demand. In addition it must be remarked that bio-PUR have biobased contents ranging from 20% to 70% depending on the type of biobased feedstock use for manufacturing polyols.

10.10.4.1 Biopolyurethane Foams The NOP level can vary from less than 20% up to more than 60% of the polyols according to the targeted properties. For example:

10.10.3 Bioisocyanate Crosslinker for Polyurethanes

• Ford Motor Company uses soy oil in the seats,

For an “all biobased” polyurethane, bioisocyanate crosslinkers are needed to react with biopolyols. That way is less advanced but Covestro (formerly Bayer MaterialScience) is showcasing a milestone in this field: Pentamethylene diisocyanate (PDI)—Desmodur eco N 7300—is commercialized with 70% of the carbon content coming from biomass without generating any direct competition for

• NOPs are also found in spray-on polyurethane

headrests, armrests, soundproofing of several car models. foam insulation for buildings and in polyurethane slab foam used to make conventional mattresses.

• CosyPUR BALANCE by BASF is a viscoelastic and supersoft system based on renewable raw materials.

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• Lupranol BALANCE: BASF provides an environment-friendly solution for flexible slabstock foam. Lupranol BALANCE is a NOP from the castor-oil plant and, according to BASF, can be used as a 100% drop-in for any other conventional slab polyol.

• Pacific BioFoam by Malama Composites (https://www.cmtc.com/made-in-california-profile/malama-composites-inc) is a pour rigid foam with high biocontent using water as blowing agent. Targeted industrial applications include insulated packaging, consumer appliances, and automotive applications, moldings, casting, and formwork.

• TSE markets EcoSpray Bio-Based Foam and PolyPour, Pour-in-Place Foam.

• Hickory Springs Manufacturing Company markets Preserve Foam—a flexible polyurethane foam that replaces a portion of its petrochemical-based ingredients with a reactive material made from a sustainable, renewable resource.

• The Woodbridge Group announces BioFoam plant-based polyurethane products. The BioFoam product line is mass-production ready for automotive applications including seat cushions, head-restraints, arm-rests, and overhead systems. The actual 25% biobased content should reach 100% as shown by lab trials.

10.10.4.2 Biopolyurethane Sprays Polyurethane Composite Resins: TSE (http:// www.tse-industries.com/products/polyurethane-composite-resins) proposes various sprays such as EcoSpray Bath Reinforcement, EcoSpray Bio-Based Resin, EcoSpray for Hot Tub Spas, EcoSpray Polyaspartic Resin, EcoWind Filament Winding.

10.10.4.3 Coatings and Adhesives Croda introduces 100% biobased Priplast polyester polyols to meet the growing market demand for high performance, 100% renewable building blocks for coatings and adhesives. Claimed benefits include durability, a unique combination of thermooxidative properties, UV and hydrolysis resistance, moisture protection barrier, flexibility at low temperatures, and adhesion to a wide range of substrates including low-polarity plastics,

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Covestro launched Impranil eco, a bio-based waterborne polyurethane dispersion for textile coatings with up to 65% of renewable resources not in direct competition with the food chain; In addition, reformulation efforts would be limited. Alberdingk renewable PUR by Alberdingk Boley (http://www.alberdingkusa.com/products/characteristics/cat2/renewable-polyurethanes.html) are based on natural castor and linseed oil polyols for high quality surface coatings such as architectural coatings, exterior wood coatings, DIY varnishes, wood flooring, sports flooring, wood care products, wood furniture, soft-feel, automotive basecoats, textiles, and polyurethane dispersions. TSE markets its EcoSpray for EPS coating.

10.10.4.4 Biothermoplastic Polyurethane Bio-TPU, for example Pearlthane ECO by Lubrizol (formerly Merquinsa), are biobased TPU resins suitable for injection molding and extrusion applications with biobased content ranging from 29% to 75% as certified according to ASTM-D6866. Table 10.39 displays some examples of properties. Data sheets may evolve and other producers may market other grades. Those data cannot be used for design purposes. OnFlex-Bio 5300 series thermoplastic elastomer compounds (PolyOne) are soft TPU compounds that contain at least 20% of renewable material.

10.10.5 Examples of Environmental Advantages Main indicators, global warming potential (GWP) and energy consumption, are benefiting for bio-PUR made out of natural sourced polyol. For example:

• GWP (kg CO2 eq/kg PUR) is claimed 2.18 for Lupranol Balance 50 versus 2.99 for a traditional PUR

• Lupranol Balance 50 consumes 12% less energy than similar traditional PUR. Some other indicators are also better for natural sourced PUR, for example:

• Ozone depletion potential (CFC eq g/t polyol) 4 versus 7 for traditional PUR

• Acidification (SO2 eq kg/t polyol) 17.6 versus 19

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Table 10.39 Examples of Pearlthane ECO Properties. Property

Units 3

82 Shore A

55 Shore D

1.10

1.18

Density at 20°C

g/cm

Shore hardness

A or D

82A

55D

Tensile strength

MPa (psi)

33 (4786)

43 (6237)

Elongation at break

%

604

360

Modulus at 100% elongation

MPa (psi)

4 (580)

18 (2611)

Modulus at 300% elongation

MPa (psi)

9 (1305)

37 (5367)

Tear strength

kN/m (lb/in.)

84 (479)

189 (1079)

20

24 ,0.1

3

Abrasion loss

mm

Moisture content

%

,0.1

Tg (by DSC)

°C (°F)

243 (245)

DSC, Differential scanning calorimeter.

• Critical water volume (norm. m3/t polyol) 929 versus 1239

• Solid waste (norm. t/t polyol) 0.11 versus 0.22

• Alberdingk

http://www.alberdingk-boley. de/en.html#

• BASF

https://www.basf.com/ (BASF collaborated with Ford Motors and formed an OEM for long-term supply of castor oil based PU foams)

• Biobased

http://www.biobased.net/ company.php

For other examples:

• For a 47% renewable content based on MB concept, calculated GHG values are 2.1 kg CO2 eq/kg (Cradle to Grave: Evyron) versus 3.5 for undefined traditional PUR

• For 16% 17% renewable contents based on MB concept, calculated GHG values are 2.5 kg CO2 eq/kg (Cradle to Grave: Evyron) For polyols or PUR containing some CO2, benefits depend on the used replacement level and the considered end products. For example:

• GHG emissions may be 2.6 3.03 kg CO2 eq/kg of polyols versus 3.2 3.4 for traditional polyols

• Fossil resource depletion in kg oil eq may be 1.5 1.87 versus 1.94 for equivalent conventional PUR.

10.10.6 Examples of Polyurethane Players The quoted company names and websites are provided “as they are” and do not constitute any legal, or professional advice. Significant players operating in biobased polyurethane market include, without claiming to be exhaustive:

Technologies

• Cardolite

https://www.cardolite.com/ products/polyols_diols/

• Croda

www.croda.com/

• Johnson

http://www.johnsoncontrols. com/content/us/en/

Controls Inc.

• Merquinsa

www.merquinsa.com/

• Rampf

http://www.rampf-gruppe.de/ en/companies-and-products/ eco-solutions/base-polyols/

Ecosystems

• Rhino Linings

http://biobased.rhinolinings. com/products/index.html

• Succinity

http://www.succinity.com/, a 50 50 joint venture of BASF and Corbion Purac

• The

Dow

www.dow.com/

Chemical Company

• TSE

http://www.tse-industries. com/products/polyurethanecomposite-resins

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10.11 Renewable Unsaturated Polyesters UPs are thermosetting resins generally resulting from the reaction of fossil di-acids or anhydrides on the one hand and diols or glycols on the other hand. Following the sustainability wave there is a trend to use renewable materials.

10.11.1 Overview Partially renewable UPs are slowly developing but renewable content, sometimes including recycled materials, can be as low as 8% up to 55%. Bio-polyols, originated for example in soy or glycerol released in the production of biodiesel, partly replace petroleum-based components. Please note that green or bio or eco UP resins may be:

• derived from biologically renewable materials, • derived from recycled materials, and/or • free of styrene. Among others, let us quote some materials formulated for casting, cured-in-place pipe (CIPP), closed molding and open mold laminating: EcoTek line by AOC, Envirez line by Ashland, Envirolite by Reichhold, Palapreg ECO by DSM, Silmar ECO Series by Interplastic, Susterra 1,3-Propanediol by DuPont Tate & Lyle Bio Products. Following information is claimed by producers. Palapreg ECO by DSM is claimed composed from the highest renewable resource (55%) without making any sacrifice to product performance or production speeds. AOC’s line of EcoTek Green Technologies for composites and cast polymers offers specific grades for:

• • • • • •

Cast Polymers Concretes CIPP Green Resins Closed Mold Green Resins Corrosion Green Resins Open Mold Laminating Green Resins

Processability and end-use performance are claimed similar to those of fossil resins.

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Table 10.40 displays some examples of properties of partially renewable UP resins aiming casting, CIPP and sheet molding compound (SMC) (class A) applications. For another example, the Envirez 1807 UP resin by Ashland is produced using 25 wt.% of grainderived organic raw materials coming from soybean oil and corn-derived ethanol. Premi-Glas 1203BBC-27 by A. Schulman is a biobased, UP composite, reinforced with a glass fiber and mineral filler. Exhibits excellent surface profile and low moisture absorption. Designed for processing by sheet and compression molding in matched die molds, Premi-Glas 1203BBC-27 targets automotive body panel, structural, and semistructural applications. Table 10.40 displays some other examples of properties of partially renewable UP resins. Data sheets may evolve and other producers may market other grades. ENVIROLITE is Reichhold’s brand for “green” products containing renewable and/or recycled materials. For example ENVIROLITE 31325-00, is an unpromoted, medium reactive, low viscosity UP molding resin derived in part from natural resources. Specifically, this product is based on soya oil derivatives and has a “green” content of 25%. The product is intended as a general purpose molding resin for SMC, bulk molding compound (BMC), and pultrusion applications. The resin leads to laminates with mechanical properties that are claimed similar to those of standard SMC, BMC, and pultrusion fossil resins. Reichhold, Inc. has studied hybridized soybean oil based UP resin systems compared to a typical UP resin system with a focus on the thermal and mechanical properties. The results (see Table 10.41) show that the HDT and mechanical properties of the modified soybean resin systems increase as the amount of urethane segments increase. Data sheets may evolve and other producers may market other grades. Table 10.41 displays property examples of a traditional UP composite and three soy-based resins with increasing level of urethanes. Polynt Composites (http://www.ccpcomposites. com/) proposes Enviroguard, a biosourced UP range, targeting all composites industry processes giving a carbon footprint 10% 30% less than traditional resins. Quoted data relate to examples only and cannot be generalized. They cannot be used for design purposes. Other data can be found elsewhere.

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Table 10.40 Examples of Renewable Unsaturated Polyester (UP) Resin Properties. EcoTek Example Processing method

Cast

CIPP

Class A SMC

Tensile strength (MPa)

61

60

54

Tensile modulus (GPa)

4.0

4.6

3.6

Tensile elongation (%)

2.1

1.7

1.8

Flexural strength (MPa)

121

75

96

Flexural modulus (GPa)

4.07

4.6

3.7

Heat distortion temperature (1.8 MPa) (°C)

59

113

113

Examples of Renewable and Fossil UPs by Ashland Composite

Renewable resins

Fossil resins

Resin biocontent (%)

10

18

20 25

0

0

Resin HDT (°C)

200

134

135 175

177

177

Elongation (%)

1.0

2.1

1.4 1.6

1.25

1.25

Tensile strength (MPa)

40

25

90

Tensile modulus (GPa)

3

2

4

Flex strength (MPa)

57

50

125

Flex modulus (GPa)

3

3

4.5

Elongation (%)

1.6

1.5

4

Clear Casting Data

SMC Properties Glass content (%)

29.5

32.5

30

29.9

29.3

Tensile strength (MPa)

80

100

103

95

86

Tensile modulus (GPa)

11.3

12.2

11 12

13.6

9.4

Flex strength (MPa)

180

235

194 250

260

170

Flex modulus (GPa)

11.7

13

9.8 12.3

14.7

10.0

Elongation (%)

1.20

1.65

1.75

1.70

1.30

Premi-Glas 1203BBC-27 Renewable UP Composite Processing Method

Compression Molding

Tensile strength (MPa)

100

Tensile modulus (GPa)

14

Flexural strength (MPa)

220

Flexural modulus (GPa)

10

Impact strength, notched izod (J/m)

1000

Poisson’s ratio

0.3

CTE (ppm/°C)

13 27

Thermal conductivity (W/m K at 25°C)

0.56

CIPP, Cured-in-place pipe; HDT, heat deflection temperature; SMC, sheet molding compound; UP, unsaturated polyester.

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Table 10.41 Property Examples of Experimental Soy-Based Hybridized Unsaturated Polyester (UP) Resins. Base

Petroleum

Soy-Based Hybridized UP Resins

Urethane level

0

Low

Medium

High

Barcol hardness

24 28

34 36

39 42

40 41

HDT (°C)

78

84

95

107

Flexural strength (MPa)

76

101

127

139

Flexural modulus (GPa)

2.1

2.7

3.1

3.2

Tensile strength (MPa)

44

58

70

73

Tensile modulus (GPa)

2

2.4

2.7

2.7

Elongation at break (%)

4.1

3.7

3.9

3.9

HDT, Heat deflection temperature.

UPM (https://www.upmbiochemicals.com/products/lignin/) claims lignin can replace 50% of the phenol used in the bonding of plywood and its goal is to increase the amount to close to 100% in the coming years.

10.11.2 Applications Some commercial or experimental applications are quoted for example without claiming to be exhaustive.

• A collaborative effort from United Soybean Board, Ashland and various partners including John Deere & Co. results in a series of molded parts for the Model 9750 John Deere Harvester combine introduced in August 2003. Deere & Co. has further specified soy-derived composite products made from SMC in most of their SMC parts, including tractor hoods. More than 100 kg of soy composite are installed on each Harvester combine. Ashland and its collaborators are working to expand the product offerings into other markets, including construction and transportation.

• Cured-In-Place-Pipe • Casting resin with reactivity, stability, viscosities, density, peak temperature and other properties similar to petrochemical-based products. A new resin system derived from renewable and recycled material is designed to be blended with aluminum trihydrate to provide fire retardant properties for mass transit applications.

• DSM develops Palapreg ECO P55-01 resin with 55% biobased content and claims the resin has been qualified in the automotive industry for vehicle body parts, including exterior panels. Tests by tier-1 Automotive OEMs have proven that this high renewable content is achieved without making any sacrifice to product performance or processing speeds. Palapreg ECO P5501 has already been commercially used to produce outdoor benches with SMC technology. Moreover, with certain variations, it can also be applied in other processing techniques such as resin transfer molding, hand lay-up, and infusion for a wide range of potential applications in building and construction.

10.11.3 General Properties Partially renewable UPs are claimed having properties and characteristics of the same order as fossil UPs and could be processed by clients’ equipment without the need for any drastic adjustments. The following information deals with general properties of UPs and, of course some properties of renewable UP can be different. So, keeping equal all the other parameters, don’t make a short-sighted replacement of fossil polymer by the same weight of biosourced material without preliminary feasibility studies. Often, the recipe and/or processing conditions must be adjusted.

10.11.3.1 General Advantages Attractive price/property ratios, good mechanical and electrical properties, fairly good heat and creep

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

behaviors, esthetics, choice of rigidities, resistance to a great number of chemicals, resistance to light, weathering and water in spite of surface deteriorations; possibilities of transparency and food contact for suitable grades, broad range of colors, ease of some manual processing methods, possibility of lightening by controlled foaming, suitability for the manufacture of very large composite parts (shipbuilding).

120% of the tensile strength of a homologous DGEBA FRP on the one hand and on the other hand 95% up to 115% of the modulus of a homologous DGEBA FRP.

10.11.3.2 General Drawbacks

The renewable resources may be the epoxy monomers or/and diamine or anhydride hardeners. The various types of renewable materials, the nature of the hardener, and the versatility of the recipes lead to very diverse chemical natures and properties. Epoxy resins can include epoxidized vegetable oils and epichlorohydrin coming from glycerol that is released in the production of biodiesel. Epichlorohydrin can be manufactured from biosourced glycerol, an unused by-product (10%) of the manufacturing of biodiesel from oil plants. Solvay has developed a process and Advanced Biochemical (Thailand) Co., Ltd. produces Epicerol since February 2012. Solvay’s comparative LCA on Epicerol and propylene-based epichlorhydrin confirms the environmental advantage of Epicerol saving 61% of GWP (34% due to carbon capture by plant growth, 27% due to lower GHG emissions). The challenge to obtain a fully biobased epoxy prepolymer is thus to replace bisphenol A (BPA) by a biobased precursor. Biobased epoxy prepolymers can be derived from natural sugars, sorbitol, and isosorbide. Sorbitol polyglycidyl ether is available commercially, while isosorbide diglycidyl ether can be synthesized either via conventional epoxidation (i.e., using epichlorohydrin) or via the diallyl isosorbide intermediate. Among other examples of epoxy resin producers using renewable resources, let us note some examples:

Natural flammability, significant shrinkage of the current grades, industrialization and reproducibility difficulties for some processes, limited behavior to bases, acids and boiling water except for special grades; decomposition by oxidizing strong acids, attack by some solvents.

10.11.3.3 Special Grades

• Hand and spray lay-up molding, impregnation, SMC, BMC, thick molding compound (TMC), ZMC; compression, injection, pultrusion, filament winding, centrifugation, long or short glass fiber reinforcement, for thin or thick parts, for shipbuilding, for gelcoat; more or less reactive, more or less thixotropic, food contact, foamed, controlled damping, low shrink, low profile, fireproofed, preaccelerated, rigid, semirigid, flexible, high elongation at break, high or very high transparency, improved light or hydrolysis or heat stability, low emission of styrene or environment friendly, cold hardening, hot hardening, toughened, light color, resistant to cracking, etc.

• For casting, encapsulation, inclusion, cements, concretes, for large blocks, buttons, molds.

• Vinylester grades for chemical and heat resistance.

• Some special grades can be UV curable.

10.12 Renewable Epoxy Resins Epoxies are thermosetting resins obtained by reaction of a multi-epoxy monomer and a hardener. The hardeners are often aliphatic, cycloaliphatic, or aromatic diamines and more rarely anhydrides. Using various levels of various depolymerized organosolv lignin and depolymerized kraft lignin, Ferdosian (2015), fabricates FRP having 67%

10.12.1 Natural-Sourced Epoxidized Oils and Epichlorhydrin

Cardolite

http://www.cardolite.com/

CVC Thermoset Specialties

http://www.cvc. emeraldmaterials.com/

Dragonkraft

http://www.dragonkraft. com/

Ecopoxy

http://ecopoxy.com/

Entropy Resins

http://www.entropyresins. com/ (Continued )

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that utilize starting materials based on renewable resources. Dragonkraft Europe proposes bioresin systems for the composite, coating and adhesive markets. Renewable carbon contents are claimed to be between 20% and near 100%. Some resins are UV curable in natural daylight. The Dragonkraft package is claimed BPA free. Dragonkraft reports that the formulation can be used for many applications and the curing speed can be adjusted to suit users’ requirements. Resins adhere to many surfaces including wood, plastics, metals, and fiber glass. When compared to traditional resins they show equivalent resistance to a number of common chemicals. EcoPoxy is a plant-based resin system formulated to be cured in a wide temperature range of 50°C 95°C. EcoPoxy adheres and bonds to fiber glass, wood, steel, aluminum, concrete, brick, tile, and foam. Hardness reaches 70 Shore D and elongation is at least 15% after full cure. Entropy resins uses by-products from the paper pulp industry, waste and nonfood grade vegetable oils and by-products of biofuels production. Table 10.42 displays some properties claimed by Entropy Resins. Data sheets may evolve and other grades may be launched. Huntsman Advanced Materials research in the framework of “The BioMobile.ch ‘sustainable mobility’ project” indicates that it is commercially possible to produce resin systems for industrial applications with a biobased content that is higher than 80%—when combining up to 100% biobased resins and up to 80% biobased hardeners. The

—Cont’d Huntsman

http://www.huntsman. com/corporate/a/

Sicomin

http://www.sicomin.com/ products

Solvay

http://www.solvayplastics. com/

Spolchemie

http://www.spolchemie. cz/en/

Systemthree

http://www.systemthree. com/

539

Cardolite offers a line of cardanol-based epoxy resins, reactive and nonreactive diluents, and modifiers. Resin portfolio includes for example:

• NC-514, Flexible Epoxy Resin based on bifunctional glycidyl ether epoxy product. Reactivity and chemical characteristics are claimed similar to a traditional BPA type resin.

• NC-547 Epoxy Novolac Resin based on polyglycidyl ether epoxy novolac resin, which brings additional flexibility and longer pot life to coatings. According to Cardolite, diluents and multipurpose modifiers lower viscosity, improve anticorrosion properties, flexibility, and water resistance. CVC Thermoset Specialties markets ERISYS modifiers and monomers including a broad range of products, from monoepoxy functional to multiepoxy functional materials. The product line has expanded in recent years to include product grades Table 10.42 Examples of Entropy Resins Epoxy. Biobased carbon content

%

15 37

Tensile modulus

GPa

2.7 3.3

Tensile strength

MPa

58 69

Elongation

%

5 7

Flexural modulus

GPa

2.3 3.1

Flexural strength

MPa

78 102

Compression strength

MPa

73 88

Glass transition (Tg) by DSC

°C

40 86

HDT

°C

65

Hardness

Shore D

70 80

DSC, Differential scanning calorimeter; HDT, heat deflection temperature.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

composite body, chassis, and most of the structural parts of the BioMobile made entirely from various vegetable fiber reinforcements impregnated with the specially developed epoxy system from Huntsman Advanced Materials contains over 50% biobased resin. Spolek’s resins portfolio comprises CHSEPOXY containing 36% and more of carbon by weight from renewable raw materials. Epoxy equivalent weights are in the range 176 340 g/mol. Table 10.43 displays some property examples. Data sheets may evolve and other producers may exist. System Three markets the System Three General Purpose Epoxy System containing as much as 30% plant-derived materials. Table 10.44 displays some System Three epoxy property examples. Data sheets may evolve and other grades may be marketed. Generally, targeted applications include:

• • • •

casting and tooling, civil engineering, coatings, adhesives,

• composites, and • encapsulation and potting. Raven Lining Systems (http://www.ravenlining. com/) has earned the USDA Certified Biobased Product Label for its AquataFlex 505 and 506 hybrid novolac epoxy urethane coatings, 100% solids, with zero volatile organic compounds, and potable water NSF/ANSI 61 certified as well. Huntsman Advanced Materials markets Araldite DY-CNO a monofunctional epoxy reactive diluent resin, based on CNSL. Targeted applications of Araldite DY-CNO include structural composites, adhesives, electronics, coatings, and construction markets. Sicomin (http://www.sicomin.com/) commercializes GreenPoxy and InfuGreen based on renewable materials (35% 50% and more) suitable for infusion, laminating, injection molding, filament winding, press processes, and casting. Targeted application sectors include among others: Arts and entertainment, automotive and transport, marine, sports and leisure.

Table 10.43 Example of Long Pot Life Epoxy System With High Heat Deflection Temperature. System Type

Amine Cured Systems

System/resin

CHS-epoxy G520 (green epoxy resin)

Viscosity (Pa s, 25°C)

3.8

Minimal curing temperature (°C)

20

Minimal potlife (23°C, h)

6

Glass transition (Tg) (°C, MDA method)

200

Flexural strength (MPa)

115

Tensile strength (MPa)

65

Elongation (%)

4 2

Impact strength (kJ/m )

20

Table 10.44 System Three Epoxy Property Examples. Renewable raw material

%

30

Tensile strength

MPa

52

Tensile elongation

%

11

Flexural strength

MPa

88

Flexural modulus

GPa

2.5

Compressive strength at yield

MPa

84

Compressive strength at failure

MPa

154

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541

10.12.2.1 General Advantages

Some Sicomin’s GreenPoxy products have been certified by Bureau Veritas, a certification body of environmental management systems. Table 10.45 displays some Sicomin epoxy property examples. Data sheets may evolve and other grades may be marketed. Sicomin PB 360 GS reportedly allows in situ production of a shaped low-density epoxy foam core and offers good adhesion to a variety of materials and low-water absorption. It is proposed for foam cored components with lightweight glass, carbon or NF laminates, such as sporting goods, paddles, and surfboards.

Good mechanical properties, broad range of moduli, good thermal resistance of certain grades, resistance to numerous organic solvents and other chemicals, good electrical properties, aptitude for adherence on a large variety of substrates, good high-energy radiation behavior, selfextinguishing grades, food contact grades, possibility of transparency, diversity of the processing methods some of which are easy to use, capacity for the manufacture of high-performance composites.

10.12.2.2 General Drawbacks

10.12.2 General Properties of Epoxy Resins

Often long and energy-expensive production cycles, health and safety considerations during manufacture, relatively high prices justified by the properties, limited heat resistance for certain grades, risks of chalking during light exposure.

Partially renewable epoxies are claimed to have properties and characteristics of the same order as fossil epoxies and could be processed by clients’ equipment without the need for any drastic adjustments. The following information deals with general properties of fossil epoxies and, of course, some properties of renewable epoxies can be different. So, keeping equal all the other parameters, don’t make a short-sighted replacement of fossil polymer by the same weight of biosourced material without preliminary feasibility studies. Often, the recipe and/or processing conditions must be adjusted. The property range is very broad and it is not possible to make a rigorous classification. As an example, the continuous-use temperature can vary from 70°C up to 200°C in the extreme cases. The following information will inevitably be general and, unless otherwise specified, will relate to the most current grades.

10.12.2.3 Special Grades Liquid, one or two components, cold or hot curing, with or without postcure; cast, compression, transfer or injection molding; impregnation, stratification, filament winding, encapsulation, coating, varnishing; syntactic foams, prepregs; for electronics, tools, repairs, etc. Transparent, food contact, fireproofed, flexible, high heat resistance, expandable. The epoxies can be mono- or bi-component, hot or cold curing, needing or not a post-cure. The main processing methods are compression, transfer, injection moldings, casting, putting, encapsulation, impregnation, stratification, filament winding, machining, varnishing, and powdering.

Table 10.45 Sicomin Epoxy Property Examples. Renewable raw material

%

50

Tensile strength

MPa

50

Tensile elongation

%

2

Flexural strength

MPa

114 123

Flexural modulus

GPa

3.2 3.3

Glass transition temperature

°C

43 120

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

10.12.2.4 Applications The epoxy resin consumption by the industrialized countries accounts for 4% 6% of the total for thermosets and is approximately 0.7% 0.8% of the total plastics consumption. The main application markets are anticorrosive and protective coatings, composites, and reinforced resins for electricity, flooring and concretes, composites, and reinforced resins for various uses. The applications are nearly always technical.

Table 10.46 Examples of Biosourced Polycarbonate Properties. Density (g/cm3)

1.31 1.36

Light transmission, 2 mm thick (%)

92

Refractive index

1.5

Water absorption, 24 h, 23°C (%)

0.2 0.3

Tensile modulus (GPa)

2.2 2.7

Tensile strength (MPa)

64 79

Elongation at break (%)

72 130

10.13 Biosourced Polycarbonates

Flexural modulus (GPa)

2.1 2.7

Flexural strength (MPa)

94 116

Thermoplastic bio-PCs can be made with isosorbide in place of BPA, in a process that avoids the use of phosgene. Mitsubishi Chemical has started production of Durabio bio-PC and Teijin proposes its Planext bio-PC. Total capacity could be about 23,000 t/year. Following information is claimed by Mitsubishi Chemical for its DURABIO bio-PC.

Notched charpy impact strength (kJ/m2)

7 10

Un-notched charpy impact strength (kJ/m2)

NB

HDT B (0.45 MPa) (°C)

92 114

HDT A (1.8 MPa) (°C)

82 102

• high

transparency properties

and

excellent

optical

• good scratch resistance, high surface hardness and good abrasion resistance

• puncture impact behavior • good durability, light exposure stability, low

CTLE, 10

25

6.9 7.3

HDT, Heat deflection temperature.

based on isosorbide from corn starch and other plants. Teijin claims properties include chemical resistance, transparency, and surface hardness, and for specific grades gasoline and UV resistance.

yellowing due to exposure to light Compared to fossil PC, Durabio could be:

• better for surface hardness, UV resistance • not as performing as fossil PC for heat resistance, and/or multiaxial impact Bio-PC aims a wide variety of applications such as for example: optical devices, energy related components, substitute for high-performance glass components, electronic equipment, automotive parts, and interior and exterior decor. Japanese electronics maker Sharp is commercializing the world’s first biobased plastic smartphone front panel screen, using biobased PC Durabio. Table 10.46 displays examples of preliminary datasheet related to Durabio bio-PC. Teijin develops gasoline-resistant bioplastic film made of Planext bioplastic, an eco-friendly bio-PC

10.14 Derivatives of Lignin: For Instance the Liquid Wood (Arboform by Tecnaro) Researchers at the Fraunhofer Institute for Chemical Technology and the Fraunhofer spin-off TECNARO GmbH have developed a biothermoplastic, known as ARBOFORM or liquid wood, made of the lignin syrup discarded by the cellulose industry. After mixing with fine NFs made of wood, hemp, or flax and natural additives such as wax, the produced thermoplastic can be melted and injection-molded in car parts, urns, and other durable components. At the end of their life, those parts can be biodegraded in suitable conditions. In addition, ARBOFORM makes use of lignin which would otherwise be burnt or used in low-value animal feeds.

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Table 10.47 displays some characteristics of Arboform (by Tecnaro) depending on the used formulation. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Arboform could be priced above USD 2/kg in 2018. It has drawn interest from the automotive industry for its ability to replicate the finish and feel of wood in 3D parts. It has also been used to produce loudspeaker casings and golf tees. ARBOBLEND grades consist of biopolymers of lignin derivatives and/or other biopolymers like PLA, PHAs, starch, natural resins and waxes, cellulose, additives, and NFs. Use of lignin is studied in phenolic resins (PF) and EP resins. UPM (https://www.upmbiochemicals.com/products/lignin/) says lignin can replace 50% of the phenol used in the bonding of plywood and its goal is to increase the amount to close to 100% in the coming years. Table 10.47 Characteristic Examples of Arboform. Unit

Range 3

Density

g/cm

Mold shrinkage

%

0.1 0.3

Water content

%

2 8

Tensile strength

MPa

10 22

Ultimate elongation

%

0.3 0.7

Tensile modulus

GPa

1 5

Flexural modulus

GPa

1 5

Flexural strength

MPa

1.3 1.4

Mechanical Properties

10 50 2

2 5

Impact strength

kJ/m

Hardness

Shore D

50 80

Coefficient of thermal expansion

1025/° C

1 5

Vicat temperature

°C

80

Thermal conductivity

W/ mK

0.384

Thermal Properties

Hot-wire test

650°C passed

Electrical Properties Conductivity, surface

Ω

5 3 109

RAW MATERIALS

543

CIMV (http://www.cimv.fr/) proposes Biolignin for commercial applications such as glues (fiber boards, laminates, and plywoods), green plastics industry: PUR, polyesters, PF, epoxy resins. Domtar (https://www.domtar.com/en/) proposes Biochoice-lignin for industrial applications including adhesives, agricultural films, coatings, and plastics.

10.15 Example of Self-Reinforced Composite Produced From Cereals Among other examples, Vegeplast (http://www. vegeplast.com) markets an agrocomposite taking advantage of inherent biomatrix, biofibers, and biocomponents of cereal. VEGEMAT, claimed to be 100% biosourced, 100% biodegradable, and compostable bioplastic, is an agromaterial containing:

• Starch

having thermoplastic properties obtained by destructuring the native granule in the presence of a solute (softening agent) under thermo-mechanical constraints. Vegeplast claims Vegemat can be shaped using traditional plastics processing techniques (injection, extrusion).

• Fibers of cereal plants composed of cellulose, hemicellulose and lignin depending on the parts and the origin of the plant. Fibers reinforce the matrix and improve the mechanical properties of parts made with VEGEMAT.

• Proteins, lipids, and additives such as plasticizers and lubricants from natural origin fulfill processing and technical requirements without altering the biodegradability.

10.16 Renewable Acrylics—Poly (Methyl Methacrylate) Renewable or fossil PMMAs are thermoplastic resins. Ways toward renewable MMA and PMMA include biobased itaconic acid and biobased acrylic acid. Altuglas/Plexiglas Rnew biopolymer resins incorporate at least 25% biopolymers produced

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

544

from plant sugar leading to a lower carbon footprint. They are claimed having properties and characteristics of the same order as homologous fossil acrylics. For example, Altuglas/Plexiglas Rnew B514 is a transparent resin for injection with high impact-resistance and good chemical resistance. Altuglas/Plexiglas Rnew B522 transparent resin for injection is slightly less impact-resistant but has higher resistance to chemicals than B514. Altuglas/Plexiglas Rnew are claimed to offer excellent optical properties without the need for coating for suitable applications; high melt flow allowing lower temperature converting, therefore resulting in a lower carbon footprint due to a lower energy consumption; and a good chemical resistance. Other producers are investigating other ways. For example, Mitsubishi Chemicals (https://www. m-chemical.co.jp/en/) studies two approaches to improve the sustainability of MMA production:

• Use of renewable feedstock resources as raw materials for existing processes.

• Development of novel routes to achieve sustainable production directly from renewable resources. Partially renewable acrylics are claimed having properties and characteristics of the same order as fossil acrylics and could be processed by clients’ equipment without the need for any drastic adjustments.

10.16.1 General Advantages The optical properties, transparency, brightness, stability of colors, and outstanding weathering resistance are the basic motivations for the choice of PMMA for optics and transparent parts for technical and aesthetic applications. Fair mechanical properties at room temperature, rigidity, rather lowwater absorption, good creep resistance, excellent electric properties (notably the arc resistance), ease of machining, and possibilities of food contact for specific grades are complementary advantages. Direct casting of the monomer or its mix with prepolymers is one of the rare liquid processing possibilities for thermoplastics.

10.16.2 General Drawbacks PMMA is handicapped by a low-impact resistance, limited heat behavior (except for the acrylic

imides), inherent flammability, sensitivity to environmental stress cracking in the presence of certain chemicals, and chemical attack by certain current solvents. For some grades, processing can be more difficult than for some other current thermoplastics. Targeted applications of Altuglas Rnew include electronics, consumer goods, optics, and automotive, for example:

• Automotive and transportation: windshields, glazing

• Building and construction: urban visual communication, door canopies and balustrades, doors, windows

• Consumer goods: household equipment, appliances, cosmetics, furniture, gifts, and tableware

• • • • •

Electronics and electrical: lighting, lamps General industry Medical Signage Toys

Table 10.48 displays examples of renewable acrylic properties (Altuglas). Data sheets may evolve and other grades may be launched. Examples of producer claiming their interest for bio-PMMA: Arkema

http://www.arkema.com/

Evonik

http://corporate.evonik. com/

Mitsubishi Rayon Co

http://www.acrypet.com/

10.17 Renewable Phenol Formaldehyde Resins Thermosetting PF are obtained by the reaction of triphenols and formaldehyde:

• In an acidic medium: a first step leads to a thermoplastic that is reticulated in a second step by a curing agent or hardener (hexamethylenetetramine). These resins are called novolac or “two step” resins.

• Reaction in an alkaline medium yields products known as resols or “one step” resins.

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Table 10.48 Examples of Renewable Acrylic Properties (Altuglas). B514

B522

28

35

Renewable carbon

%

GWP

kg CO2 eq/kg

Melt flow index, MFI, 230°C, 3.8 kg

g/10 min

3.9

3.9

Mold shrinkage

%

0.2 0.6

0.2 0.6

Water absorption

%

0.3

0.3

Rockwell hardness L

L

49

77

Yield stress

MPa

36

50

Yield strain

%

3

3

Stress at break

MPa

36

33

Strain at break

%

23

5

Charpy impact strength (123°C)

kJ/m2

124

75

4.7

3.2

2

2.8 3.3

Charpy notched impact strength (123°C)

kJ/m

Flexural modulus (23°C)

GPa

1.6 1.7

2.2 2.4

Izod Impact notched (23°C)

J/m

107

43

HDT B (0.45 MPa)

°C

68

67

HDT A (1.8 MPa)

°C

58

57

Vicat softening temperature (10 N)

°C

68

67

Vicat softening temperature, 50°C/h (50 N)

°C

62

62

HB

HB

UL94 flame rating (3.2 mm) Density

g/cm3

1.16

1.19

Haze

%

,5

,4

Light transmittance

%

86

87

1.48

1.48

Refractive index GWP, Global warming potential; HDT, heat deflection temperature; MFI, melt flow index.

Two ways can lead to renewable resins: use of renewable phenols and replacement of formaldehyde by a renewable alternative. Cardolite (http://www.cardolite.com/), a producer of CNSL derivatives proposes binder resins for use in the transportation and brake industries. These thermosetting resins are used to hold brake linings, pads, blocks, and belts together. Cashewbased resins are claimed to offer all of the desirable characteristics of a straight PF (impact resistance, flexibility, thermal stability). Cardolite binder resins are offered in a wide range of viscosity, solids (special solvents or solvent-free), and modifications to suit different applications requirements. These resins can be used as binders for friction products

rolled lining and calendared segments as well as heavy-duty blocks and rail applications. These resins are also useful in other applications such as a replacement for tong oil in brake belts, and tire bead filler. Asian Lignin Manufacturing Pvt. Ltd. (http:// www.asianlignin.com/) has extensively worked on the development and optimization of PF resins based on Protobind 1000, 2000, and 2400 for several applications including shell molding resins. Although various substitution levels are possible, 10% 25% phenol replacement offers performance and cost savings as compared to the use of phenol. Fudow Company (https://fudow.co.jp/en/; Mitsubishi Gas Chemical Company, Inc.) proposes

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

its ECOFUDOWLITE F8000, a plant-derived biomass phenol-based thermoset resin (biobased content of 51%) suitable for processing by injection molding. Targeted uses include plates/utensils, lacquer, and other general applications. Claimed characteristics are: Specific gravity

1.37

Flexural strength

59 78 MPa

Flexural modulus

5.880 6.860 GPa

Charpy impact strength

2.2 3.2 kJ/m2

Dielectric strength

8 11 MV/m

Insulation resistance

109 1010 Ω

AVA Biochem (http://www.ava-biochem.com/) proposes biobased 5-hydroxymethylfurfural as an alternative to formaldehyde. Ramires and Frollini (2011) —demonstrate a potential to replace completely the formaldehyde in the preparation of PF by glyoxal, which is a dialdehyde obtained from several natural resources. The novolac glyoxal phenol composite showed better results for all the tested properties than the resol glyoxal phenol composite, demonstrating that the acid medium was more suitable for the preparation of the glyoxal phenol resin. Glyoxal obtained from several natural resources is claimed to be nontoxic. Partially renewable phenolics properties depend on the nature and level of alternative renewable sources. Sometimes mechanical characteristics may somewhat differ concerning flexibility and toughness. The following information deals with general properties of fossil phenolics and, of course, some properties of renewable phenolics can be different. So, keeping equal all the other parameters, don’t make a short-sighted replacement of fossil polymer by the same weight of biosourced material without preliminary feasibility studies. Often, the recipe and/or processing conditions must be adjusted. The PF may be filled with more or less high levels of materials of very diverse natures: short or long glass fibers, glass beads, wood flour, mica, cellulose, cotton, fabrics, rubber, graphite, polytetrafluoroethylene, molybdenum sulfide, and so forth. They are also used as a composite matrix. Consequently their properties and uses cover a very broad range.

10.17.1 General Advantages Attractive price and price/property ratios, good heat resistance, high glass transition temperature, good creep behavior, good mechanical properties, resistance to chemicals such as most common solvents, weak acids, natural oils, fats, greases, petroleum products, and automotive fluids; resistance to light and weathering in spite of slight surface deteriorations. Fire ratings: in a fire, relatively low amounts of smokes at a relatively low level of toxicity are produced by specific grades. Usable as a matrix for composites.

10.17.2 General Drawbacks Opaque, dark colors, significant shrinkage, unusable for food contact, low-arc resistance except for special grades, water or ammonia degassing, low resistance to bases except for special grades, decomposition by oxidizing strong acids, limited flexibility, and low elongation at break. A lot of applications are outside the scope of this book, such as adhesives, resins for foundry, paints, and so forth. Examples of PF producers potentially active in the renewable domain. Ashland

http://www.ashland.com/

Asian Lignin Manufacturing Pvt. Ltd.

http://www.asianlignin.com/

AVA Biochem AG

http://www.ava-biochem. com/

Borden Chemical Inc. (Hexion Specialty Chemicals)

https://www.hexion.com/

Cardolite

https://www.cardolite.com/

Fudow Company

http://www.fudow.co.jp/en/

Georgia-Pacific Corporation

http://www.gp.com/

Hexion Specialty Chemicals

https://www.hexion.com/

Momentive Specialty Chemicals Inc.

https://www.hexion.com/

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10.18 Renewable Polypropylene Two ways are under consideration but industrial development is low for economic reasons. Braskem is the pioneer in the production of renewable PP made from a 100% renewable raw material. Braskem claims renewable PP:

• Can be processed on the same equipment as oil-based PP

• Having similar properties to oil-based PP • Recyclable • Decreasing the greenhouse effect and global warming as it absorbs more CO2 from the atmosphere than it emits throughout its production cycle—from the cultivation of sugarcane to final PP resins. Bio-PP helps capture and sequester 2.3 t of CO2 for each ton produced. LyondellBasell and Neste use another way and have jointly announced the first production at a commercial scale of biobased PP using renewable hydrocarbons derived from waste and residue oils. Several thousand tons of biobased plastics approved for the production of food packaging are marketed under Circulen and Circulen Plus tradenames dedicated to circular economy products. Examples of EP Circulen Plus properties provided to give a rough idea only:

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—Cont’d Charpy impact strength— notched (23°C)

kJ/m2

Charpy impact strength— notched (23°C)

kJ/m2

Ductile/ brittle transition temperature

°C

245°C

HDT B (0.45 MPa, unannealed)

°C

90 92

55.5

3.2

2.5 3.2

HDT, Heat deflection temperature.

Data sheets may evolve and other grades may be marketed. Involved companies operating in this domain of renewable PP include:

• Biobent Polymers (http://www.biobent.com/ products/)

• Braskem (https://www.braskem.com.br/) • Du Pont (https://www.dupont.com/productsand-services/plastics-polymers-resins.html)

Melt flow rate (230°C/ 2.16 kg)

g/ 10 min

48 70

Density (23° C)

g/cm3

0.9

Tensile modulus

MPa

1200 1250

Tensile stress at yield

MPa

24 27

Tensile strain at break

%

30

Tensile strain at yield

%

• Global Bioenergies (https://www.global-bioenergies.com/?lang 5 en): bio-propylene

• LyondellBasell

(https://www.lyondellbasell. com/en/sites/circulen/) Circulen Plus products will contain a measurable and guaranteed biocontent which had been verified by an accredited third party laboratory. By measuring carbon 14 traces (carbon dating), the renewable biocontent is confirmed.

• Neste (https://www.neste.com/companies/solutions/circular-plastics-solutions)

• Trellis Bioplastics: Trellis Earth Products Inc. 4 5

(Continued )

has (http://www.trellisbioplastics.com) acquired the assets of bioplastics company Cereplast Inc.

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10.19 Renewable Polyvinyl Chloride Renewable PVC resin could be produced according to the ethylene ethanol route but the chlorine itself cannot be renewable. Several projects are based on dehydration followed by chlorination of bioethanol. Fossil PVC may also be modified with bio-PHA. Soft bio-PVC compounds can be obtained thanks to fossil PVC plasticized by high levels of bioplasticizer. (https://www.inovyn.com/) Recently, Inovyn has launched its Biovyn claiming it is the world’s first commercial producer of bio-attributed PVC using a supply chain fully certified by The Roundtable on Sustainable Biomaterials (RSB). Biovyn could substitute the use of virgin fossil feedstocks without compromising lifetime, flexibility and recyclability. The first application will be by Tarkett, who will source it for a new flooring collection. Positive climate impact includes a high greenhouse gas reduction (up to about 90%). Partially renewable PVC are claimed having properties and characteristics of the same order as fossil PVC and could be processed by clients’ equipment without the need for any drastic adjustments. The following information deals with general properties of fossil PVC and, of course some properties of renewable PVC can be different. So, keeping equal all the other parameters, don’t make a short-sighted replacement of fossil polymer by the same weight of biosourced material without preliminary feasibility studies. Often, the recipe and/or processing conditions must be adjusted.

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Flexible PVC is appreciated for the versatility of its characteristics according to the formulation. Significant quantities of fillers and plasticizers are used to optimize some of the characteristics such as behavior at low temperatures, fire resistance, flexibility and hardness in the elastomer range, low price, electric insulation, easy welding and joining, possibility of transparency, food contact, and fireproofing. Plastisols allowing the use of particular liquidstate processing techniques: casting, roto-molding, dipping, coating, and so forth.

10.19.2 General Drawbacks PVC by itself cannot be processed, it must be compounded with at least a stabilizer, a lubricant and, if flexible, a plasticizer. PVCs are currently handicapped by the ecological problems associated with chlorine and also with some of the plasticizers for the flexible products. Rigid PVC inherent sensitivity to UV without protection (but adequate compounds exist); softening and creep when the temperature rises; attack by aromatic or chlorinated hydrocarbons as well as by esters and ketones; impact sensitivity, the more so as the temperature decreases; high density; fume toxicity and corrosivity in the event of fire; less easy to inject; tool corrosion. Flexible PVC suffers from the same drawbacks as rigid PVC the more so as the amount of plasticizer increases, increasing creep, fire sensitivity (except for FR plasticizers), fume toxicity and corrosivity, and decreasing chemical resistance and thermal aging resistance.

10.19.1 General Advantages PVC is regarded as perhaps the most versatile thermoplastic resin, due to its ability to accept an extremely wide variety of additives such as plasticizers, stabilizers, fillers, processing aids, impact modifiers, lubricants, foaming agents, biocides, pigments, reinforcements, and so forth. General advantages depend on the type of compound. Rigid PVC is appreciated for its rigidity at room temperature, low price, chemical resistance except to certain solvents, dimensional stability, easy welding and joining, resistance to weathering for well-optimized compounds, possibility of transparency, food contact, and fireproofing.

10.20 Thermosetting Cyanate Ester Resins The US Department of Defense leads a project “Cyanate Ester Composite Resins Derived from Renewable Polyphenol Sources (WP-1759)” to demonstrate the feasibility of converting polyphenols that are extracted or derived from sustainable and renewable plant sources to cyanate ester resins for use in high-performance polymer composites. Renewable resources include, among others, creosote bush leaves and stems, vanillin, resveratrol, and single-ring systems derived from resorcylic acid.

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Glass transition temperatures (Tg) are in the range of 150°C up to 315°C (TMA) and thermal stability can reach 310°C (TGA-IR). Water uptake in these resins depends on the chemical structure.

10.21 Thermosetting Furanic Resins Furfural, a precursor for furan resins, can be produced from processing of polysaccharide hemicellulose constituents by digestion and dehydration. The preferred biomass is bagasse, a residue from sugar cane. The main applications of furan resins concern the foundry industry and special chemical resistant parts. To expand uses, the Biocomp project studies two types of furan resins, Biorez and Furalite furan resins, for same applications as standard resins. Parts of one to some meters have been produced as demonstrators. Compression molding of mats with the resin sprayed up leads to an automotive door panel prototype. Example of producer without claiming to be exhaustive: TransFurans Chemicals (TMC; www. transfurans.be/) (https://www.polyfurfurylalcohol. com/products) which claims:

• BioRez resins are available as molding resins or as water soluble impregnation resin and are generally curable at elevated temperatures. Due to its adhesive properties and compatibility with NFs, BioRez resins find application as thermoset matrix material in: • Compression molded NF reinforced composites • Wood modification • Wood-based panels and boards • Glass and NF insulation material • ...

• Furolite resins are formulated for applications where stability under heat, fire or corrosive environment is needed. To fulfill these requirements, these resins are mostly reinforced with glass fibers, carbon fibers or mineral fillers. Furolite can be used to make components highly resistant to fire with a low-smoke toxicity without the use of flame retardant additives. Furolite thermoset resins find application as matrix material for fiber reinforced plastics,

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polymer concrete, impregnating solutions, ceramic/carbon aggregate binder, and so forth. Targeted markets include biocomposites for automotive and furniture applications, fire resistant composites for mass transport applications, wood modification, and so forth.

10.22 An Endless List of Alloys Many alloyed materials have been already implicitly or clearly quoted but there are many other solutions involving traditional polymers, two or more biopolymers, and proprietary formulations taking into account local or professional contexts. The following examples show the diversity of solutions without claiming to be exhaustive.

10.22.1 Alloys of Renewable Polymers Compatibility between renewable polymers depends on their chemical and physical properties. Sometimes treatments may achieve a sufficient compatibility. For example the literature quotes studies on compatibilization of PLA with PHA, PLA/TPS, PHB.

10.22.2 Hybrid Alloys of Renewable and Fossil Polymers For example PLA could be compatibilized with ABS, polyoxymethylene, PC, PP, PE, polyphenylene ether, PBT, PMMA, hydrogenated styrenebutadiene-styrene block copolymer (SEBS), and others according to the used polymers and treatments of compatibilization. For example, Toray commercializes environment-friendly ECODEAR PLA, based on plant-derived raw materials and Toray technology that can help to reduce fossil fuel consumption and prevent global warming. Toray’s ECODEAR PLA has been introduced in the production of fibers, resins, and films used in areas including consumer electronics, office automation equipment, automotive, and packaging materials. A number of different high-performance grades are being developed and deployed, from FR injection grades to extrusion grades.

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Table 10.49 Property Examples of Solaplast Containing Algae and Fossil Plastic. Fossil Plastic 3

PP Ho

PP Co

EVA

1.12

1.16

1.23

Density

g/cm

Tensile strength

MPa

20.8

11.4

3.6

Tensile modulus

GPa

1.14

0.74

0.047

Tensile elongation

%

4.1

5.7

180

Flexural strength

MPa

21.5

Flexural modulus

GPa

0.9

EVA, Ethylene vinyl acetate; PP, polypropylene.

Table 10.50 Property Examples of APINAT Bio. Example

A

B

C

D

E

Hardness, Shore

60A 40D

66D 75D

48D

58D

70D 77D

Density

1.15 1.18

1.20 1.40

1.22

1.22

1.22 1.25

Tear Strength (MPa)

22 107

72 190

114

100

90 150

Tensile Strength (MPa)

2.7 14

30 43

23.5

17.6

25 45

Elongation at break (%)

411 786

15 450

650

54

3 50

10.22.3 Others 10.22.3.1 Examples of Algae and Fossil Polymer Compounds Algix (www.algix.com) markets proprietary blends (Solaplast) based on algae derivatives and fossil plastics (e.g., ethyl-vinyl acetate). Resins can be used for sheet extrusion, thermoforming, and injection molding. Targeted markets include footwear, foams, consumer packaging, durable consumer goods, horticultural, and agricultural applications. Table 10.49 displays examples of properties of Solaplast containing algae. Data are only given to provide a general idea and cannot be used for designing any parts or goods.

10.22.3.2 Various Bioplastics Derived From Renewable Raw Materials APINAT Bio (https://www.apiplastic.com/en/ products/) by API comes from renewable sources and is suitable for the production of 100% biodegradable hard soft products using overmolding and comolding processing.

Table 10.50 displays examples of properties of APINAT Bio. Data are only given to provide a general idea and cannot be used for designing any parts or goods. According to the producer, the physical and mechanical properties of APINAT Bio could satisfy all the requirements for creating a smartphone cover, in particular the need for a high degree of flexibility and softness to protect the smartphone from bumps and falls, as well as also having a practical, antislip surface. API and BIOMOOD Ltd have launched on the market the iPhone covers for iPhone 6 and iPhone 6 Plus. APIGO Bio by API (http://www.apiplastic.com/ en/) is a family of thermoplastic olefin (TPO) compounds containing from 20% up to 90% raw materials from renewable sources, showing physical and mechanical properties comparable to conventional TPOs derived from fossil fuels. Available in hardnesses ranging from 70 ShA up to 66 ShD, they can be processed using the traditional technologies of injection molding, extrusion, extrusion-blow molding, and overmolding and are available in various grades suitable for contact with food.

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Table 10.51 Property Examples of APIGO Bio. Example

A

B

C

D

E

Biocontent (%)

20

23

25

51

67

Hardness, Shore

70A

80A

90A

40D

50D

Density

1.03

1.05

1.06

0.90

0.92

Tensile strength (MPa)

4

5.6

7.7

6.3

12

Elongation at break (%)

450

650

660

390

800

0.120

0.260

Flexural modulus (GPa) Processing method

Injection

Injection

Injection

Injection

Injection

Food contact

Yes

Yes

Yes

Yes

Yes

Example

F

G

H

Biocontent (%)

95

97

87

Hardness, Shore

60D

60D

62D

Density

0.97

0.95

1

Tensile strength (MPa)

23

27

26

Elongation at break (%)

100

200

70

Flexural modulus (GPa)

0.680

0.720

0.800

Processing method

Extrusion

Injection extrusion

Injection

Food contact

Yes

Yes

Yes

Example

I

J

K

L

M

Biocontent (%)

68

70

29

60

30

Hardness, Shore

63D

65D

66D

67D

69D

Density

0.93

0.93

0.91

0.96

0.91

Tensile strength (MPa)

27

32

31

28

35

Elongation at break (%)

80

14

8

35

10

Flex modulus (GPa)

0.850

0.900

1

1.1

1.3

Processing method

Injection

Injection

Injection

Injection

Injection

Food contact

Yes

Yes

Yes

Yes

Yes

The APIGO Bio compounds target different application fields including personal care, building, packaging, furniture, and automotive thanks to the wide range of formulations. Table 10.51 displays examples of properties of APIGO Bio. Data are only given to provide a general idea and cannot be used for designing any parts or goods. In addition, API also commercializes:

• APINAT F BIO, a range of biodegradable TPE-E bioplastics which are compostable in accordance with the standard EN 13432.

• MEGOL bio, styrene-based thermoplastic bioplastics (TPE-S or TPS) whose raw materials come from renewable resources.

• APILON 52 BIO, urethane-based thermoplastic bioplastics (TPE-U or TPU) containing raw materials from renewable sources. PolyOne’s GLS Thermoplastic Elastomers business markets OnFlex BIO series thermoplastic elastomer compounds that are soft or glass-reinforced TPU compounds made from renewable natural sources. These compounds contain at least 20% renewable material as certified according to ASTM-D6866.

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Table 10.52 Examples of Some Fasal Bio Compound Characteristics. Examples

A

B

C

Density

g/cm3

1.28

1.16

1.26

Tensile strength

MPa

51

33

23

Tensile strain

%

1.25

1.9

0.5

Tensile modulus

GPa

4.9

3.9

5.2

Flexural strength

MPa

79

57

46

Flexural strain

%

1.2

3.1

0.9

Flexural modulus

GPa

4.6

3.5

6

8.7

9.6

Impact strength (Charpy)

kJ/m

2

Good Natured, previously Solegear Bioplastic Technologies Inc. (https://goodnatured.ca/) and rpac International have collaborated with a USbased consumer electronics retailer to produce smartphone case packaging. The line of renewable composites by fasal (http://www.fasal.at) is composed primarily of wood and corn, renewable natural raw materials. The main component, wood, comes from sustainably managed forests certified under the PEFC system. Additionally, fasal contains resins and small amounts of plasticizers which are also of natural origin. For the toys industry fasal was certified in accordance to EN 71. Claimed renewable and biodegradable contents are up to 100%. Table 10.52 displays some Fasal Bio compound characteristics. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Table 10.53 displays some examples of experimental WPC characteristics based on PLA. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Composites evolution (http://www.compositesevolution.com/) markets, among other products, preconsolidated sheets based on NF and PLA or PP. Biotex Flax/PLA is claimed to be 100% bioderived, manufactured from commingled natural flax fiber textiles and PLA biopolymer. Typical processes for Biotex Flax/PLA sheets are stamp forming and compression molding allowing to manufacture semistructural and decorative components in applications such as sporting goods and consumer products. Table 10.54 displays some characteristic examples of preconsolidated sheet based on PLA and flax

Table 10.53 Wood Plastics Composite Based on Polylactic Acid: Examples of Properties. Density

1.1

Vicat temperature

°C

72

Tensile strength @yield

MPa

34

Tensile modulus

GPa

3.8

Elongation @yield

%

3.8

Flexural modulus

GPa

3.7

Table 10.54 Examples of Properties of Flax Fiber Reinforced Polylactic Acid Preconsolidated Sheets. 232 Twill

Weave Style Fabric weight

g/m2

400

Typical ply thickness

mm

0.25 0.3

Typical Mechanical Properties of Molded Laminates Fiber volume fraction

%

40

Density

g/cm3

1.33

Tensile modulus

GPa

14

Tensile strength

MPa

110

Elongation

%

1.6

Flexural modulus

GPa

7.1

Flexural strength

MPa

123

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Table 10.55 Composite Based on Polylactic Acid (PLA) and Flax Fibers: Examples of Properties. PLA 40% Flax Fibers Density

1.33

Tensile strength (MPa)

102

Tensile modulus (GPa)

13.2

Flex modulus (GPa)

7.8 PLA Flax Prepreg Woven

Density

1.55

Tensile strength (MPa)

34 115

Tensile elongation (%)

4

Tensile modulus (GPa)

3.8 Unidirectional

Fiber volume (%)

40

3

Density (g/cm )

1.6

Tensile Strength (MPa) Reinforcement direction

265

Transverse

55

Tensile elongation (%)

5

Tensile modulus

6.2 60 PLA/40 Nonwoven Flax Fiber Prepreg

3

Density (g/cm )

1.15

Tensile strength (MPa)

30 70

Tensile modulus (GPa)

5 8 2

Notched Izod impact strength (kJ/m )

5 12 40 PLA/60 Nonwoven Flax Fiber Prepreg

3

Density (g/cm )

1.15

Tensile strength (MPa)

40 75

Tensile modulus (GPa)

9 10 2

Notched Izod impact strength (kJ/m )

10 25 60 PLA/40 Flax Fiber Preconsolidated Sheet

3

Density (g/cm )

1.33

Tensile strength (MPa)

110

Tensile modulus (GPa)

14

fibers. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Table 10.55 outlines the versatility of NF/PLA composites through some examples of compound

characteristics. Of course, mechanical performances greatly depend on reinforcement form and rate but also of processing conditions. Tensile strength ranges from 30 up to 265 MPa and modulus from

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3.8 up to 14 GPa. Some formulations include heavy additives leading to density higher than those of PLA and flax. Data are only given to provide a general idea and cannot be used for designing any parts or goods. Moreover, other data may be found elsewhere. EcoTechnilin Products (https://eco-technilin. com/en/) proposes NF mats and natural sourced composites, for example:

• FibriMat—100% NF mats including reinforcements for composites, underlay mats, and customized fiber mats designed for special applications.

• FibriPlast—Nonwoven felts for compression molding. FibriPlast products are composed of a reinforcement fiber (NF or glass fiber) combined with thermoplastic (PP, PLA, PA, etc.) ensuring the cohesion and the mechanical performances of the final part. Targeted applications include automotive interior parts such as parcel shelves, door panels, headliners, trunk side trims, among others, for all kinds of vehicles (cars, small cars, trucks, agricultural, and industrial vehicles).

• FibriBoard—precompressed mats with thermoplastic binders. FibriBoard preconsolidated sheets are produced from FibriPlast nonwoven mats after an additional precompression step that bestows the rigidity of a thermoplastic composite.

• FibriPreg—100% natural mats preimpregnated with thermoset resin. Typical resins are claimed to be 100% biosourced and thus offer a fully biosourced prepreg. Acrylic and other thermoset resins can also be used. OrganoClick (http://www.organoclick.com/products/fiber-composites-paper-products/? q 5 organocomp) proposes OrganoComp, a biocomposite combining cellulosic fibers with OrganoClick’s binder technology and molding the material in 3D molds. Following property data are provided to give a general idea and cannot be used for designing any parts or goods.

• • • •

Density E-modulus Tensile strain at break Tensile strength

0.65 1.03 g/cm3 701.86 6 53.76 MPa 5.55% 6 0.68% 23.71 6 1.60 MPa

Other data may be found elsewhere. Targeted applications include, for example:

• Interior design products • Burial coffins • Risk waste containers Of course, there are many other solutions than those cited in this chapter.

References Abad, L.V., Relleve, L.S., Aranilla, C.T., Aliganga, A.K., San Diego, C.M., Dela Rosa, A.M., 2002. Polym. Degrad. Stab. 76 (2), 275 279. Cerruti, P., Malinconico, M., Rychly, J., MatisovaRychla, L., Carfagna, C., 2009. Polym. Degrad. Stab. 94 (11), 2095 2100. Dopico Garcı´a, M. S. and Coll., 2011. Natural extracts as potential source of antioxidants to stabilize polyolefins, J. Appl. Polym. Sci. 119 (6), 3553. Ferdosian, F. 2015. Synthesis, Characterization and Applications of Lignin-Based Epoxy Resins (Thesis). Hauenstein, O., Agarwal, S., Greiner, A., 2016. Bio-based polycarbonate as synthetic toolbox. Nat. Commun. 7, Article number: 11862. In˜iguez-Franco, F., et al., 2012. Antioxidant Activity and Diffusion of Catechin and Epicatechin from Antioxidant Active Films Made of Poly(l-lactic acid). J. Agric. Food Chem. 60 (26), 6515 6523. Ramires, E.C., and Frollini, E. 2011. Resol and novolac glyoxal-phenol resins: use as matrices. In: Ferreira J.M. (Ed.), Bio-Based Composites, 16th International Conference on Composite Structures ICCS 16A. r FEUP, Porto.

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Further Reading Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Biron, M., 2016. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2014. Thermosets and Composites. Elsevier Ltd. M-Base Matweb Plastics Additives & Compounding, ISSN: 1464391X Elsevier B.V., https://www.journals.elsevier.com/plastics-additives-and-compounding.

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Modern Plastics Encyclopaedia, McGraw-Hill Publications. Modern Plastics International, Canon Communications LLC, Los Angeles, CA. Plastics News.com, Crain Communications. https:// www.crain.com/brands/plastics-news. Reinforced Plastics, ISSN: 0034-3617, https://www. journals.elsevier.com/reinforced-plastics/.

11 Plastics Sustainability: Drivers and Obstacles Plastic materials must satisfy, now and in future, the essential challenges relating to climate change, energy and resource efficiency, consumer protection, and the circular economy. Obviously that new way has a cost that must be agreed upon by users or explained by legislation requirements. Of course, many laws, directives, regulations, and other requirements as diverse as REACH (Registration, Evaluation, Authorization and Restriction of Chemicals), Eco-Design Directive, WEEE (waste electrical and electronic equipment), etc., are mandatory. It is necessary to contribute to a low-carbon society by reducing greenhouse gases (GHGs) emitted in the value chain:

• Extending the actual life of products, goods, and complete solution systems

• Reducing carbon dioxide (CO2) from produc-

Diverting the maximum amount of total waste away from the landfill avoids landfill costs and generates revenue by recycling. Be careful about general information such as “recyclable,” which often involves the technical possibility of recycling without realistic practical fulfillment for lack of a recycling stream, economic reasons, insufficient quality of the recyclate, or lack of market for recyclates. Sustainability is everybody’s responsibility and all employees must be engaged in environmental efforts. So, the economy scheme evolves from a linear economy based on easy options and immediate profits neglecting environmental issues to a circular economy aware of the environment at a competitive cost. Fig. 11.1 displays a theoretical scheme of a circular economy in comparison with the old scheme.

tion and logistics

• Reducing CO2 from the use phase • Reducing CO2 from end-of-life wastes All used or emitted substances including raw materials, utilities, and by-products must be managed on mandatory and voluntary bases, minimizing their environmental footprint. Waste must obey the “R rules:”

• Reduce waste toward “zero net waste” • Reuse, repair, refurbish, remanufacture, rebuild

• Recycle and efficiently reuse the ultimate waste

• Redesign from a sustainable point of view, minimizing waste; sustainable design works to make it easier to recycle all types of plastics for all types of parts and system solutions

11.1 The Vast Range of Waste Strategies: From Waste Minimization to Landfilling Every case is specific and all ways must be studied to find the best one (or less wrong) for ones’ own problem. Generally speaking, the main ways, in a decreasing order of interest, are:

• Waste minimization, the best desirable management strategy

• • • • •

Repair and reuse Recycling and reuse Energy recovery Composting Landfilling, the least desirable management strategy

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00011-2 © 2020 Elsevier Ltd. All rights reserved.

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(A)

Resource consumption

Manufacturing

Use

Waste

(B) Lower resource consumption

Recycling and reuse

Sustainable manufacturing

Long-lasting use

Figure 11.1 From linear to circular economy schemes: (A) linear economy and (B) circular economy.

But there are exceptions due to issues concerning one or several steps of waste management:

• Collection of used sets of parts: use of an existing stream or obligation to create a specific one

• • • •

Long lasting parts minimize total waste during the use life, notably end-of-life, or postconsumer waste, due to the cancellation of some manufacturing runs. However, the formulation of the compound and the weight of individual parts may be affected and the environmental benefit depends on the particular case.

Dismantling Depollution, cleaning Repairing Effective commercialization

An economic cost may be unacceptable, particularly when virgin plastics are cheap. Laws and regulations can be mandatory and unavoidable or voluntary.

11.2 Waste Minimization Waste minimization must be thought at the beginning of a project. The involved teams must favor a careful design, easing the processing on the one hand and a careful manufacturing process on the other hand. Of course, manufacturing yields are affected, which leads to beneficial economic consequences.

11.3 Repair and Reuse Repairing is an increasing trend for all industrial domains. Of course, repairing makes sense only if reuse is real and efficient. Generally speaking, repairing and real reuse of plastics save:

• • • •

money energy resources pollution

Provided they comply with the technical requirements and conform to specific rules. However, every step of the life cycle must be carefully studied to check the final benefit. An important point is the modification of the design, affecting all the life phases of the part to favor a possible, but hypothetic, later repairing.

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Disassembling vehicles, repairing, and checking parts is a way to extend their life cycle, thus, eliminating the need to consume energy or raw materials to manufacture new parts. However, keep in mind that these operations use energy, etc., that must be taken into account in the final balance. Gas tanks, lights, dashboards, bumpers, and other plastic parts from automobiles may be separated from other components and, if they are not damaged, they can be used again.

At the opposite end, for a consumer product, collecting, reconditioning, and reusing of refillable bottles for beverages is an important way to reduce packaging waste, but is not always beneficial for the environment because of collection costs, cleaning, etc.

AND

11.3.1 Overview Reuse and repairing have the environmental cost of the relevant steps including, but not limited to:

• • • •

Collection of used sets of parts

• • • •

Depollution, cleaning

Dismantling Storage of potentially reusable parts Inspection of actual geometry, shape, color, defects, etc. Repairing Storage of ready-to-use parts Delivery

Repairing is applied from a long time for more or less sophisticated products such as, for example anticorrosion inner layers, conveyor belts, rehabilitation of underground pipes thanks to cured in place pipe products (CIPP), boat hulls, shuttle packaging, etc. More recently, aircraft repairing uses composites for structural repair. Disregarding the material nature, the example provided here displays the high benefits of repairing a heavy metallic part; compared to new manufacturing, remanufacturing could reduce:

• • • • • • •

energy consumption by 66% global warming potential (GWP) by 67% acidification potential (AP) by 32% eutrophication potential (EP) by 79% ozone depletion potential (ODP) by 97% photochemical ozone creation potential by 32% abiotic depletion potential by 25%

This is an example only, not a rule.

11.3.2 High-Tech Repairs: Example of Aircraft Structural Repair Boeing and Airbus make huge efforts to develop aircraft structural repair methods for their new models based on composites. The methodology of structural repair processes at once involves inspection methods, composite processing technologies, and traditional repairing steps including for example:

• • • • • • • • • • •

Damage inspection Composite analysis Repairing method Strength and stiffness analysis Prepreg repair process Wet lay-up repair process Prepreg composite sandwich repair process Wet lay-up composite sandwich repair process Bonded patches Bolted patches Repair inspection

Repairing aircrafts is traditional work, but repairing reinforced plastic fuselages is a new challenge. For instance, the General Accounting Office expressed some queries about repairing composites in aircraft structures including:

• the difficulty of detecting damages • the limited standardization of composite materials

• the limited standardization of repair techniques • the limited experience of workers handling composites

• the lack of information on the long-term behavior of aircraft composites due to limited in-service experience.

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From an economic point of view, repairing is obviously a necessity. From an environmental point of view, various studies estimate that environmental damages coming from the production step are also reduced. Assuming that a composite structure weighs about 20% less than comparable aluminum components, the use of carbon fiber (CF) reinforced polymers (CFRP) could reduce aircraft weight by about 1500 kg. This could save about 43,000 gal of fuel per year in a round figure. To give another rough idea of environment damage, it is expected that a global transition of aircrafts to composite architecture could contribute to reaching 15% 25% industry CO2 reduction targets in the coming decades.

11.3.3 Benefits of Reused Drums Manuilova (2003) concludes her study on the reuse of plastic drums for the packaging of chemicals in the general interest of reusing, considering that:

• Resource consumption is about half of the traditional scenario

• Emissions of CO2, SO2, CH4, and NOx are reduced by 30% 48%

11.3.4 Refillable Bottles: May Be a Counterexample Reusing bottles is an important way to reduce packaging waste, but it changes and increases the steps of the life cycle including:

• Production of special bottles able to endure several use cycles

• • • •

Collection and returning of used bottles Cleaning and decontamination Refilling New distribution phase of refilled bottles

This method is economically and environmentally relevant when the costs of collection, returning, cleaning and decontamination, and refilling are less than those of using new bottles. Negative and questionable points include:

• A possible special design of bottles to endure harder use conditions involving thicker walls or better performing resins. Heavier bottles

lead to higher material consumption, higher energy for transportation, etc.

• The actual number of use cycles that may be expected, for example, about 10 times in round figures for usual polyethylene (PE) terephthalate (PET) bottles and some tens for crates and trays.

• Cleaning and decontamination depending on the packed liquid. Various life cycle analyses of PET bottles found insignificant or marginal differences between single use and refillable beverage packaging. However, from an oil shortage point of view, refillable bottles are of interest.

11.3.5 Refurbishing and Upgrading Machinery: Benefits of Industry 4.0 Best practices for the manufacture of parts based on any material include a careful maintenance of the process equipment. But at one time or another, one must ask themselves the question of its replacement and choose between upgrading or purchasing of new equipment.

11.3.5.1 Overview Machines may begin to show signs of aging after 10 20 years, particularly for electronic equipment, which leads to the question: What is best, buying a new machine or refurbishing the old model? On the one hand, modern machines operate around 20% 25% faster than old homologous machines, may be less energy demanding, and can be easier to operate and manage, which improves productivity and quality. On the other hand, retrofitting an old machine, if done by a specialist, may be a beneficial solution, bringing a replacement or revision of the control system, electronic equipment, wiring, and/or thermal system. For a lower investment, the installation of high-performance hardware and software will make the machine fit for another 10 20 years of use and allow for a smooth integration into the factory management system. In addition to careful maintenance and compliance with current safety standards, modernization, complete overhaul, makeover, retrofitting, upgrading, reengineering, modification, and performance enhancement of plastics processing machines allow

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for the lifetime of heavy and complex plastics machinery to be extended for a limited environmental and economic cost. Basic reasons may be as diverse as, for example:

complex automatic storage and retrieval system. A few robots may have payback periods without economic interest, but can bring irreplaceable advantages such as worker safety.

AND

• Performance enhancement • Processing of better performing polymers • Ability to operate new processing methods: Modification of machines for special applications, for example, upgrading of plasticization units to accommodate new injection molding techniques or extending monocomponent machines to allow for multicomponent processing

• Productivity improvement, shorter cycle times, reduction of off-specs, limitation of overproduction and unsold inventory

• Energy savings for thermal purposes, implementation of energy-saving measures

• Shifting from step-by-step to continuous processes

• Upgrading and modernization of control systems, state-of-the-art control technology

• Automation due to software and hardware, robotization, integration in workcells, connection to factory software

• IT-aided diagnostics techniques and training Of course, automation is a major upgrading of used and new plastics machinery, but as with other investments, the return on the investment must be viable. Fig. 11.2 displays examples of payback periods for a broad panel of robots or cobots offering services as diverse as welding, artificial vision, injection handling, assembly, shaping, packaging, cutting, coffee capsule finishing, sealing, storage, etc. The payback mean is about 1.5 years with a minimum of 0.3 years (nearly 4 months) for a welding device and a maximum of 5 years for a

11.3.5.2 Industry 4.0: A Modern Way to Inspire an Efficient Retrofitting Refurbishment, upgrading, and specialization of equipment may ease, strengthen, and finalize the shift toward industry 4.0, building on the digital revolution and creating a continuous and smooth flow of information along the entire value chain. All areas may be involved such as virtualization, connectivity, collaborative work, real-time, customization, and flexibility, etc. Upgraded equipment can be linked to existing software such as computer aided design, computer aided engineering, computer aided machining, simulation, product life cycle management, manufacturing execution system, manufacturing resource planning systems, enterprise resource planning, robot management systems, etc. Sensors are able to detect and/or quantify just about all properties linked to raw materials, machines, processing, quality, products, failures, traceability, etc. Robots can work alone or in collaboration with human workers, handling tiny or heavy loads with reaches ranging from a few centimeters to several meters. Multiple tasks may be processed due to versatile end-of-arm tooling targeted at the plastics industry. The goal is to improve:

• Sustainability as a whole • Customer satisfaction due to higher quality, lower cost, timeous and quantitative delivery

• Resource optimization, raw material saving, energy saving, lower emissions

Fréquence

15 10 5 0 0.3

1.5

2.65 Payback (years)

Figure 11.2 Examples of payback of robots.

3.8

or more

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• Worker satisfaction due to robotization, smooth production, reduction of unexpected shutdowns and restarts, better training, higher quality

• Efficient collaboration between stakeholders from the providers to the customers

• • • • • •

Higher productivity Quality improvement Affordability Cost-effectiveness Waste reduction Remote troubleshooting, etc.

Specialized software solutions aim at more or less general or specific materials, application areas, industries, cores of business, geometrical shape, etc., allowing for the study of special requirements.

• Virtual prototypes are far cheaper and more rapidly obtained than physical prototypes, which allow for the examining of numerous hypotheses.

• Virtual simulation consumes only virtual parts, requires no testing machines, and is faster and cheaper than physical testing.

• Software facilitates planning changes due to the speed and low cost of parametric recalculations easing the study of multiple scenarios.

Of course, industry 4.0 has a cost and before getting into it, some fundamental questions must be studied, for example, without claiming to be exhaustive:

• Zero default manufacturing systems avoid the

• Where is the real value of digitalization? Is it

• Software dedicated to administrative functions

in production costs, marketing, sales, quality, or other factors? Most likely, the answer is probably a mix of several answers.

• What are the estimated expenses and benefits? What are the balance and the expected return on investment (ROI)?

• Prioritize actions, search for those that are unnecessary and plan others.

• Digitalization is a long-term commitment, is expensive, needs new thinking, and possibly new recruitment. This needs a strategic plan that must involve all stakeholders.

• Digitalization is a deep change of behavior, thinking, and methodology, which generally worries workers and may create a source of uncertainty for customers. Instructive and informative efforts must be deployed in-house and outside to reassure customers and workers. Industry 4.0 opens the door to flexibility and customization, reversing the 20th century trend toward standardization. Progresses driven by digitalization allow flexibility in all stages of life cycle including identification of customer requirements, design, planning, production, storage, delivery, maintenance, customer assistance, logistics:

• Modularity of design and processes ease the study and production of customized products derived from general purpose families.

disastrous effect of defective parts, especially for short runs. minimize the cost of the management of low billing orders. Flexibility of production systems brings attractive final benefits due to improved reactivity to customer requirements, inventory reduction, and shortened lead times. This justifies the extra investment in system design, hardware, software, and training efforts. Fig. 11.3 displays costs/units according to the type of production system. Whether it be a large or short run, parts are always cheaper with digitalized systems. Of course, cheap customized parts can be sold at a niche price.

11.4 Recycling and Actual Reuse Recycling makes sense only if recyclate is really reused for manufacturing products of fair marketable quality.

11.4.1 Environmental Benefits of Recycling To make the comparisons easier between several materials or routes, CO2 emission has been chosen as a standard to quantify the greenhouse effect of the manufacture, use, recycling, and discarding of any product or good. The carbon footprint can be defined, in a simplified manner, as the sum of all emissions (and capture) of CO2 and other GHGs, expressed in

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Cost/unit

Parts per run Traditional system Digitalized system

Figure 11.3 Cost of short runs versus production system.

CO2 equivalent. So, the capture of CO2 due to plant growth or incorporated in monomers as raw material for polymerization is negatively accounted. The balance includes all the steps of the product life, that is, raw material synthesis, manufacture, transport, and use and end of use treatments. Upstream and downstream steps are to be accounted. It can be noted that the carbon footprint of recycling any plastic product, part, or good depends on:

• • • • •

The product to be recycled The waste collection method The actual state of the end-of-life product The recycling method The used energy sources, for example, electricity from wind turbines has a negligible impact on the carbon footprint

• The final purity of the recyclate • The form of the recyclate • The calculation method of the carbon footprint, etc. Consequently, data can dramatically differ according to the source. Most used recyclates are classified as commodities, but engineering plastics are marketed or inhouse recycled. As already said:

• Recycling makes sense only if the material is effectively reused in the same way (closedloop) or in another way that is less demanding (open-loop).

• Recycling yield is never 100%, often much less.

11.4.2 Closed-Loop Recycling Overview Table 11.1 displays examples of GWP gains induced by the use of recycled fossil polymer instead of the same weight of the equivalent virgin fossil polymer. Apart from errors, the studied polymers are in pellet form, but the actual end-of-life form, nature of the energy source used, recycling method, purity, upgrading, etc., are unknown. That explains the high standard deviations close to the mean or the median. Two examples lead to negative data, which relate to a higher GWP for recyclate than for virgin polymer; from a GWP point of view, recycling in these cases makes no sense, but may be interesting for other purposes. Of course, other different data may be found elsewhere. As already said, the data in Table 11.1 generally relating to pellets and the gains of GWP for end products may be different because of upgrading, poorly performing materials requiring formulation, and design or processing adjustments. For example:

• SoRPlas by Sony, made from recycled DVDs and optical sheets from TVs, cuts CO2 emissions by 77% over the manufacture of conventional plastic materials.

• By using 100% postconsumer recycled (PCR) resin for bottles, the carbon footprint is claimed to be lowered by 57%.

• For the recycling of PET, the carbon cost of producing food-grade recycled PET (rPET) 78 pellets in 2010 was 254 kg/t, while the carbon cost of producing virgin PET was 681 kg/t, which is a gain of 63%.

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Table 11.1 Examples of Net Carbon Footprint Gains Due to Recycling. Net Carbon Footprint CO2 equiv./kg Plastic Gain (%) Mean

34

Median

31

SD

27

Mean 2 2SD

219

Negative data are detrimental examples

Actual minimum

223

Negative data are detrimental examples

Actual maximum

70

Mean 1 2SD

87

Samples

20

SD, Standard deviation.

• According to Envision Plastics, using its recycled resins has an energy use saving of 90% and reduces GHG emissions by 78%.

11.4.3 Recycling of HighPerformance Materials: Example of Carbon Fiber Recycling high-performance materials such as CF may kill two birds with one stone, solving environmental and economic issues simultaneously such as:

• Economic cost saving • Environmental cost saving due to mitigated GWP

• Reduction

of disposal of composite manufacturing and end-of-life waste

• Alternative source for virgin CF supply For instance, ELG CF claims for its recycled Carbon Fiber (rCF) (Carbiso) the advantages:

• GWP reduced by more than 80% versus virgin CF

• Energy required for production reduced by more than 80% versus virgin CF

• Cost reduction of 80% versus virgin CF

Retained tensile properties are on the order of more than 90%.

11.4.4 Global Warming Potential of Specific Recycled Polymers Table 11.2 displays three distinct cases that confirm the environmental benefits of recycling from a GWP point of view:

• Recycled PE (rPE) with a mean gain of 22% and

a broad range of 223% to 63%. The negative data are losses relating to a higher GWP for recyclate than for virgin polymer; from a GWP point of view, recycling in such cases makes no sense, but may be interesting for other purposes. The broad range may be induced by the diversity of applications and high consumption of PE leading to a higher level of recycling.

• Recycling of commodity resins with a mean gain of 20% not significantly different from that of PE, but with a narrow range of 14% 31%.

• Recycling of engineering resins with a high mean gain of 61% (3-times that of commodity resins) and a narrow range of 50% 70% in round figures. This may be explained by the selection of end-of-life streams leading to relatively clean materials and the high environmental cost of engineering plastics.

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Table 11.2 Gains of Global Warming Potential Due to Recycling. rPE

Commodity (rPP, rPET)

Engineering (rPA, rPC)

Mean

22

20

61

Median

22

18

62

SD

39

7.5

6.9

Mean 2 2SD

256

5

48

Actual minimum

223

14

51

Actual maximum

63

31

70

Mean 1 2SD

99

35

75

Samples

5

7

6

rPA, Recycled polyamide; rPC, recycled Polycarbonate; rPE, recycled polyethylene; rPET, recycled polyethylene terephthalate; rPP, recycled polypropylene; SD, standard deviation.

Of course, other different data may be found elsewhere.

11.4.5 Global Warming Potential of End Products Incorporating Recycled Polymers Life cycle assessment (LCA) taking into account all the steps of the life cycle, injection, or extrusion, for example, the effect of recycled polymer use is somewhat different to that estimated for pellets. For example:

• Bottles recycling can reduce the emission of CO2 and other GHGs by an estimated 30% 70%.

Table 11.3 Fossil Energy Gains Due to ClosedLoop Recycling. Gain (%) Mean

49

Median

50

SD

13.4

Mean 2 2SD

23

Actual minimum

18

Actual maximum

71

Mean 1 2SD

76

Samples

28

SD, standard deviation.

• According to the UK’s Waste and Resources Action Programme (WRAP), recycled PET requires between 10% and 40% of the energy used to produce virgin PET according to waste collection and disposal operations.

11.4.6 Examples of Fossil Energy Gains Due to the Use of Recycled Resins Fossil energy demand represents a depletion of finite reserves. For example, regarding PE, the fossil energy demand for petrochemical PE includes the fossil feedstock (ethylene) that is converted into the PE polymer itself as well as the fossil energy process usage for this conversion. It can be expressed in MJ per product unit (weight, length of pipes, number of bottles, etc.).

Table 11.3 displays examples of fossil energy gains induced by the use of recycled fossil polymer instead of the same weight of the equivalent virgin fossil polymer. Apart from errors, the studied polymers are in pellet form, but the actual end-of-life form, the nature of the energy used, recycling method, purity of recyclates, upgrading, etc., are unknown. This explains the standard deviations of close to one-third of the mean or the median. Obviously, gains are high due to the reuse of the polymer, which otherwise is polymerized from crude oil fractions. Of course, other different data may be found elsewhere. Fossil energy requirement gains are about 45% for commodity resins and about 61% for engineering plastics.

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Table 11.4 Fossil Energy Gains Due to Closed-Loop Recycling of Commodity Polymers. PE

PET

PP

Mean

50

40

40

Median

50

45

40

SD

11

16

8.4

Mean 2 2SD

27

8

23

Actual minimum

33

18

27

Actual maximum

68

55

54

Mean 1 2SD

71

72

57

Samples

7

6

6

PE, Polyethylene; PET, polyethylene terephthalate; PP, polypropylene; SD, standard deviation.

Table 11.4 displays examples of fossil energy gains induced by the use of recycled commodity polymers instead of the same weight of the equivalent virgin fossil polymer. Apart from errors, the studied polymers are in pellet form, but the actual end-of-life form, the nature of the energy used, recycling method, purity of recyclates, upgrading, etc., are unknown. This explains the standard deviations of one-fifth to one-third of the mean or the median. Obviously, gains are high due to the reuse of the polymer, which otherwise is polymerized from crude oil fractions:

• rPE with a mean gain of 50% and a range of 33% 68%. The range may be induced by the diversity of applications and the high consumption of PE, leading to higher levels of recycling.

• The recycling of PET with a mean gain of 40% is less beneficial for energy consumption than for PE and the range is significantly broader.

• The recycling of polypropylene (PP) with a mean gain of 40% is less beneficial for energy consumption than for PE and the standard deviation is approximately half of PET SD in round figures. Of course, other very different data may be found elsewhere.

11.4.7 Fossil Energy Demand of End Products Based on Reused Materials and/or Recycled Polymers LCA taking into account all the steps of the life cycle, injection, or extrusion, for example, the effect of recycled polymer use is relatively different from that estimated for pellets. For reusable products, a new initial design may be needed, which may lead to higher raw material consumption and higher weight, leading to higher energy consumption for distribution. For example: Lerche Raadal et al. (2003) conducted a life cycle analysis of nonrefilled (NR) bottles (NRPET) and refilled (REF) bottles (REF-PET), but found little difference, to the advantage of nonrefilled bottles:

• Energy consumption for the production and recycling of beverage bottles for NR-PET bottles was 116 kWh per 1000 L beverage and for REF-PET bottles it was 120 kWh per 1000 L beverage.

• Total CO2 emission during the production and recycling for NR-PET bottles was 35.2 kg CO2 per 1000 L beverage and for REF-PET bottles it was 37.6 kg CO2 per 1000 L beverage.

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Table 11.5 Life Cycle Assessment Indicator Comparison of Bottles Made Out of Recycled and Virgin Polyethylene Terephthalate (PET) and Polyethylene (PE). Energy GJ per 1000 kg of Resin

Solid Waste (kg of Waste per 1000 kg of Resin)

GHG (kg per kg of Resin)

rPET

42

272

2

Virgin PET

73

251

2.7

rHDPE

46

148

1.3

Virgin HDPE

84

148

1.8

GHG, Greenhouse gases; HDPE, high-density polyethylene; PET, polyethylene terephthalate; rHDPE, recycled high-density polyethylene; rPET, recycled polyethylene terephthalate.

Table 11.6 Example of Environmental Indicators for Recycled and Virgin Polyethylene Terephthalate (PET). Virgin PET

Recycled PET

Advantage for

Mean

Mean 2 2SD

Mean 1 2SD

NREU

52

26

76

95

Recycled

Abiotic depletion

24.3

12

36

45

Recycled

Human toxicity

1790

1370

2210

4390

Recycled

GWP100

2.9

1.3

4.5

4.06

Uncertainty

Acidification

13.7

3

25

21

Uncertainty

Eutrophication

1.6

0

3.4

1.2

Uncertainty

Terrestrial ecotoxicity

10.7

0

22

12

Uncertainty

Photochemical oxidant formation

0.6

0.2

1

1

Uncertainty

Freshwater aquatic ecotoxicity

285

224

346

58

Virgin

The total impact for the Norwegian market would be a reduction of 7000 t (18%) of CO2 emissions for the NR-PET bottles. This is partly explained by a new design of bottles requiring more raw material for refillable bottles, which leads to a higher weight for the beverage distribution. For the production of bottles, by using 100% PCR resin, the cradle-to-gate energy consumption of the resin compared to virgin is reduced by 52%. FRANKLIN ASSOCIATES (https://plastics. americanchemistry.com/Education-Resources/ Publications/Life-Cycle-Inventory-of-PostconsumerHDPE-and-PET-Recycled-Resin.pdf, 2009) compare LCAs of bottles made out of recycled PET and PE (Table 11.5). Energy and GHG emissions are respectively reduced by 42% and 45%, and 26%

and 28% when using recycled resins. Solid waste emissions are not significantly different.

11.4.8 Example of Inconsistency Between Indicators Relating to a Recycled Polymer Family Table 11.6 displays examples of fossil energy required for recycled (three methods) and virgin PET. The studied polymers are reused in an identical application, while the nature of the energy used, the purity of recyclates, upgrading, etc., are not specified, but are expected to be similar. Data for virgin PET are slightly higher than those previously quoted. Deliberately, units are not quoted. Indicators may be divided into three families:

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Cost saving (%)

50 40 30 20 10 0 LDPE

PP

PS

HDPE

PET bottle

Figure 11.4 Pellets: recycling saves costs.

• Recycling is probably advantageous for nonrenewable energy use, abiotic depletion, and human toxicity.

• There is more or less uncertainty regarding five indicators. GWP, acidification, and photochemical oxidant formation are perhaps advantageous for recycled PET, while eutrophication is perhaps disadvantageous for recycled PET and terrestrial ecotoxicity is perhaps advantageous for recycled PET.

• Recycling is probably disadvantageous for freshwater aquatic ecotoxicity.

11.4.9 Examples of Cost Savings Due to Recycling Fig. 11.4 displays the plastic pellets cost saving percentage when totally replacing virgin polymer with recycled, but, often in real life, only a fraction of the polymer is replaced by a recyclate. Different cost savings may be found according to prices of crude oil and virgin polymers. For the quoted examples, it can be remarked that, according to the polymer, costs savings range between 10% and 40% in round figures. If there is a high demand for recyclates, the prices rise and the converse is true. The prices of polymer and crude oil are highly volatile making these data unusable for economic forecasts.

11.4.10 Example of Environmental Benefits of Recycling a Commodity Plastic: rPVC According to calculations by Axion Recycling, manufacturing new building products from recycled polyvinyl chloride (PVC)-U has about 6% of the

global warming impact of using virgin polymer. In addition to environmental advantages, there are significant cost savings. Collecting and mechanically recycling 1 t of PVC, which can directly substitute virgin polymer in a new application, will generate about 0.120 t of CO2. The latest eco-profile data from Plastics Europe for virgin PVC indicates that producing 1 t of virgin PVC from its primary raw materials (salt and oil) will generate about 1.900 t of CO2. Using recycled PVC creates a 94% saving in CO2 emissions compared to the production of 100% virgin PVC polymer. Please note that recycling produces waste, therefore, the reusable weight of recycled polymers is lower. The 560,000 t of end-of-life PVC that were recycled through Recovinyl during 2016 will have saved up to 1 million tons of CO2 emissions because the majority of this material will have been used in applications that directly substitute virgin polymer.

11.4.11 Recycling, Reuse, or Use Virgin Polymer: The Right Answer Depends on the Actual Context For the same multinational enterprise, the use of recycling and/or reuse depends on the whole context and must be adapted to regulations, local conditions, technical possibilities, economics, habits, etc. For example, PepsiCo claims:

• It was incorporating up to 10% PCR content into its PET plastic, beginning in 2004. Prior to being transformed into a new plastic bottle, the plastic is sorted, cleaned, and tested in accordance with food safety standards.

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• In France, PepsiCo is achieving up to 50%

example, directives dealing with the disposal of end-of-life vehicles. According to the deposit and bill strategy, consumers are charged a small fee when they purchase a product and the fee is refunded when the product is returned after use. Legislation continually evolves and changes with the considered locations, products, etc., and it is the responsibility of the reader to search the ins and outs concerning their own case.

AND

recycled content in individual product lines.

• In Germany, PepsiCo achieved its 2015 goal of utilizing 25% recycled PET in approved bottles in 2013.

• In Canada, 7UP bottles were the first 100% postconsumer content bottles for a carbonated soft drink.

• PepsiCo Brazil is now utilizing 2L PET bottles with 100% rPET for Teem carbonated soft drinks.

• Naked Juice uses 100% PCR PET in its bottles.

• Since 2004, PepsiCo has been incorporating, on average, up to 10% postconsumer rPET in its primary soft-drink containers in the United States

• In 2014, PepsiCo used more than 65,000 t of food-grade rPET in its packaging.

• PepsiCo announced new goals to strive to design 100% of its packaging to be recoverable or recyclable by 2025 and to partner to increase packaging recovery and recycling rates. Remember that recyclable matter is not necessarily recycled.

11.5 Policy, Legislation, Fees, Taxes, Bans, Deposit and Bill Strategies, and the Green Wave Are Real Game-changers Legislation, fees, taxes, bans, deposit and bill approaches may be used to:

• encourage

virgin

or

recycled

plastic

consumption

• dissuade or ban ingredients (e.g., plasticizers) and virgin or recycled plastics use

• control recycled plastics use • boost collection of postconsumer waste and, consequently, increase the recycling rate Legislation linked to other application domains can also interfere with plastics consumption, for

11.5.1 Incentive Legislation Example: Extended Producer Responsibility Extended producer responsibility (EPR) (https:// www.oecd.org/env/tools-evaluation/extendedproducerresponsibility.htm) places the responsibility for the postconsumer phase of certain goods on producers, which assume significant responsibility— financial and/or physical—for the treatment or disposal of postconsumer products.

• Advantages include reduction of wastes, enhancement of product design for the environment, and supporting the achievement of public recycling and materials management goals. Theoretically this principle ensures effective end-of-life collection, environmentsound treatment of collected products, and improved reuse and recycling. Effectively, the collection partially depends on the end user.

• On the other hand, EPR adds all of the environmental costs associated with a product throughout the product life cycle to the market price of that product. EPR may take the form of a reuse, buyback, or recycling program. The producer may also choose to delegate this responsibility to a third party, a socalled producer responsibility organization, which is paid by the producer for used-product management.

11.5.2 Example of Regulation Restraining the Use of Plastics: Carrier Bags For example, regulations strengthen against disposable plastic parts; many countries develop legislation to reduce the use of disposable carrier bags.

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16

Million

14 12 10 8 6 4 2 0 2004

Carrier bags Min Max 2006

2008

2010

2012

2014

2016

2018

Figure 11.5 Carrier bags (number) used in a panel of nations.

Passing mandatory laws as well as their implementation and monitoring usually receive a lot of opposition, but may be efficient and can lead to a noticeable reduction. Fees are also effective. For example, the demand of plastic carrier bags is expected to decrease by 2022 by about 5.3% p.a. in France. Fig. 11.5 shows the expected evolution of carrier bags consumption for an arbitrary panel of industrialized countries having passed mandatory laws, bans, or fees since 2006. Carrier bags made of bioplastics are often exempt from bans and fees, national legislators making explicit references to these products. Yet, composting of these bags in dedicated facilities may pose some problems and composting in natural environments may be ineffective.

11.5.3 Example of Regulation Boosting Recycling: End-of-Life Vehicles Directive 2000/53/EC of the European Parliament and of the Council of September 18, 2000 on end-of-life vehicles lays down rules for the monitoring of the reuse/recovery and reuse/recycling targets for end-of-life vehicles. Member states shall take the necessary measures to ensure that the listed targets are attained by economic operators: 1. By no later than January 1, 2006, for all endof-life vehicles, the reuse and recovery shall be increased to a minimum of 85% by an average weight per vehicle and year. Within the same time limit the reuse and recycling shall be increased to a minimum of 80% by an average weight per vehicle and year.

100 90 80 70 60 50 40 30 20 10 0 2006

2008

2010

Total (%)

2012

2014

2016

Minimum (%)

Maximum (%)

Figure 11.6 EU: percentage of recycling and reuse of end-of-life vehicles. EU, European Union.

For vehicles produced before January 1, 1980, member states may lay down lower targets, but not lower than 75% for reuse/recovery and not lower than 70% for reuse/ recycling. Member states making use of this subparagraph shall inform the Commission and the other member states of the reasons therefore. 2. By no later than January 1, 2015, for all endof-life vehicles, the reuse and recovery shall be increased to a minimum of 95% by an average weight per vehicle and year. Within the same time limit, the reuse and recycling shall be increased to a minimum of 85% by an average weight per vehicle and year. Fig. 11.6 shows the expected recycling and reuse rates for EU27, and countries having the minimum and maximum rating.

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LFRT TPE ETP ETP ETP ETP TPE ETP

%

TPE 0

10

20

30

40

50

60

Figure 11.7 Examples of regrind levels for various thermoplastics.

11.5.4 Example of Recycled Plastics Limitations First of all, recycled plastics as all virgin plastics, must obey national, regional, and global directives, rules, regulations, and other requirements related to the targeted parts, subsets, and devices. Countries to be considered include those of the production, transformation, use, and disposal. That being, the use of recycled plastic may be nonrecommended, limited, or banned according to the actual case. Let us remind examples of limitation of regrind by the UL (but many other rules or regulations exist). UL accepts:

• No regrind for thermosets, thermoplastic elastomers and recycled materials.

• Regrind up to a maximum of 25% by weight with the same grade of virgin thermoplastic at the same molder facility without further testing. For regrind levels exceeding 25% in the same virgin thermoplastic, UL requires a special evaluation of relevant performance tests such as mechanical, flammability and aging tests. Of course, these statements can evolve with time. Producers propose other recommendations. Fig. 11.7 displays some examples of maximum levels recommended by producers for long fiber reinforced thermoplastics (LFRTs), engineering thermoplastics, and TPEs. Maximum levels recommended for LFRTs are low because

of the breakage of long glass fibers (GFs), which leads to a decrease of mechanical performances. For other thermoplastics, levels depend on the sensitivity to hydrolysis and thermo-oxidation and the processing parameters. These indications relate to the regrind of materials carefully processed and cannot be used without severe testing.

11.5.5 Example of “Deposit and Bill” Approach: Beverage Bottles The “deposit,” typically ranging from 5 to 30 US cents, is paid by the buyer. The consumer receives the same amount back when they return the bottle to a collection point. As expected, the higher the deposit, the higher the return level. According to the Container Recycling Institute (http://www.container-recycling.org/), the deposit and bottle bills strategy leads to an average of 76% of recycled carbonated beverage containers, while states without deposit laws recycle only 37% of these containers (2006).

11.6 Renewable Materials: Alternative to Oil Becoming Scarcer and Use of NaturalSourced Materials Two main ways are investigated to replace fossil polymers:

• Mimic traditional polymers using drop-in precursor solutions; many examples are already

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Table 11.7 Environmental Indicator Comparison for Polylactic Acid (PLA) and Melamine (MF) Cups.

Energy consumption

PLA

MF

3 4

9

a

2065

1600

GHG

251

Abiotic depletion

0.006

0.014

Freshwater ecotoxicity

0.04

0.05

Terrestrial ecotoxicity

0.007

0.008

a Disposal with energy recovery. GHG, Greenhouse gases.

described (see Chapter 10: Transition of Plastics to Renewable Feedstock and Raw Materials) such as green PE, biopolyesters, etc.

• Using biobased polymers satisfying to required functionalities; the issue is to find materials with at least the performance of incumbents (or better).

PHB PO

11.6.1 Success Story Examples Taengwathananukool et al. (2013) study the replacement of melamine (MF) with polylactic acid (PLA) for production, use and disposal of cups. Table 11.7 compares PLA and MF cups with comparable units for each indicator. In the case of disposal with energy recovery, all the environmental indicators are favorable to PLA. In the case of disposal without energy recovery, GHG emission is better for the MF cups, but all the other environmental indicators are better for PLA cups. EcoPaXX polyamide 410 made out of 70% tropical castor beans and certified 100% carbon neutral from cradle-to-gate was used to build a body panel for an e-car that was at least 50% lighter than a metal version. In another case, Mercedes-Benz states in the Life Cycle Environmental Certificate for the A-Class that the production of an engine cover in biobased polyamide results in only around 40% of the quantity of CO2 emissions needed to produce the same component from a conventional polyamide. An LCA validated the sustainability of DuPont Sorona. DuPont Sorona polyester contains 37% annually renewable plant-based ingredients by weight. The polymer production uses 30% less nonrenewable energy and reduces GHG emissions by 63% compared to the production of an equal

Figure 11.8 PHB versus PO: comparison of 10 environmental indicators. PHB, Polyhydroxybutyrate; PO, polyolefin.

amount of nylon 6. The LCA also showed that no catalysts containing any heavy metals were used in the polymerization of Sorona. Harding et al. (2007) compare polyhydroxybutyrate (PHB), PP, and PE as for LCA and engineering performance. Fig. 11.8 diagrammatically shows the generally better environmental behavior of natural-sourced PHB versus polyolefins (POs) including PP, highdensity PE, and low-density PE for six environmental indicators:

• GWP100 (kg CO2 equiv.): 1960 for PHB versus about 2510 3530 for POs

• ODP (kg CFC-11 equiv.): 0.00017 for PHB versus about 0.000766 0.0018 for POs

• Photochemical oxidation (kg C2H2): 0.78 for PHB versus about 1.7 17.5 for POs

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• Terrestrial ecotoxicity (kg 1,4-DBeq): 8.98 for

• Second, cold-cement assembly uses less

AND

PHB versus about 33 44 for POs

• Freshwater aquatic ecotoxicity (kg 1,4-DBeq): 106 for PHB versus about 176 234 for POs

• Human toxicity (kg 1,4-DBeq): 857 for PHB versus about 1870 2890 for POs However, four PHB indicators close to those of POs are questionable:

• • • •

EP ADP AP Marine aquatic ecotoxicity

The engineering performances of PHB including service temperatures (230°C to 120°C) can be similar to those of PP under suitable conditions of fabrication and refining.

energy than vulcanization.

• Third, some natural materials such as natural rubber that are thought to cause less environmental damage through cultivation can be more harmful than synthetic materials. For soles:

• For EP, natural rubber data is about 9-times the average of other materials. This high level of eutrophication is due to the intense agricultural processes required to grow rubber trees and to process rubber sap.

• For AP, natural rubber data is about 2.9-times the average of other materials.

• For FAETP, natural rubber data is about 1.5times the average of other materials.

• For GWP, natural rubber data is slightly superior to the average of other materials.

• For HTP, natural rubber data is slightly superior to the average of other materials.

11.6.2 A Questionable Case Ariana Arcenas et al. describe a software, EcosSTEP, aimed at footwear designers (see “The Development of a Standard Tool to Predict the Environmental Impact of Footwear” https://www.bren. ucsb.edu/research/documents/Footprint_finalreport. pdf, March 2010). Once shoe designers enter designs into the model, the inputs are translated into five specific impact potentials:

• • • • •

GWP Human toxicity potential (HTP) AP Freshwater aquatic ecotoxicity potential (FAETP) EP

Designers can choose to view the impacts of one pair of shoes or to compare impacts of multiple pairs to aid their decision-making processes during shoe design. The creation and testing of the model led to several insights regarding materials and assembly:

• First, materials derived from livestock should be avoided in favor of other materials such as cotton and hemp.

11.6.3 A Textbook Case: Replacement of ABS for Lego Bricks The LEGO Group believes a new sustainable material must have an ever-lighter footprint than the material [acrylonitrile-butadiene-styrene (ABS)] it replaces across key environmental and social impact areas such as fossil resource use, human rights, and climate change. The LEGO Group investigated two ways:

• renewable monomers leading to green ABS • new renewable polymers 11.6.3.1 Drop-in Solutions for Green ABS ABS is made out of acrylonitrile, butadiene, and styrene. Several companies are at some time or another active in these fields, for example:

• Renewable acrylonitrile is the less advanced precursor, but some actors are active such as, for example, Cargill that acquired OPX Biotechnologies, which was focused on 3-

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hydroxypropionic acid via fermentation, which is then converted in one step to biobased acrylic acid.

• PE furanoate (PEF) is expected to enter the

• Renewable butadiene is targeted by, for exam-

• PLA, if upgraded to the ABS level could be

ple, without claiming to be exhaustive: Genomatica, Versalis LanzaTech, INVISTA, Arzeda, Global Bioenergies, Synthos, Axens, IFP Energies Nouvelles, Michelin, etc.

• In the area of natural-sourced benzene, toluene, and xylenes, Anellotech targets the processing of nonedible renewable biomass using fluidized-bed reactors.

11.6.3.2 Substitute Biobased Polymers for ABS

market in 2020. PEF is said to feature superior properties. another alternative.

11.7 Ecological Features Boosting the Growth of Plastics General trends toward the mitigation of energy consumption due to lightweighting and better thermal insulation are pushing the use of plastics that are among the materials of choice for the integration of functionality, leading to energy savings at the application step in addition to manufacturing savings.

New biobased polymer(s):

• must have at least a good balance of the properties of ABS, notably the clicking ability, the colorability, and the cosmetic and aging properties

• must allow for new bricks to be blended seamlessly with old ones already in children’s hands

• must be competitive • must come from a nonfood feedstock • must be available from dual (or more) sources, with multiple production locations, so that resin can be provided from another site if there are any problems For instance, polyhydroxyalkanoate (PHA) could be the starting blocks. Among others, Newlight Technologies (https://www.newlight.com/technology/), which has partnered with IKEA, claims its AirCarbon PHA has the potential to replace ABS. (AirCarbon is polymerized from concentrated methane and/or CO2 inserted into Newlight’s polymerization system). Other quoted hypotheses include, without claiming to be exhaustive:

11.7.1 Functionality Integration Due to Design Freedom Chapter 5, Eco-Design Rules for Plastics Sustainability, dealt with the eco-design strategy and only a few rules will be repeated here. From a sustainability point of view, plastics, polymers, and their composites or hybrids offer:

• Design freedom: the realization of parts of all shapes and sizes, which is virtually unfeasible with metals, glass, or wood.

• Integration of several functionalities using property versatilities such as a structural feature allied with collateral properties: damping, shock and noise absorption, heat insulation, electrical insulation, translucence or transparency, rigidity of unidirectional (UD) composites or flexibility of some polyurethanes, thermal stability of silicones, polyimides, etc. The large sizes permitted by certain processing methods and the particular processes of assembly lead to environmental and economic cost reductions in assemblage, to smoother surfaces without rivets or welding, which is favorable to the aesthetic quality and to a greater aerodynamic optimization.

• Oak Ridge National Laboratory (https://www.

• The versatility of production processes allows

ornl.gov/news/ornl-researchers-invent-toughercould plastic-50-percent-renewable-content) provide acrylonitrile-butadiene-lignin in which lignin replaces styrene, but the natural content is limited at this time.

• Coprocessing, comolding, coextrusion, over-

for the adaptation from short run-ups to mass production. molding, etc., offer the possibility to combine two or more polymer materials to ensure

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several functionalities if all the desired characteristics are not brought together in a single polymer. For example, a polyurethane flexible foam and a rigid polyurethane can combine structural and damping properties in the same part.

easily test design efficiency and changes linked to wall thickness, gate location, material, and geometry, and, generally, can evaluate the manufacturability of plastic materials. Software provides simulation and modeling tools for:

AND

• The possibility of selective reinforcement in the direction of stresses by selecting particular composites or by part drawing, which allows for a lightweighting of certain parts of a product.

• The rather short design and production set-up times easing design changes and adaptation to the miniaturization of electronics and other devices.

• Weight reduction due to good mechanical properties being combined with low density. The resulting fuel saving in automotive applications, the labor and handling savings in building and civil engineering, etc. allow for the reduction of operating costs.

• The aesthetics, the possibilities of bulk coloring and in-mold decoration to obtain the aspects of wood, metal, or stone that remove or reduce the finishing operations. Most inmold decoration processes mitigate volatile organic compound emissions.

• The opportunities of repairing thermoplastics and composites permit the recovery of expensive parts after damage.

• The selection of low maintenance solutions allows for energy consumption and pollution to be avoided during the use phase.

11.7.2 Lightweighting: Energy and Resource Savings, Pollution Mitigation 11.7.2.1 Overview of General Plastics Solutions Simulation and modeling tools optimize design and save material, resources, energy, pollution, money, time, etc. Part design is a difficult exercise (see previous chapters) carried out by skilled technical staff and leading to ecological, technical, and economic consequences. Designers, mold makers, and engineers, through simulation setup, modeling, and the resulting interpretation, can more or less

• • • •

plastic part design mechanical performance analysis development of preprocessing models injection molding and a wide range of specialized process applications, that is, gas-assist, coinjection, etc.

• filling, heating, and cooling of plastic materials

• fiber orientation and breakage in plastic part designs

• failure analysis and optimization studies • manufacturability (assembly, operability, etc.) • optimization of noise vibration harshness performance, etc. From a sustainability point of view, software can help manufacture good parts on the first try saving raw material, energy, and other resources. This also mitigates carbon, water, and air footprints, and contributes to the cost-effectiveness of produced items. Performance and durability can be improved, which minimizes later issues. Faster studies allow for the studied cases to increase and/or the costs to be reduced.

11.7.2.2 Environment-Friendly Structural Solutions From an environmental point of view, the optimal solution seems at a first glance to use biosourced matrices and natural reinforcements, but half-solutions can be of interest as a first step, combining biosourced matrices and GF or CF, or combining natural fibers and oil-sourced polymers or alloying fossil and biosourced polymers. For matrices, there are, for example:

• Cellulose, which is the most commonly used natural polymer, but particularly in the textile, paper, and construction industries. However, cellulose acetate and other derivatives are used as structural and aesthetic plastics.

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• Starch-based products and PLA are the second and third most used biopolymers.

• Bio-PE is now available in industrial amounts. • Renewable polyamide (PA); Rilsan Polyamide 11, Pebax, and Platamid are biobased, highperformance polymers produced from renewable resources. Ultramid BALANCE (by BASF) is a PA 6.10 based on an extent of about 60% of sebacic acid, a renewable raw material derived from castor oil.

• Other future biopolymer ways include, for example, the synthesis of polymers using CO2 as a raw material or genetically modified bioplastics. A large number of other polymers, already produced from petroleum, open the door to a multitude of applications from packaging, to automobile, electrical and electronics, wood plastic composite, consumer goods, etc. With the higher costs of oil, biopolymers become more competitive, cost effective, and efficient. Natural fibers for polymer reinforcement are highly diversified, which is due to the versatility of sources, chemical compositions, physical structures, eventual posttreatments, and the cost. Chemically speaking, vegetable fibers are generally made out mainly of cellulose and secondarily of lignin. Theoretically, natural fibers can have similar applications to GFs:

• Short fibers randomly distributed • Long fibers more or less randomly distributed • Arranged continuous fibers including mats, nonwovens, fabrics, etc.

• UD reinforcements, etc. One of the crucial issues is to achieve the right wetting with the polymer matrix, which is the secret of improved performances.

11.7.2.3 The Main Potential Boosters and Brakes for Natural Fiber Reinforced Composites The main potential boosters for natural fiber reinforced composites are LCA and sustainability. Table 11.8 displays examples related to fibers and fiber-reinforced composites. Data are generally favorable, but there are some exceptions induced by fertilizers used for plant growing.

On the other hand, natural fibers suffer of some drawbacks such as, for example:

• the difficulty of ensuring regular supply of large quantities

• higher variations of quality due to the natural origin of vegetal fibers, growing areas, batches, years, and seasons

• • • •

the lower performances compared to fiberglass the high moisture uptake the possible poorer surface aspect of end parts a sensitivity to high temperatures, limiting high-temp applications

• an ultraviolet (UV) resistance, limiting outdoor exposure To a certain extent, lower performances may be compensated for by using a higher weight of composite, but the LCA degrades. The lack of experience, the routine, and a nonqualification in a number of industrial domains are also major obstacles to their application.

11.7.2.4 Fully Renewable Solutions: Natural Fibers and Biosourced Polymers Table 11.9 displays some environmental and engineering properties of PLA reinforced with flax fibers. LCAs are limited to cradle-to-gate gains versus traditional GF reinforced polyester resin. For the use phase of transport applications, actual weight may have a decisive effect on fuel consumption and as a result on the emissions of GHGs and other pollutants. The quoted weight gains, low or even negative (mass increase) before the use phase, may dramatically change in the case of the dynamic use phase. For static applications the actual data should be close to those mentioned. Engineering properties are an example among many others. As another example, the Technical University of Eindhoven has built a two-seat city car with the chassis and bodywork made up of light sandwich panels based on natural fiber flax and Luminy PLA supplied by Total Corbion PLA. The car reaches a top speed of 110 km/h and the battery lasts for up to 240 km. The weight, about 360 kg excluding the battery, is less than half the weight of comparable

Table 11.8 Life Cycle Comparisons of Natural and Glass Fibers (GFs) and Corresponding Reinforced Plastics. Life Cycle of a Natural Fiber Compared to a GF GF

NF

Data

Data

% of GF Data

Energy use (MJ/kg)

48.33

3.64

8

Water chemical oxygen demand (mg/kg)

18.81

2.27

12

SOx emissions (g/kg)

8.79

1.23

14

Water BOD (mg/kg)

1.75

0.36

21

Particulate matter (g/kg)

1.04

0.24

23

CO2 emissions (kg/kg)

2.04

0.66

32

NOx emissions (g/kg)

2.93

1.07

37

Carbon monoxide (CO) emissions (g/kg)

0.80

0.44

55

Phosphates to water (mg/kg)

43.06

233.6

543

Nitrates to water (mg/kg)

14.00

24,481

175,000

According to “Are natural fiber composites environmentally superior to GF-reinforced composites?” S.V. Joshia, L.T. Drzalb, A.K. Mohantyb, S. Arora. Life Cycle Environmental Performance of China Reed Reinforced and GF-Reinforced Transport Pallets GF Pallet

China Reed Pallet

% of GF Composite

Cumulative nonrenewable energy use (MJ)

1400

717

51

CML Greenhouse effect (kg CO2 equiv.)

75.3

40.4

54

Sulfur oxides (SOx) air emissions (g)

289

163

56

CO2 emissions (kg)

73.1

42

57

Eco-indicator 95: carcinogenicity (1027 kg PAH equiv.)

7.11

4.48

63

Eco-indicator 95: acidification (kg SO2 equiv.)

0.65

0.41

63

Water emission: BOD (mg)

414

266

64

NOx air emissions (g)

513

349

68

CO (g)

74.3

54.6

73

BOD, Biochemical oxygen demand; NF, Natural fiber; PAH, Polycyclic aromatic hydrocarbons.

Table 11.9 Property Examples of Flax Fabric Reinforced Polylactic Acid (PLA). Environmental Gains: Examples of Flax Fabric Reinforced PLA Versus Traditional GF Reinforced UP Cradle-to-Gate Gains Gain of weight according to functional unit (%)

3 to 227 (negative data are mass increase)

Gain of nonrenewable energy per functional unit (%)

49 55

Gain of GHG emission (%)

59 60

Examples of Engineering Properties of Biotex Flax Fabric (40% in Volume) Reinforced PLA Tensile elongation (%)

1.6

Flexural modulus (GPa)

7.8

Flexural strength (MPa)

131

2

Charpy impact (kJ/m ) GF, Glass fiber; GHG, greenhouse gases; UP, unsaturated polyester.

30

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production cars. Of course, for the use phase, actual weight has a decisive effect on fuel consumption and as a result on GHG and other pollutant emissions.

density, leading to a noticeable weight saving. Natural fiber densities are in the range 1.3 1.5 versus 2.5 for GF, that is to say, an advantage of about 45%, but the mechanical performance being not so good, the end advantage on various parts is not so high. It can be seen in Table 11.10:

11.7.2.5 Hybrid Solutions Combine Renewable and Fossil Components

• weight savings of 24% to 85% for various

Hybrid solutions combine biosourced polymers reinforced with GFs, or fossil polymers reinforced with natural fibers, or alloys of fossil and biosourced polymers. Fig. 11.9 shows properties of GF-reinforced PLA and PP for comparison: modulus (Mod), tensile strength (TS), and heat deflection temperature are in the same ranges for the same GF level. The second partial solution, fossil polymer reinforced with natural fibers, has the benefit of a lower 15% GF

fossil composites (24% is an increase of the weight).

• weight savings of 0% 27% for various hybrid composites combining renewable and fossil components. Theoretically, weight saving should be higher than 27% (about 40%). Traditional parts used as a basis for comparison may be made out of steel, concrete, plastics, etc., including thermoplastic matrices reinforced with GF or talc. Bcomp (www.bcomp.ch/en/products/powerrib) proposes power Ribs material designed for manufacturing fiber-reinforced composite products with high performance and low environmental impact. This special fabric creates a rib structure on one surface of the composite layer, significantly increasing the flexural stiffness and damping properties of thin composite shells with little additional weight. Table 11.11 displays property examples of power Ribs.

35% GF

200 150 PLA

100 50 15% GF Mod 0 Mod TS

PP

HDT

15% GF

Mod

TS

HDT

35% GF

Figure 11.9 GF-reinforced PLA and PP. GF, Glass fiber; PLA, polylactic acid; PP, polypropylene.

Table 11.10 Examples of Weight Savings (%) Due to Composites. Actual Literature Data All Parts

Traditional Parts (Steel, Concrete, Plastics, etc.)

Hybrid Composites

Fossil Composites

Mean

Base

20

42

0 27

24 to 85 (negative data is an increase of the weight)

Range Detailed Results Conventional Part

Natural Fiber Reinforced Part

Weight Saving (%)

Auto center console

Talc-PP

Sisal-PP

20

Auto insulation panel

GF-PP

Hemp-PP

26

Transport pallet

GF-PP

China reed-PP

22

General purpose parts

Talc-PP

Jute-PP

5 10

GF, Glass fiber; PP, polypropylene.

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Table 11.11 Property Examples of power Ribs. Density (kg/m3)

265.1

363.6

Thickness (mm)

1.6

1.21

Young’s modulus in the wavy ribs direction (GPa)

1.92

3.45

Young’s modulus in the flat ribs direction (GPa)

1.89

2.65

Shear modulus (MPa)

280

280

Poisson’s ratio

0.04

0.04

The natural power Ribs flax grid is environmentfriendly and has comparatively low rates of CO2 emission, water usage, and embodied energy. Compared to CF reinforced plastics, power Ribs composite material (flax fiber reinforced plastics) has significantly lower environmental impact due to its weight advantages and lower material input. Water usage, CO2 footprint, and embodied energy, are about 85% lower while using flax fiber reinforced plastics. For the recycled plastics demonstrator XC60 vehicle by Volco Cars, Bcomp provides its natural fiber reinforcement technology powerRibst using upgraded ocean plastic to form a novel renewable composite material. This enables the use of ocean plastic in semistructural automotive interior parts, and simultaneously cuts to 50% the weight compared to standard parts. Among other companies, Ford, for example, has studied several ways:

• Using PP reinforced with 30% sisal fibers for injection molding. The 30% sisal fiber reinforced parts have already passed the Ford Motor Company crash and head impact test requirements. A center console made using the material weighs 20% less than talc-filled PP. Other advantages include a 20% lower melt temperature and a 10% faster cycle time. However, further work is needed to solve issues in terms of odor and color matching with parts made with nonnatural fibers.

• 50% kenaf fiber reinforced PP is used in the Ford Mondeo, Focus, and Fiesta door panels.

• Ford is also looking at using 30% hemp fiber reinforced PP in electrical/electronic housing and engine compartment applications. Material and component tests also indicated that this type of material is also “close to implementation,” says Ford.

• Another successful use of a sustainable material is Ford’s use of AgriPlas BF20H-31 wheat straw reinforced PP compound from Schulman for the quarter trim bin and inner lid of the storage bins of Ford’s 2010 Flex car.

• Molding trials revealed that the liquid wood can be molded into complex shapes and cutouts. Remaining challenges for liquid wood include optimization for cost-effective industrial production, stable supply, and color management. For the third half-solution, fossil and biosourced plastic alloys, some examples are given to give a rough idea, but data cannot be used for designing:

• Reinforced thermoplastic (RTP) Cy commercializes compounds based on Ingeo PLA including high-impact PLA/ABS (RTP 2099 X 121216G) with 80% biocontent and notched Izod impacts of 135 J/m, competitive with high-impact polystyrene (PS). A 30% glassfilled, nucleated PLA (RTP 2099 X 124752B) with 70% biocontent bridges the gap between a glass-filled PP and a glass-filled nylon 6. Good long-term heat and humidity resistances are also claimed.

• A number of polymer blends containing PLA and acetals, along with additional additives and fillers have been patented. Good heat resistance and other properties have been claimed. In addition, blends containing up to 30% acetal are reported to be transparent. Acetals are unstable in the presence of acid, which can be generated during the processing of PLA, and it is recommended that buffers or neutralizing agents be considered for these blends.

• Polycarbonate (PC) is combined with PLA to take advantage of its heat resistance and

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Table 11.12 Property Examples of Unreinforced Terraloy With 40% Biocontent. Biocontent

40

Flexural modulus (MPa)

82 86

TS (MPa)

20 26

Tensile elongation (%)

500 520

TS, Tensile strength.

toughness. PC is also easy to modify with nonhalogenated fire retardants (FRs). Fujitsu and Toray have developed an FR resin made of a blend of PC and PLA (50/50) designed for notebook computers. This composition is claimed to have the processability, heat resistance, and flame resistance required in larger IT devices. The incorporation of high levels of PC into PLA (greater than 50%) requires processing temperatures close to the thermal decomposition temperature of PLA, making it difficult to prepare these types of blends. Low levels of PC (e.g., 20%) result in opaque blends with properties similar to PLA.

• Teknor Apex proposes Terraloy based on thermoplastic starch or PLA. Table 11.12 displays the properties for soft grades. A typical grade based on PLA, Terraloy BP34001D with a renewable content of 78%, exhibits a heat distortion temperature of 112°C and Izod impact strength of 135 J/m. By comparison, approximate values for a PLA grade are 65°C and 33 J/m respectively.

11.7.2.6 Sustainable Solutions Based on “Unsustainable” Composites Sustainability of a system is the accumulation of the sustainability of each step from the production up to the end-of-life. So a material unsustainable at the production step can saves enough energy during the use phase to make the overall system sustainable. CF production is estimated to be much more energy-intensive than conventional metal production, but according to the intended application, the primary energy of the life cycle may be estimated to be quite beneficial. The Boeing 787 makes greater use of composite materials in its airframe and primary structure

than any previous Boeing commercial airplane. Undertaking the design process without preconceived ideas enabled Boeing engineers to specify the optimum material for specific applications throughout the airframe. The result is an airframe comprising of nearly half CF reinforced plastic and other composites. This approach offers:

• weight savings on average of 20% compared to more conventional aluminum designs

• about 20% more fuel efficiency than the previous aircraft in the same class

• GHG reduction linked to weight reduction and gain of fuel efficiency

• aircraft maintenance cost saving of around 30%

• the option to perform bonded composite repairs For another case, air cargo containers, also known as unit load devices, were usually made of aluminum, but weight, fuel, CO2 emission, and money could be saved by switching over to CF air cargo containers. According to a recent study:

• CF composite container weight saving may be up to 40%, leading to fuel saving and GHG emission reduction

• Overspending is 36% • ROI is about 1 year or less 11.7.2.7 Automotive: A Promising Domain for Traditional Fossil Plastics Plastics, composites, and multimaterial structures are promising ways for next weight savings inducing fuel economy, CO 2 emission mitigation, and reduction of nonrenewable fuel depletion.

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For the period of 2017 2025, organizations such as Environmental Protection Agency (EPA) and National Highway Traffic Safety Administration (NHTSA) consider that a 10% weight reduction corresponds to roughly a 5% decrease in fuel consumption without downsizing powertrains, which leads to higher performances. If the rest of the car is adapted to maintain the same performances, an over lightweighting would be on the order of 1% 2%, that is to say, a total of 6% 7% fuel economy. Of course, the emission variation of CO2 for the use phase is in the same order. A tolerable overcost could be about $1.5 $3.5/kg reduction. The use of plastics, composites, and hybrids is slowed due to several reasons including:

For the past few years, the weight reduction percentage of new models has been about 10% on average for a range of 4% 15%. A few examples of plastics, composites, and hybrid parts include, but is not limited to:

AND

• Cost of materials • Low production rate for technologies coming from aerospace

• Competition with high-strength steel, aluminum, and magnesium

• Poor image of plastics On the other hand, plastics and composites open the way for introducing multiple functionalities, that is, mechanical functions, vibration control, aesthetics, insulation, transparency, acoustics, etc. In the end, this leads to an affordable total price. Potential applications, without claiming to be exhaustive, include:

• • • • • • • • • • • • • • •

Bumper carriers Pedestrian beams Engine cradles Front-end carriers Instrument panel carriers Seating hatchback structures Underbodies Instrument panel toppers Tunnel covers Door panel inserts Headliners Parcel shelves Load floors Seat back covers Trunk liners

• Magna International, in cooperation with Ford Motor Company, developed a prototype CF composite subframe that reduces mass by 34% compared to making a stamped steel equivalent, and achieves an 87% reduction in the number of parts. The moldings are joined by adhesive bonding and structural rivets.

• Long GF reinforced PP, when replacing metal, saves about 50% in weight in front-end modules, door modules, inner tailgate components, and instrument panels.

• A fender made of thermoplastic saves about 60% weight versus a steel fender.

• Lexan PC automotive glazing is a weight reducing technology that can also improve the thermal insulation with the potential to reduce the load on heating, ventilation, and air conditioning systems. Computer simulations show, for example, that PC glazing can cut emissions by as much as 3 g CO2/km.

• Aachen Center for Integrative Lightweight Production and its partner companies BMW AG and Al. combine thermosetting and thermoplastic fiber reinforced plastic (FRP) using a technique suitable for large series automobile production. The potential savings in material and operating costs throughout the process chain are approximately 20%.

• The “one-shot technology” developed by Audi AG directly combines continuous fiberreinforced profiles with short fiber reinforced molding materials. Structures manufactured using this technology are typically 15% 25% lighter than the comparable parts made from aluminum, and 50% 60% lighter than those made from high-strength steel.

• Car doors made with GF reinforced PP UDMAX GPP (SABIC) for internal combustion powertrains achieved a lower GWP than steel (26%), aluminum (21%), and magnesium (37%). For cumulative energy demand, the thermoplastic composite doors also achieve low levels, that is, 10% less than

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steel, 13% less than aluminum, and 26% less than magnesium for the internal combustion powertrain. Key reasons for these results begin with the lighter weight of the UDMAX GPP based laminate as part of the application, being 40% lighter versus steel, 15% lighter versus aluminum, and 7% lighter versus magnesium. More specifically, for car fuel systems the use of plastics allows for:

• Weight reduction leading to fuel economy and lower CO2 emissions; an average plastic tank gains about 30% weight versus a steel tank

• Design freedom; plastic fuel tanks can fit in the space of the car chassis, thus, increasing fuel storage capacity

• Corrosion resistance • Noise attenuation mitigating the slosh impact • Cost-effectiveness

• For a trailer made of traditional GRP and plywood, the weight savings could be approximately 18% when made with organosandwich materials. Remember that for a full-size trailer, fuel savings are about 6% 8% per 10% reduction in trailer weight. Traditional Composites

Fiberline composites (https://fiberline.com/) reduce the weight of a lifting yoke used for installing individual blades on offshore wind turbines by 75% due to the system being redesigned using GRP profiles instead of steel. Daniel (2003) compares five materials including GFRP, painted steel, and concrete. Table 11.13 displays some results proving that no solution is perfect:

• GFRP is the lightest and the least energy consuming, but is the costliest

• Painted structural steel is the most demanding on energy, weighs more than GFRP, is costlier than concrete, and is the costliest in maintenance

11.7.2.8 Composites Save Weight and Mitigate Pollution Organosandwich

EconCore, ThermHex Waben, and Fraunhofer (http://www.econcore.com/en/technology/thermhex) have launched lightweight and stiff organosandwich materials combining PP honeycombs with GF reinforced plastic (GFRP) faces. The continuous process connects the production module fabricating the honeycomb core with the in-line bonding of skins. For example:

• The honeycomb core panels are claimed to be 22% lighter than solid-core composite panels.

• A trailer built with organosandwich made of a PP honeycomb core with PP/GF composite skins could be 60% lighter than a traditional glass reinforced plastic (GRP) laminated plywood.

• Concrete is the heaviest, but the cheapest For emitted pollution also, no solution is prevailing. For instance, considering cadmium, copper, manganese, mercury, zinc, and cobalt, concrete is the best in three cases, and GFRP and steel are the best in the other two cases. TRB Lightweight Structures Ltd (http://trbls. com/) offers the rail industry a sustainable, biocomposite material option for carriage door leaves at a comparable cost to aluminum bonded door leaves with a 35% weight saving. This biocomposite meets the demanding fire, smoke, and toxic fumes specifications in subterranean rail applications. It is based on a polyfurfuryl alcohol resin derived from a renewable alcohol produced from a natural waste

Table 11.13 Footbridge: Environmental and Economical Features. Mass (kg)

Energy (MJ)

Initial Costs (h)

Maintenance (h)

GFRP (GF/UP)

4000

120,000

70,000

17,000

Painted structural steel

6000

294,000

40,000

30,000

Concrete

28,000

277,200

30,000

10,000

GFRP, Glass fiber reinforced plastic; UP, unsaturated polyester.

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by-product from refined sugar production. The foam core of the composite structure is produced from 100% recycled consumer plastic. The manufacture does not use volatile organic solvents.

including type of aircraft, used materials, running conditions, etc. Generally speaking, a few examples give a rough idea of the issue without claiming to be exhaustive and, of course, different data may be quoted for different cases:

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11.7.2.9 Mobility Solution Examples According to the International Energy Agency (IEA), nearly 26% of the global energy production and nearly 58% of the global oil production have been consumed by transport in 2001. In the industrialized OECD (Organisation for Economic Cooperation and Development) countries even one-third of the energy is consumed by transport. The lightweighting of transport vehicles is an important method to reduce the energy consumption and the CO2 emissions caused by the transport sector. The whole energy chain is reduced including, of course, the direct consumption of the vehicle, but also all upstream processes during the entire operational lifetime of the vehicle. All fuels are affected including electricity and nuclear sources. Following approximate data, here is a rough idea of CO2 emissions per carried units:

• • • • •

20 for railway 50 for bus 110 for aircraft

• A 1% reduction in weight should lead to an approximate 0.75% fuel saving.

• The cost of carrying 1 kg extra in weight can be up to $300 in fuel over 5000 flying hours.

• For 1 kg weight saving the fuel saving during the total life is expected to be on the order of 4 t and CO2 emissions are reduced by about 12 t.

• The use of composites in one new aircraft has generated a weight saving of 20% over traditional aluminum alloys.

• One major airline has saved over 300 kg per aircraft with new lightweight seating and innovative seat design. The new seats weigh under 10 kg resulting in the airline being able to save over 600 kg per aircraft, that is to say, a 0.1 weight reduction in round figures and a 0.075% fuel reduction.

• CO2 emission may be increased in the material production phase, but the total CO2 emission is reduced. Using 1 t of CF to build an aircraft should reduce CO2 emission by 1400 t for the total life of an aircraft.

170 for cars

Road Transportation

380 and more for trucks and so on

Weight and fuel efficiency are closely tied together. Fuel consumption, CO2 emission, lightweighting, and total cost evolutions depend on many parameters including type of vehicle, used materials, and running conditions such as city or road travels, etc. In addition to performance, light materials must be suitable for mass production and overspending is not tolerable or very low. Every weight saving results in a lower fuel consumption, a cheaper fuel cost, and a lighter carbon footprint. For some lightweight materials, CO2 emission may be increased in the material production phase, but the total CO2 emission will be reduced. Generally speaking, the examples listed below give a rough idea of the issue, without claiming to be exhaustive, and noting that different data may be quoted for different cases:

These figures are only examples and of course different data may be found in the literature taking into account different running conditions, vehicle design, type of travel, etc. Lightweighting may be obtained in to two main ways:

• Design • Use of lightweight performing materials and plastics composites, among others. Aircraft

Weight and fuel efficiency are closely tied together. Every increase in weight results in a higher fuel consumption, a fuel cost increase, and a broader carbon footprint. Fuel consumption, CO2 emission, lightweighting, total cost evolutions depend on many parameters

• For the period of 2017 25 rulemaking, EPA, and NHTSA found that a 10% weight reduction corresponds to roughly a 5% decrease in

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fuel consumption with an improvement of performance. The agencies estimate that downsizing powertrains and other components to maintain performance on a lightweighted vehicle would result in a 6% 8% saving in fuel consumption.

• CF should reduce, by 5 t, the CO2 emission if it were applied to average automobiles.

• Plastics and GF composites should induce a 20% weight saving, while CF composites should save up to 50% weight.

• Over the next two decades, the cost decline for automotive CF applications is expected to be from h42/kg currently to h23 in a conservative cost scenario and h14 in an optimistic cost scenario by 2030.

• For the past few years, the weight reduction

• In Europe, the average emissions of all models

percentage of new models has been about 10% on average for a range of 4% 15%

sold by carmakers in 1 year needs to drop from about 140 g CO2 per kilometer to 95 g in 2020 and to 75 g (possibly less) in 2025 and beyond (with some exceptions/adaptations regarding the vehicle class).

• A number of lightweight materials are now in production including high-strength steels, aluminum alloys, magnesium, plastics, composites, and hybrids.

• A single-piece front bumper energy absorber made from a polycarbonate/polybutylene terephthalate blend is claimed to be 40% lighter and 10% less costly than a comparable part made out of steel.

• Long GF reinforced PP when replacing metal saves about 50% in weight in front-end modules, door modules, inner tailgate components, and instrument panels.

• A fender made of thermoplastic saves about 60% weight versus a steel fender.

• Carmakers will be willing to pay up to h20/kg saved depending on the powertrain or vehicle segment.

• A study found that for every 100 kg reduction, the combined city/highway fuel consumption could decrease by about 0.3 L/100 km for cars and about 0.4 L/100 km for light trucks.

• Another study estimates the fuel cost saving to be $65 $85 for a 10 kg weight reduction for cars and light trucks. Marine

Gurit (www.gurit.com/-/media/.../gurit-delegatepack-composite-work-boats) studies the case of a passenger ferry (20 m, 22 kn, 150 persons) highlighting the high cost of CFRP per kilogram mitigated by a lower weight and made profitable through fuel savings. Percent price increases and savings are linked to the equivalent ferry made of metal alloy (see Table 11.14).

Table 11.14 Economics of Alloy and Composite Ferries.

Full load total (kg)

Alloy

GFRP

CFRP

43,817

39,290

35,085

210

220

2,853,867

3,076,366

111

120

25

61

192

1370

Weight saving (%) Total vessel sell price ($)

2,562,364

Price increase (%) Material cost ($/kg)

13

Price increase (%) Annual fuel burn (L)

525,410

471,703

415,009

Annual fuel cost ($)

493,275

442,852

389,626

210

221

12,500,000

11,500,000

24%

211%

Fuel cost saving (%) Full life cost about ($)

13,000,000

Full life cost Saving (%) GFRP, Glass fiber reinforced plastic; CFRP, carbon fiber reinforced polymers.

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According to another example for a 40 m Catamaran ferry, due to the use of plastics and composites, the reduction of CO2 could be about 40% and the reduction of NOx could be approximately 50%. For high-speed passenger vessels, ranging from 20 to 40 m in length, the structural weight should be reduced by 40% over aluminum, cutting fuel consumption by up to 40%.

• Making damping parts • Increasing flexibility • Reducing material weight while partly preserv-

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Railway

Mass distribution of a modern multiple unit train weighing 93 t is on the order of about:

• Car bodies: 20% • Interior: 17% • Others: 63% Mass per seat may be reduced by increasing the number of passengers (double deck, wide body, reduction of unnecessary space, etc.). For example, mass per seat may vary from about 400 to about 1300 according to the design and materials used for 325 650 seats. For a current version of a high-speed train, there are 75% more seats and 14% lower mass per train versus the preceding version, resulting in significantly enhanced speed, comfort, and energy performance. Please note those performances result from all the improvements, not lightweighting only. The Great Britain Business Plan forecasts potential savings over d11 million at present, and over d31 million by the end of Control Period 6 (CP6). In carbon terms, saving over 37,000 t of carbon in CP5 and nearly 86,000 t over both CP5 (from April 1, 2014 to March 31, 2019) and CP6 (from April 1, 2019 to March 31, 2024).

11.7.3 Take Advantage of the Unique Insulation Efficiency of Plastics Foams: “Zero Energy” Housing Examples and Others Unlike industrial solid polymers, which are processed as carefully as possible to avoid the formation of bubbles, vacuoles, etc., alveolar materials result from the desire to introduce, in a controlled way, a certain proportion of voids with the aim of:

• Improving the thermal and/or phonic insulating character

ing the structural properties The intrinsic properties come from those of the polymer with some disadvantages:

• A reduction in the mechanical properties due to the small quantity of material and the strong proportion of gas.

• A reduction in the chemical behavior due to the highly divided nature of the material. The thin cell walls immediately absorb liquids and gases and are rapidly damaged. Polymer foams have a 55% share of the market for insulation materials in building and construction for multiple applications including, for example, thermal insulation, soundproofing; heat insulation of roofs, walls, ceilings, floors, sandwich panels, refrigerating pipes, cold stores, district heating pipes, and oil tanks and pipelines. Fossil polymer foams are well established, but natural-sourced foams are emerging. Almost all plastics may be produced in foams. Some can be used to construct or modernize buildings and apartments saving energy and pollution. Now the trend toward zero-heating houses may be followed due to the energy-efficient modernization of old buildings or the construction of environment-friendly new homes or commercial buildings. Building must be well lined with traditional foams or advanced thermal insulation panels made of new foams containing tiny graphite particles that reflect thermal radiation. Windows are advantageously triple-glazed and are filled with an inert gas between the panes. As for other plastics applications, renewable solutions are emerging or actively investigated according to three main ways:

• Recycled polymers • For example, according to EPS Industry Alliance, more than 59,000 t of EPS were recycled in the United States during 2016. This figure includes 53% of postconsumer packaging and 47% of postindustrial recovery. • The Envirofoam Sustain range of formulated polyols (by IFS) are derived from recycled

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vegetable oils. For example, Enviropol R201 has been independently analyzed and found to have a biobased content of 86%. This product is used to produce a fully formulated polyol component with 45% 60% biobased content and is currently being supplied to manufacturers of polyurethane for cold-room panels, commercial refrigerators, hot water storage appliances, structural insulated panels and supermarket display cabinets.

• Natural polymers • For example: • The Mater-Bi Wave foam sheet is an alternative to polystyrene, polyurethane, and PE foams commonly used in protection packaging. Starch is expanded using water, extruded into sheets, and then assembled into blocks that can be cut into any shape. Mater-Bi Wave has a robust and resilient closed-cell structure. Sheets and blocks are available in different sizes with densities from 30 to 400 kg/m3. • Synbra Group launched the production of BioFoam based on PLA developed by Sulzer Chemtech and Purac Biochem. BioFoam will be positioned complementarily to the wide range of polystyrene foam products offered today. The process of molding is adapted to suit the expansion of the raw beads (called BioBeads) in existing EPS shape molding equipment. The reduction of CO2 emission compared to expanded PS could be as high as 60% 70%.

• Bioblocks used to synthetize biopolymers mimicking fossil ones or leading to innovative macromolecules. For example: • Biopolyols, natural oil polyols or vegetable oil polyols, and PP carbonate polyols can partly replace petroleum-based components. The used level can vary from less than 20% to more than 60% (possibly 100%) of the polyols according to the targeted properties. • The use of Braskem’s Green PE in the production of 1 t of Sealed Air’s foam equates to 3.09 t of CO2 captured from the atmosphere. Thermal insulation made from foams, thermoplastic window frames, etc., help to reduce heat

loss. This is important in cold countries because domestic heating can represent almost one-quarter of the total energy consumption. Consequently:

• fuel consumption is reduced • natural resources are preserved Of course, insulation is also a main solution for the mitigation of the environment impact of air conditioning, cold warehouses, etc., in warm climates. CO2 emission is highly reduced (by two- to fivetimes) even taking into account the CO2 emissions from plastic production. For example:

• BASF quotes the case of the new row houses in Ludwigshafen. Energy efficiency lies in thermal insulation with Neopor panels up to 60 cm thick and triple-glazed windows filled with inert gas. This combined with a controlled ventilation system with thermal recovery and a small block-type thermal power generator provide a one-liter house with electricity and hot water.

• For XPS (extruded polystyrene) foam, Owens Corning quotes (http://www.wilkeseastna.org/ files/Owens_Corning_Life_Cycle_Analysis_ Sept%2024%202007.pdf) examples of residential and commercial US buildings insulated with XPS foam. The use of the foam results in significantly lower use-phase energy and other environmental impacts. The use phase savings dominate most of the environmental categories. The GWP reductions associated with the energy savings due to use of foam are more than sufficient to offset the impacts of the manufacturing process and the small releases of blowing agent over the installed life of the foam.

• For spray polyurethane foams, Bayer quotes (http://www.resnet.us/blog/wp-content/uploads/ 2013/03/SPFA-LCA-Resnet-3-1-13.pdf) environmental payback periods of about 0.4 years to about 8 years according to the foam, building type, building location, considered environmental indicator, etc.

• For the past few decades, passive solar building and house design have demonstrated heating energy consumption reductions of up to

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90% in many locations without active energy harvesting. The additional construction cost for materials is claimed to be low or negligible versus equivalent conventional buildings.

smoke emission with constraints concerning the opacity, toxicity, and corrosivity of fumes.

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11.8 Examples of Bottlenecks for the Growth of Plastics Many technical, economical, regulatory, safety etc. features may penalize the use of plastics. Let us briefly overview three different examples:

• Fire behavior is an old, but actual issue, extensively studied, but unsatisfactorily solved.

• Nanomaterials are more current and their real hazards are not completely known even if they have been used in their traditional form from a long time.

• 3D printing is a new technology aimed at audiences from average people to plastics experts through to specialists from other areas.

11.8.1 Fire Behavior In the United States alone, it is estimated that there are approximately 400,000 residential fires each year, 20% involving electrical distribution and appliances and another 10% concerning upholstered furniture and mattresses. These fires kill about 4000 people, injure another 20,000 people, and result in property losses totaling about US$4.5 billion. Across Europe, fires kill 5000 people (see Chapter 2: Plastics overview: Outline of the Current Situation of Plastics). This brief overview shows the need of FR plastics in such sectors as electrical and electronics, building and construction, automobile, etc., and moreover, it is pointed out that the use of flame retardant materials had cut fire deaths by 20% in the past few years, although there is a marked increase in the number of electric and electronic devices in every home. Usual polymers are based on carbon and are potential fuels more or less easily flammable. Please note that fire retardancy does not mean nonflammable, noncombustible, unburnable, and so on. Fire behavior is complex for several reasons:

• Technically: it is necessary to converge on a difficult balance of fire retardancy and low

• Legally: standards, regulations, and specifications are complex and evolving and vary according to country and industrial sector. Certain fire-retardant solutions may be restricted or banned by some nations, application sectors, or even companies.

• Environmentally: fire-retardant solutions use special chemical entities entailing special environmental consequences. Certain solutions may induce health hazards/risks.

• Economically: fire-retardant grades are costlier versions.

• Fire retardants can modify mechanical properties and aesthetics, etc. Fire behavior depends, initially, on the nature of the polymer. However, the use of fire-proofing agents, special plasticizers, and specific fillers can modify this behavior significantly. Finally, plastics are based on carbon and may be decomposed by heating, which frees gases more or less combustible (and possibly toxic and corrosive). To give a rough idea of the subject, 29 Standards and/or projects under the direct responsibility of the ISO/TC 61/SC 4 Secretariat “Burning behavior” deal with the burning behavior of plastics in general. Of course, many other subjects should be taken into account linked to end products for all application fields (fire classification of construction products and building elements, Federal Aviation Regulations or FARs, etc.), other ISO TC groups, other standard systems (ASTM, etc.), professional requirements (Airbus, Boeing, etc.), etc. Standards and/or projects under the direct responsibility of the ISO/TC 61/SC 4 Secretariat include:

• ISO 871:2006 Plastics—Determination of ignition temperature using a hot-air furnace

• ISO 4589-1:2017 Plastics—Determination of burning behaviour by oxygen index—Part 1: General requirements

• ISO 4589-2:2017 Plastics—Determination of burning behaviour by oxygen index—Part 2: Ambient-temperature test

• ISO 4589-3:2017 Plastics—Determination of burning behaviour by oxygen index—Part 3: Elevated-temperature test

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• ISO/AWI

4589-4 [Under development] Plastics—Determination of burning behaviour by oxygen index—Part 4: High flow velocity test

• ISO 13927:2015 Plastics—Simple heat release

• ISO 5659-2:2017 Plastics—Smoke genera-

use of intermediate-scale fire tests for plastics products—Part 1: General guidance

tion—Part 2: Determination of optical density by a single-chamber test

• ISO

9772:2012 Cellular plastics— Determination of horizontal burning characteristics of small specimens subjected to a small flame

• ISO 9773:1998 Plastics—Determination of burning behaviour of thin flexible vertical specimens in contact with a small-flame ignition source

• ISO 9773:1998/Amd 1:2003 Specimens • ISO 9994:2018 Lighters—Safety specification • ISO/DIS 9994 [Under development] Lighters—Safety specification

• ISO/PRF TR 10093 [Under development] Plastics—Fire tests—Standard ignition sources

• ISO/TR 10093:2017 Plastics—Fire tests— Standard ignition sources

• ISO 10840:2008 Plastics—Guidance for the use of standard fire tests

• ISO 11907-1:1998 Plastics—Smoke generation—Determination of the corrosivity of fire effluents—Part 1: Guidance

• ISO/DIS 11907-1 [Under development] • Plastics—Smoke generation—Determination of the corrosivity of fire effluents—Part 1: General requirements and applicability

• ISO 11907-2:1995 Plastics—Smoke generation—Determination of the corrosivity of fire effluents—Part 2: Static method

• ISO 11907-3:1998 Plastics—Smoke generation—Determination of the corrosivity of fire effluents—Part 3: Dynamic decomposition method using a travelling furnace

• ISO 11907-4:1998 Plastics—Smoke generation—Determination of the corrosivity of fire effluents—Part 4: Dynamic decomposition method using a conical radiant heater

• ISO 12992:2017 Plastics—Vertical flame spread determination for film and sheet

test using a conical radiant heater and a thermopile detector

• ISO 15791-1:2014 Plastics—Development and • ISO/TS 15791-2:2017 Plastics—Development and use of intermediate-scale fire tests for plastics products—Part 2: Use of intermediatescale tests for semi-finished and finished products

• ISO/DTR

20118 [Under development] Guidance on fire characteristics and fire performance of PVC materials used in building applications

• ISO 21367:2007 Plastics—Reaction to fire— Test method for flame spread and combustion product release from vertically oriented specimens

• ISO 22702:2003 Utility lighters—General consumer-safety requirements

• ISO/DIS 22702 [Under development] Utility lighters—Safety specifications

• ISO 25762:2009 Plastics—Guidance on the assessment of the fire characteristics and fire performance of fibre-reinforced polymer composites

• ISO 30021:2013 Plastics—Burning behaviour—Intermediate-scale fire-resistance testing of fiber-reinforced polymer composites Previous information is only of samples and many other standards must be searched for, consulted, and studied by the reader.

11.8.2 Nanomaterials Nanotechnology is an emerging and rapidly expanding technology of which the effects on humans and the environment are not fully known. The ultimate division of the material promotes additional and unfamiliar risks for all stakeholders meaning that designers, workers, users, etc., must be careful of new regulations concerning their use. There is currently little available information on the fire, explosion, and health risks of nanopowders. Consequently, each potential user must specifically

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study their own case. For an example of general information, the European Union information agency for Occupational Safety and Health Administration (EU-OSHA), expects that there are significant concerns regarding the health effects of nanomaterials. The Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR) found that there were proven health hazards associated with a number of manufactured nanomaterials. A lot of projects (https://nanopartikel.info/en/projects/) include funding research and development projects, and data bases (for instance, DaNa 2.0 “Data and knowledge on Nanomaterials”) on the topic of synthetic nanoparticles. Not all nanomaterials necessarily have a toxic effect, however, a case-by-case approach is necessary while ongoing research continues. Global, national, and local regulations are numerous and evolutionary and it is the responsibility of the designer to verify the suitability and the compliance of the studied solutions. It must be remarked that nanomaterials are also subjected to other general regulations such as food contact, for example.

• Skin or respiratory irritants/sensitizers; certain

AND

11.8.3 3D Printing and Other Additive Manufacturing Techniques 3D printing is a set of new technologies using plastics and aimed at all audiences from average people to plastics experts through to specialists from other areas and those that are ignorant of plastics technology. Studies suggest that 3D printers are capable of generating potentially harmful:

• concentrations of ultrafine particles • chemical vapors during the printing process and through postprinting treatments

• exposure to processing conditions Inhalation and related systemic exposure to hazardous agents may potentially include:

• Ultrafine particle clouds and fumes in the nanoparticle range. Nanoparticles can possibly penetrate, interact with, and/or traverse the skin, lungs, nervous and brain tissues, etc., at the cellular level.

thermoplastics and photopolymers when activated by heat or UV light may contain toxic or hazardous monomers. Heat, UV light, and other parameters may also pose a hazard to the eyes, skin, etc.

• Support materials may also pose some hazards. The Danish Environmental Protection Agency has published (May 2017) a study “Risk Assessment of 3D Printers and 3D Printed Products” (https://www2.mst.dk/Udgiv/publications/2017/05/978-87-93614-00-0.pdf) with conclusions for fused deposition modeling 3D printing, on the emission of particles (including ultrafine particles) and volatile components according to the used plastic (PLA, ABS, PA).

11.9 Where We Stand Today: Global, Regional, Sectorial Inequalities 11.9.1 Global Landscape Data for some indicators, for example, waste of plastics, are rare, vague, and questionable, meaning that different figures may be found elsewhere. In 2016, according to the World Bank, global annual waste generation was expected to be:

• 2 billion tons as a whole. Without urgent action, global waste generation will increase by 70% of the current levels by 2050.

• 242 million tons of plastics, that is to say about: • 12% of total waste • 70% of plastics consumption in round figures Fig. 11.10 shows another evolution overview of plastics consumption, (identified) waste generation, and recovery, pointing out low levels of total recovery. This poor image hides different situations and opens the door to more promising forecasts. Fig. 11.11A and B plot historical data for plastics recycling, recovery, and landfilling at the

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350

MT

300 250 200

Plastics consumption

150

Waste generation

100

Total recovery

50 0 1985

1990

1995

2000

2005

2010

2015

2020

Figure 11.10 Plastics: Global consumption, waste, and recovery.

(A) 90% 80%

%

70%

Landfilled

60% 50%

Energy recovery

40% 30%

Recycled

20% 10% 0% 1985

1990

1995

2000

2005

2010

2015

2020

(B) 60% 50% 40%

Recycling

30%

Energy recovery

20%

Landfill

10% 0% 2004

2006

2008

2010

2012

2014

2016

Figure 11.11 (A) Global plastics waste: share of recovery, recycling, and landfilling. (B) EU plastics waste: share of recovery, recycling, and landfilling. EU, European Union.

global level and in the European Union, showing rises of recycling and energy recovery when landfilling, the worst solution, decreases. The trends are clearer for the European Union. Of course, the progress margin is enormous. These figures are linked to a multitude of nations, which obscures the promising results of the more advanced countries.

11.9.2 Plastics Waste Treatment: Promising Results of Advanced Countries Table 11.15 displays the results of the best performing countries, the whole panel of 29 countries, and the worst performing countries listed by the

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Table 11.15 Distribution (%) by Plastics Waste Category. Recycling and Composting (%)

Incineration With Energy Recovery (%)

Incineration and Landfill (%) 15

Ten Most Performing Countries Mean

54

31

Median

53

35

Standard deviation

6.1

17.8

16.8

Minimum

45

1

0

Maximum

65

50

50

Countries

10

10

10

8.5

Panel of 29 Countries Mean

38

25

36

Median

40

21

36

Standard deviation

15

20

28

Minimum

1

0

0

Maximum

65

71

99

Countries

29

29

29

About 15

About 70

5

5

Ten Less Performing Countries Mean

14

Median

19

Standard deviation

9.1

Minimum

1

Maximum

24

Countries

10

same sources of statistical data. Of course, the panel of 29 countries does not reflect the totality of nations, meaning that other different figures can be found elsewhere. It can be expected that unlisted countries are not high performing from an environmental point of view. That being said, the progress margins are broad:

• From 38% to at least 54% or more for the average recycling rate, with the most developed countries being able to advance further.

• From 25% to 31% for average incineration with energy recovery rate.

• Reductions from 36% down to 15% for landfilling, the worse waste solution. Furthermore, the progress margins of worse performing countries are even more exciting:

• From 14% to 54% for average recycling rate, that is to say nearly four-times

• From 15% up to 31% for average incineration with energy recovery rate

• Reductions from 70% down to 15% for landfilling, the worse waste solution.

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Table 11.16 Europe: Wastes of Building and Construction Sector. Waste Generation (kt)

Mechanical Recycling (%)

Energy Recovery (%)

Landfilling (%)

PVC

840

32

30

38

PE

160

24

49

27

PP

60

18

52

30

PS

150

7

58

35

Others

248

7

73

20

Total

1458

24

43

33

PE, Polyethylene; PP, polypropylene; PS, polystyrene; PVC, polyvinyl chloride.

11.9.3 Brief Jumble of Facts and Figures

• For 13 studies: Incineration with energy recov-

From 2006 to 2016, for a panel of more than 20 countries:

• Landfilling is always the worst solution

• the volumes of plastic waste collected for recycling increased by 79%

• energy recovery increased by 61% • landfilling decreased by 43% Plastic weight reductions for packaging due to new design allowing for:

• A reduction of 28% over the past 10 years of the packaging weight in Europe.

• The use of only 17% of the total packaging weight on the market, while over 50% of all European goods are packaged in plastics.

ery is the best solution according to 1 of the 13 studies.

Waste generation and treatment depend on the industrial sectors and plastics family:

• The packaging, consumer goods, electrical and electronics, transportation, and building and construction sectors, etc., exhibit to rare and inconsistent statistical data, but it is established that, generally, recycling rates are low and several sectors are not at the cutting edge of waste recovery.

• The

building and construction sector: Table 11.16 displays waste treatment distribution by plastics family pointing out the low level of mechanical recycling, the broad range of energy recovery, and the too-high level of landfilling.

From a GWP point of view:

• For 23 studies: Recycling is the best solution according to 19 of the 23 studies.

Of course, these facts and data are special cases, not rules and many different elements may be found in the literature.

• For 19 studies: Incineration with energy recovery is the best solution according to 3 of the 19 studies.

• Landfilling is never the best solution. From a total energy use point of view:

• For 14 studies: Recycling is the best solution according to 13 of the 14 studies.

References Daniel, R.A., 2003. Environmental considerations to structural material selection for a footbridge. In: European Bridge Engineering Conference, Lightweight Bridge Decks, Rotterdam, March 2003.

11: PLASTICS SUSTAINABILITY: DRIVERS

AND

OBSTACLES

Harding, K.G., Dennis, J.S., von Blottnitz, H., Harrison, S.T.L., 2007. Environmental analysis of plastic production processes: comparing petroleum-based polypropylene and polyethylene with biologically-based poly-beta-hydroxybutyric acid using life cycle analysis. J. Biotechnol. 130, 57 66. Manuilova, A., 2003. Life Cycle Assessment of Industrial Packaging for Chemicals (thesis). Sweden. ,https://pdfs.semanticscholar.org/68dc/ d9613bc478d1656d706536482ccd6a6e6126.pdf.. Taengwathananukool, S., et al., 2013. Environmental impact assessment of bioplastic and MF-based coffee cup production. J. Sustain. Energy Environ. 4, 103 111.

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Further Reading Biron, M., 2014. Thermosets and Composites. Elsevier Ltd. Biron, M., 2016. Material Selection for Thermoplastic Parts. Elsevier Ltd. Biron, M., 2018. Thermoplastics and Thermoplastic Composites. Elsevier Ltd. Modern Plastics Encyclopaedia, McGraw-Hill Publications. Modern Plastics International, Canon Communications LLC, Los Angeles, CA, USA. Plastics Additives & Compounding, Elsevier Ltd. Plastics News.com, Crain Communications. Reinforced Plastics, Elsevier Ltd.

12 Plastics Sustainability: Prospective Of course, the future of plastics (as other topics) is based on a multitude of objective or subjective, manageable or unmanageable, known or unknown factors, making the forecast particularly dangerous. The reader should be cautious of the pitfalls inherent in the forecasts, which include many errors, uncertainties, and even the silence of unknown applications today. Possible active factors may be as diverse as:

• Demand and growth potential of plastics, itself depending on global population and standard of living

• Economics • Rethinking time management • Authoritarian restrictions, bans, and incentive actions

• Emerging technologies such as new polymers and new applications

• Brand image • Circular economy including recycling and renewable raw materials

• Possible oil shortages • Sustainability involving

everyone

and

governments

• Wastes and recycling management and collection and financing schemes

• Solving the ocean litter problem The problem is at a system level and cooperation is key, involving individuals, companies, corporate organizations, and governments. These entities must open new schemes of dialogs, start concerted actions aimed toward sustainability and circular economy, develop and deploy projects that minimize and manage resource depletion and plastic waste, and promote plastic postuse solutions. Cooperation, partnership at a precompetitive level,

horizontal collaboration, and teamwork across the value chain should facilitate the shift toward this new landscape of the plastics industry.

12.1 Demand and Growth Potential of Plastics Plastics consumption depends on many factors that evolve with time, economic context, scientific and industrial progress, objective and subjective opinions of consumers, among others. Some points deserving brief explanations are:

• • • • • •

demography standard of living time management emerging technologies plastics brand image specificities linked to sustainable plastics

Of course, the effect on plastics demand is not predictable and depends on the evolution of the unknown general context. Obviously, many other factors can affect plastics demand.

12.1.1 Overview of the Future Global Plastics Industry Worldwide plastics consumption is on the order of 335 million tons annually in round figures with a turnover of US$680 billion (or less) to US$1000 billion (or more). Over the past 5 years, global plastics consumption has grown consistently by an average annual rate of 2.5%. One hypothesis, among others, forecasts consumption on the order of 400 million tons annually in round figures for 2025 with a turnover of US $800 billion (or less) to US$1200 billion (or more).

A Practical Guide to Plastics Sustainability. DOI: https://doi.org/10.1016/B978-0-12-821539-5.00012-4 © 2020 Elsevier Ltd. All rights reserved.

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• Energy saving: lightweighting, insulation,

Of course, other figures can be found in other sources according to the polymers and applications taken into account and the considered areas. For the coming years, plastics promise a bright future due to:

etc.

• Rapid urbanization and climate change favoring plastic foam use for insulation, etc.

• Population growth, an increase of the standard

To be honest, plastics may suffer from potential cons including, but not limited to:

of living, improvement of plastics consumption per capita

• Growth slowing down to zero or negative

• Breakthrough of multiple innovations • Sustainability trends, etc. For the coming decades, the future is most uncertain with global trends being unclear. Some parameters may play a role or its inverse according to the circumstances. For example, the green wave may push plastics use for thermal insulation and other traditional applications or conversely, plastics use may be banned such as with carrier bags, single-use items, or polystyrene foams in certain locations. That being said, without any guarantee, we take gambles on the future expecting an optimistic development due to a global economic progression and innovation efforts. Innovations include, but are not limited to:

• Polymers: programmable, smart, self-healing polymers, high-performance plastics, nanomodified compounds and composites such as carbon nanotube (CNT), graphene, etc.

• Artificial intelligence (AI) • Design methods: modeling and simulation, function integration, etc.

• Sustainable material management • Industrialization: robotics, digitalization, 3D printing, step integration, etc.

• Marketing methods: extreme customization, shifting from owning toward sharing, big data utilization

• Environment: requirement compliance, optimization throughout life cycles, namely production, use, and recycling after use, etc.

• Circular economy minimizing resource input, energy consumption, waste, and emission: • Energy transition toward renewable energy encompassing wind, hydropower, solar power, geothermal, and ocean power

growth

• • • • •

Climate change disrupting the global economy Petroleum scarcity Sustainability issues, difficult recycling Poor brand image of plastics New technologies ousting plastics from their traditional application fields, for example, wireless techniques reducing plastics coatings of metal wires for electrical and electronics uses.

In brief, advancements in polymer science are at a turning point. On the one hand, innovative applications may unlock new avenues for the plastics industry and solve some burning issues, but on the other hand, the road from lab to production is long and strewn with pitfalls and uncertainty. In the past, a lot of wonder materials have failed because of many and various causes linked to the economy, technology, industrialization, safety, pollution, and other environmental trends, among others.

12.1.2 Effects of Demography and Standard of Living The evolution of the global population is a key factor leading to deep adaptations in food and feed production, energy consumption, housing, material requirements, and pollution. Scientific, technical, and industrial progress will modify our daily lives and futures. Many scenarios lead to a broad range of population estimates by 2050, for example, from 7 to 11 billion people, that is to say, an increase of approximately 15% 80% from the year 2000. Moreover, it can be remarked that some scenarios forecast stabilization or even a decline of the global population between 2050 and 2100. In addition, the population increase could be combined with a growth of plastics consumption per capita.

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

12.1.3 Rethinking Time Management New activities and technologies will probably change our occupational and private time distribution. Newly available time freed due to the suppression, mitigation, or automation of tedious, boring, and repetitive tasks may be allocated to work, home life, and/or leisure. According to chosen options, individuals may extend their working day (studying documents, making video calls on connected screens, etc.) or they may extend their leisure time (surfing the internet, online shopping, reading, relaxing or sleeping). Of course, these options have consequences on the used tools and devices. As a result, plastics demand may be increased, mitigated, and/or changed. Among the many new trends, please find a few examples that are far from representing the all new possibilities:

• Autonomous vehicles: compared with conventional vehicles, driving time is freed and can be used for other private or professional activities such as, for example, working, training, communication, relaxation, and/or entertainment. This involves more or less complete mutation of vehicle interiors and auxiliary functionalities. Autonomous vehicles will change the perception of distances extending opportunities for travelers to live further from city centers or work sites and, thus, open up new regions. Autonomous vehicles will create the opportunity for new users (young, old, or disabled persons) to move around more easily.

• Car sharing of autonomous (or traditional) vehicles will change new car demand expanding the use to new users, but mitigating the number of owners. Returns on investment by increasing the utilization of vehicles may overcome psychological motivations linked to appearance.

• Teleworking or coworking would lead to a shifting of the means between organizations and employees with consequences on tools and devices. Travel times and means for coming and going are broadly decreased or suppressed freeing time and money for other activities using different tools and devices. The protection of sensitive data at home causes specific issues needing specific solutions.

597

• e-Commerce, online shopping, videoconferencing, virtual tourism, and so on would avoid business and private moving, involving deep changes to used means, tools, and devices.

12.1.4 Authoritarian Restrictions, Bans, and Incentive Actions Worldwide there are many partial or total bans released by nations, states, territories, cities, or even organizations or companies concerning disposable single-use items made out of fossil plastics. Some are already in force, but many are scheduled for in future, often up to 2030. Bans are often limited to fossil plastics and non-compostable items. For example, thin plastics bags made out of natural-sourced polymers may be authorized. The list provided below is incomplete and can include inaccuracies due to the confusion between reality, wishes, intentions, and media hype. Until 2018:

• Bans or taxes on single-use plastic bags were entered into force in numerous countries as diverse as those in Africa, Australia, China, and Europe, among others. For some of them, bans or taxes are limited to certain areas. The list provided here includes some examples, without claiming to be exhaustive and without guarantee: • Africa: Botswana Cameroon Ethiopia Kenya Malawi Mali Morocco Rwanda South Africa Tanzania Uganda • Asia: Bangladesh Cambodia Hong Kong India Indonesia Malaysia Taiwan • Europe:

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598

England Italy Wales Scotland Germany • America: Argentina Brazil California Canadian provinces and territories Chile Colombia District of Columbia Hawaii Maine Mexico New York Puerto Rico Rhode Island Seattle South America

• Launch of a public consultation to determine the scope of a legislative initiative on singleuse plastics at the EU level to be tabled by the concerned commission, following the approach used for light-weight plastic bags.

• The European Union Commission has, therefore, started the process of restricting the use of intentionally-added microplastics, by requesting the European Chemicals Agency to review the scientific basis for taking regulatory action at the EU level.

• Danone uses 14% recycled polyethylene (PE) terephthalate (PET) in its water and beverage bottles.

• BMW as of 2009: 15% of the plastic parts approved for the BMW Group for the production of vehicles are made from recycled materials

• Mercedes: 14% of plastics parts can be manufactured party from high-quality recycled plastics.

• Mercedes: 8% of plastics parts can be manufactured party from renewable polymers.

• PSA Group: 30% “green” polymers (2015). • In 2018, Adidas produced more than 5 million pairs of shoes containing recycled plastic waste. The company now plans to more than double that figure this year.

• December 2018: The European Parliament and the Council of the European Union have reached a provisional political agreement on the ambitious new measures proposed by the commission to tackle marine litter at its source, targeting the 10 plastic products most often found on beaches as well as abandoned fishing gear. Products banned from the market should include: • plastic cotton buds, cutlery, plates, straws, drink stirrers, sticks for balloons • products made of oxo-degradable plastic • food and beverage containers made of expanded polystyrene

• On December 28, 2015, US President Barack Obama signed the Microbead-Free Waters Act of 2015, banning plastic microbeads in cosmetics and personal care products.

• The United Kingdom has banned microbeads in cosmetic and personal care products

• The Indian state of Maharashtra (116 million residents) banned many types of plastic bags, disposable cutlery, cups and dishes, and containers and packaging.

• The European Union financed h125 million to help develop alternative feedstocks and h100 million for more recyclable plastics materials.

• Opening of first supermarket with plastics-free aisles.

2019:

• The new cross-value chain Alliance to End Plastic Waste (AEPW) targets advanced solutions to eliminate plastic waste in the environment, especially in the ocean. The AEPW will: • Develop and bring large-scale solutions that will minimize and manage plastic waste • Promote solutions for used plastics by helping to enable a circular economy The AEPW gathers: • Chemical and plastic manufacturers • Consumer goods companies • Retailers • Converters

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

• Waste management companies The founding members include BASF, Berry Global, Braskem, Chevron Phillips Chemical Company LLC, Clariant, Covestro, Dow, DSM, ExxonMobil, Formosa Plastics Corporation USA, Henkel, LyondellBasell, Mitsubishi Chemical Holdings, Mitsui Chemicals, NOVA Chemicals, OxyChem, PolyOne, Procter & Gamble, Reliance Industries, SABIC, Sasol, SUEZ, Shell, SCG Chemicals, Sumitomo Chemical, Total, Veolia, and Versalis (Eni).

• As

reported by EcoWatch, Taiwan’s Environmental Protection Agency put forward a 12-year plan that will officially begin in 2019 with a blanket ban on plastic straws in stores and restaurants.

• The United Kingdom announced that cotton buds, drinking straws, and various single-use plastics could be banned from sale in England from 2019, as part of a Commonwealth-led campaign to stop the pollution of the world’s oceans and waterways.

• Adidas plans to produce 11 million pairs of shoes containing recycled ocean plastic in 2019. 2020:

• The

US Biomass Technical Advisory Committee has set the goal to produce 18% of chemicals and materials from biomass in 2020.

• By 2020, the USDA forecasts that there will be $375 $441 billion biomass-based chemical sales in the global chemical sales market; this is approximately 11% of the global chemical market.

• The Taiwan ban on plastic straws will be extended to all dining establishments.

• Nestle´ aims to reduce the amount of packaging by 140,000 t by 2020 from a 2015 baseline.

599

2022:

• India announced that it would be removing single-use plastics by 2022.

• Danone forecasts using up to 95% bio-based material in its PET bottles. 2023:

• Iceland, a big supermarket chain in the United Kingdom, says it will ban plastic packaging use on its own brand products in 2023. 2025:

• According to the USDA, the global market share of biomass-based chemicals is projected to increase to 22% in 2025.

• Henkel aims to use 35% recycled plastic for its consumer goods products in Europe.

• 100% of the Henkel’s packaging will be recyclable, reusable, or compostable.

• Nestle´’s ambition is that 100% of packaging is recyclable or reusable by 2025.

• Mondi Group will boost the use of recycled content in its products to ensure a minimum of 25% of postconsumer waste is incorporated across all its plastic packaging by 2025.

• Mondi Group will use its expertise in paperbased and flexible plastic packaging to enhance its product design and thereby achieve 100% reusable, recyclable, or compostable plastic packaging by 2025.

• By 2025, Danone aims to reach 25% recycled material on average in its plastic packaging, 50% on average for water and beverage bottles, and 100% for Evian bottles.

• Danone also aims to offer consumers bottles made from 100% bioplastic.

• Volvo wants 25% of the plastics used in its new cars to be recycled by 2025.

2021:

• Costa Rica announced plans to ban single-use plastics by 2021.

• Danone will use up to 75% bio-based PET bottles. • Danone will launch 100% recycled PET bottles in all its major water markets.

• Taiwan people will have to pay a fee to use plastic straws, bags, cups, and disposable utensils. Although the specific pricing was not disclosed, it could be high enough to deter people from using plastic items.

• Under the new Taiwan plans, the hope is that the average Taiwan citizen uses roughly 100

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

600

plastic bags a year versus the 700 bags used previously.

• The European Union pledged to a campaign to ensure that by 2025, 10 million tons of recycled plastics find their way into new products. 2030:

• The American Chemistry Council’s (ACC) Plastics Division announced its members have set an ambitious goal, that is, to ensure that 100% of plastic packaging is recyclable or recoverable by 2030.

• The

US Biomass Technical Advisory Committee has set the goal to produce 25% of chemicals and materials from biomass in 2030.

• The Japanese government set a “Biomass Nippon Strategy” with the goal of 24% of renewable material being consumed in Japan by 2030.

• Taiwan plans to ultimately phase out all disposable plastics items by 2030 and replace them with reusable and biodegradable items.

• All plastics packaging placed on the EU market must either be reusable or recyclable in a cost-effective manner.

• More than half of plastics waste generated in Europe must be recycled.

• Sorting and recycling capacity has increased fourfold since 2015, leading to the creation of 200,000 new jobs.

• Under the new Taiwan plans, the hope is that the average Taiwan citizen uses roughly 0 plastic bags a year versus the 100 bags used by 2025 and the 700 used prior to that. 2040:

• Six European organizations from the plastics value chain have committed, in cooperation with the European Commission, to launch Circularity Platforms aiming to reach 50% plastics waste recycling by 2040.

• PlasticsEurope will aim at achieving the goal of 100% reuse, recycling, and/or recovery of all plastics packaging in the European Union by 2040.

• The ACC’s Plastics Division announced its members have set an ambitious goal to ensure to reuse, recycle, or recover 100% of plastic packaging by 2040. 2042:

• The UK government has launched an environmental plan spanning the next 25 years forecasted to eliminate all avoidable plastic waste by 2042 and urging supermarkets to set up “plastic-free aisles” for goods with no packaging.

12.1.5 Emerging Technologies: Example of Vehicles Of course, the effect on plastics demand of new technologies is not predictable and depends on the evolution of emerging or unknown parameters. Only a few examples are given here and obviously many other factors can affect plastics demand.

12.1.5.1 Electric Vehicles According to the International Energy Agency (IEA) some 1 million plug-in hybrid and fully electric vehicles were sold worldwide in recent year, representing about 1% of the total car market. About 3 million hybrid and electric vehicles are on the road today. By 2020, that number will climb to between 9 million and 20 million, and from there it will more than triple by 2025. Other forecasters are projecting a two-digit compound annual growth rate (CAGR) (28% to more than 40%) during the coming years. By 2025, according to IHS Markit (https://ihsmarkit.com/index.html), electric and hybrid electric vehicles could account for 33% of the total vehicle production worldwide. There is no consensus in the industry that a full transition to electric vehicles will happen eventually. A number of forecasters are confident that internal combustion engines are not necessarily dying even in the mid-term. On the other hand, there is a broad global adoption of regulations calling for an end to internal combustion engines by the year 2040. In 1960, according to the ACC, the average US car used 8 kg of plastic and composites. About 50 years later, the typical car is made with approximately 150 kg of plastics and composites, that is to say, almost 19-times more.

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

Composites and plastics must shift from current key features (resistance to temperature and fuels) toward the specific requirements of electric cars including:

• inescapable lightweighting that must compensate for the weight of the batteries

• specific polymers suitable for batteries • longer lifetime linked to the expected longer lifetime of e-cars, among others. The demand for plastics should increase rapidly, benefiting from the fast growth of e-vehicles. Market growth is driven by stringent emission regulations for fuel vehicles pushing the growth of ecars, the lightweighting of vehicles, favorable government policies, and incentives measures for electric vehicles. Innovative high-performance plastics could be particularly required. In the future, some forecasters are projecting a longer life cycle for evehicles, which could limit demand.

12.1.5.2 Autonomous Vehicles Fully autonomous vehicles are in the testing phase, needing a human supervisor and special traffic conditions. Technological advances in autonomous vehicles depend upon advances in sensors, cameras, control devices, inverters, and tireless and truthful software solutions. The increased use of plastic components is expected to serve as an effective solution to reduce the weight of vehicles. In addition to evehicle plastics applications, plastics demand will increase for connectors and housings for the many electrical and electronic components required, but conversely, the use of plastics for fuel lines, air intake manifolds, oil pans, fuel tanks, and other parts specific to internal combustion engines will gradually decline. Cameras, radar, lidar, and other sensor housings need to maintain extremely tight tolerances, dimensions, and chemical and thermal resistances, requiring a shift toward better performing plastics and composites. Innovative coatings can support a longer lifetime in harsher conditions and new requirements induced by new share habits. Worldwide, cars could kill more than 1 million people each year. Generally speaking, one can hope that autonomous vehicles could do better due to their top-quality software being highly sophisticated, reliable, and rigorously tested.

601

12.1.6 The Dream of Almost Perfect Polymers The dream of plastics researchers is to discover and put on the market new polymer families bringing together all the features required by a circular economy:

• Being made out from renewable sources using green chemistry

• • • • •

Right performances for the targeted applications Affordable cost Environment-friendly Public opinion acceptance Recyclability including ease of collection and sorting, efficient recycling technologies, effective demand, and reuse for recyclates, etc.

Of course, it is a hypothetical material family, but polymers used today have many of these required features and pave the way for further research.

12.1.7 Alternative Fuels There is intensive and extensive research on biofuels that can directly or indirectly lead to rich sources of monomers used in the polymerization of traditional or innovative polymers (see Chapter 10: Transition of Plastics to Renewable Feedstock and Raw Materials). On condition of a sustainable choice of feedstock and processing method, this can be an interesting way toward more sustainable plastics.

12.1.8 Plastics Brand Image Social networks reflect mass opinion of social structures including sets of social actors such as individuals, organizations, and business players. Choosing a specialized social network and examining the flow of exchanges during a defined period of time may give a rough idea of the interest of the actors on a defined subject. For a defined social network analyzed for a certain period of time, flows of posts concerning plastics show that environment topics clearly prevail over all other considerations gathering more than 64% of all posts. Pollution is the main concern followed by recycling, sustainability, the environment, and a circular economy.

602

Of course, these data are examples and other figures may be obtained using other keywords.

12.1.9 Specificities Linked to Sustainable Plastics Long-term sustainability requires new thinking, strategic revamping of the current way of life, societal choices, innovative economy, and more generally new rules of the game. Sustainability should trigger a deep impact on the economy, an evolution of society, lifestyles, practices, regulations, and others, to reshape current systems for long-lasting and systemic change. Sustainability is an emerging issue that will continue to grow in importance over the coming decades and become the most important challenge for society and companies, beating cost and other issues. The world needs to aim toward a more circular economy that is less oil-dependent, more efficient, and less polluting. On the one hand, plastics offer a unique combination of light-weight, durability, and other intrinsic features contributing to emissions reduction and more efficient use of resources across a range of different sectors and everyday applications. However, on the other hand, plastics must achieve progress in circular and resource efficient economy. In all likelihood, the solution to this harsh situation will take decades to obtain. For example, PlasticsEurope aims at achieving the goal of 60% reuse, recycling, and/or recovery of all plastics packaging in the European Union by 2030 and 100% by 2040. Members of the ACC’s Plastics Division have set the goal for capturing, recycling, and recovering plastics that 100% of plastic packaging must be reused, recycled, or recovered by 2040. Many threatened plastics products are under serious pressure from environmentalists and legislators such as plastic bags, coffee cups, polystyrene takeout packaging, plastic straws, closures and water bottles, frozen food packaging, single-use items, cotton swabs, among others., and more general products that are not recyclable in practice.

12.2 Economics of Renewable Plastics and Bio-additives: Quantified Expectations The economy is dominated by fossil energy (petroleum, coal, natural gas) for producing fuels,

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

electricity, power, chemicals, and materials. A bio-industry could produce energy and many chemical building blocks from biomass [crops, trees, grasses, crop residues, forest residues, animal wastes, agricultural residues, and municipal solid waste (MSW)]. Biomass is naturally abundant. For example, in the continental United States, about 500 600 million tons of plant matter can be grown and harvested in addition to food and feed needs. A bio-industry could be encouraged by environmental regulations and could provide many benefits such as productive use of agricultural and forestry wastes, lower emissions of greenhouse gases (GHGs) and pollutants, and growth in rural economies, but some parameters must be evaluated such as pollution from fertilizers and pesticides:

• Rural development: A bio-industry would require an increase in the production and processing of biomass and would require new processing, distribution, and service industries.

• Environment: A key benefit in the move toward bioproducts is perhaps the potential for reducing pollutants emitted into the environment, but some products used for agricultural purposes are disputed. When comparable bioproducts are produced, the environmental impacts are sometimes less or eliminated since many bioconversion processes occur at or near room temperature, atmospheric pressure, and neutral conditions. However, water pollution can be an issue if plants are specially grown for the bio-industry. Particulate emissions generated during grain crushing and grinding operations can also be an issue concerning air pollution. Deforestation is also an issue for cultivated sources of biomass.

• Plants sequester carbon via photosynthesis and potentially reduce the amount of CO2 emitted into the atmosphere. An important point for the bio-industry strategy is to avoid competition with crops that are normally used for food, feed, and industrial applications such as corn, textiles, and so forth. Organic products of municipal waste and agricultural wastes and food and feed industry by-products are ideal from this point of view. CO2 could be also an abundant feedstock with the advantage of sequestering a harmful GHG.

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

Being emerging materials, bioplastics consumption data broadly vary with sources, depending on the concept of bioproducts, a certain confusion between consumption and production capacity, and the optimism of the forecaster. In any case, bioproducts are specialty materials that now represent less than 5% of total products, but with a higher growth rate than fossil plastics. The global market share of biomass-based chemicals is projected to increase from 2% in 2008 to 22% in 2025. For cultivated renewable materials, freeing ground for cultivation through deforestation is also a problem.

603

1000 (A) 900 800 700 600 MT 500 400 300 200 100 0 2020

Year

1000 (B) 900 800 700

12.2.1 Renewable Plastics Consumption and Capacity Forecasts It is necessary to anticipate the growing scarcity and the possible drying up of petroleum, which is the source of virtually all plastics. In this context, many countries study the replacement of oil-based products with bio-sourced equivalents or innovative products. So, for example, in the “Vision for Bioenergy and Biobased Products in the United States,” published by the Biomass Technical Advisory Committee, a goal was set to produce 12% of chemicals and materials from biomass in 2010, 18% in 2020, and 25% in 2030, compared with the 5% produced in 2000. Remember that renewable plastics can be broken down according to their origin in bio-sourced polymers and in recycled plastics.

12.2.1.1 Renewable Plastics Consumption Overview at Mid- and Long-Term Although they obey similar targets, scenarios for recycled and bio-sourced plastics are quite different. Recovery Volume

Modeled data are quite different if based on the volume of recycled plastics or based on the percent of overall plastics consumption. Starting from a few million tons, that is to say, a small percent of total plastics today, modeling may lead to some tens of millions of tons by 2030. Of course, the gap grows the longer the term of the estimate.

600 MT 500 400 300 200 100 0 2020

Year

Figure 12.1 (A) Forecast of plastics recovery up to mid-century. (B) Consumption forecast of renewable plastics up to mid-century.

Fig. 12.1A shows the broad range of forecasts due to the lack of precise statistics, the accounting method possibly taking into account energy recovery, the lack of knowledge of the global economy, the point of view and the optimism of the forecaster. Obviously, those data are only a possible scenario among others and cannot be used to make economic predictions. Other higher data may be found elsewhere when taking into account an increase of percent of recycling versus total consumption of plastics. This hypothesis is credible according to crude oil scarcity and the strengthening of environmental regulations. According to Plastics News:

• PET (60%) • PE (35%) account for about 95% of the recycled plastics, far ahead of polypropylene (PP), accounting for 2%. In the far distant future, recycling should closely follow the consumption of virgin plastics to optimize sustainability.

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At mid-term, forecasts are in a broad range, for example:

• According to https://www.prnewswire.com/ news-releases/recycled-plastic-market-toreach-us-30-billion-by-2025---persistence-marPersistence ket-research-654446003.html, Market Research, the recycled plastic market is projected to be worth just over US$30 billion by 2025.

• MarketsandMarkets (https://www.marketsandmarkets.com/PressReleases/recycled-plastic. asp) estimates that the global recycled plastics market was worth US$37 Billion in 2017 and is projected to reach US$50 Billion by 2022, at a CAGR of 6.4% between 2017 and 2022.

• According to Market Research Future (https:// www.marketresearchfuture.com/reports/plasticrecycling-market-2859) the market value is projected to reach US$54 million by the end of 2023. Bio-sourced Plastics Consumption

Consumption data broadly vary with sources, depending on the concept of bioplastics, a certain confusion between consumption, actual production, and production capacity, the retained data for partial biopolymers, the retained global economy hypotheses, and the optimism of the forecaster. According to various market studies (NovaInstitute, BCC Research, MarketsandMarkets, Fig. 12.1B European Bioplastics, etc.), “Consumption forecast of Bio-Plastics—2020/ 2060” shows the broad range of forecasts due to the low levels of consumption for each class, the lack of precise statistics, the accounting method (how is a PET based on 30% natural resources accounted?), the lack of knowledge on the global economy, the point of view and the optimism of the forecaster. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere. Until 2030, the production level of each family can be classified as specialty plastics. Of course, even for cheap feedstocks, the cost could be higher than that of commodities. According to some hypotheses, bioplastics and fossil plastics consumptions could be balanced in the middle of this century.

For longer-term forecasts, a mathematical model is proposed taking into account several assumptions related to:

• the starting year being set to 2000 for significant commercialization

• the final level of fossil plastics replacement set to a cautious 80%, a consensual level according to experts

• the growing demand cycle valued to 70 years according to the growing demand cycles of fossil commodities

• the standard logistic law for mathematical modeling Modeling is a purely mathematical exercise, which does not take into account unexpected technical and economic events, and does not properly foresee the economic evolutions as soon as the experimental limits are left behind. Modelling is a game of the mind based on factual and mathematical hypotheses. Often the real world can evolve differently making that the use of models is more or less hazardous. Being conscious of those drawbacks, Fig. 12.2 shows a plausible hypothesis (possibly false in light of the long forecasting period) for the replacement rate of fossil plastics by bioplastics. These forecasts are based on smooth evolutions that can be shattered by important parameters such as a petrol drying-up, a harsh stiffening of environmental requirements, and any other upheavals. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere.

1000

MT Total plastics (MT) Bioplastics (MT)

500

0 2000

Fossil plastics (MT)

2050

Year 2100

Figure 12.2 Consumption forecast for bio- and fossil plastics—2000/2070.

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

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Table 12.1 Rating of the Seven Main Bioplastics Families.

Table 12.2 Examples of Forecast Capacities by Bioplastics Families.

%

Capacity

MT

Bio-PET

40

Bio-PE

80

Bio-PE

15

PLA

50

PLA

15

Bio-PET

30

Starch derivatives

10

Starch derived

20

Biodegradable polyesters

10

Other known and unknown families

180

Other known and unknown families

10

Total production capacity

350

PE, Polyethylene; PET, polyethylene terephthalate.

In that rather optimistic hypothesis, total plastics consumption is moderate and bioplastics account for 50% of the total plastics consumption by approximately 2035. According to a SpecialChem poll asking “Bioplastics are growing fast but now their consumption is weak. In your opinion, bioplastics can catch 50% of the plastics market by. . .?” The answer from the respondents having a positive opinion of bioplastics was about 2040.

12.2.1.2 Market Shares by Bioplastic Family Table 12.1 (according to European Bioplastics) proposes a rating of the five main bioplastics families valued at their total gross weight. Please note that bio-PET and some others can be far from 100% bio-content. Bio-PE, PLA, bio-PET, and starch derivatives account for more than 75%. Obviously, these data are only a possible scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere.

12.2.1.3 Production Capacities by Bioplastic Family Production capacities are questionable for marketing reasons, with high uncertainties concerning new families of bioplastics. Table 12.2 displays examples of forecast capacities by bioplastics families. Please note the main item refers to “known and unknown families,” which would require huge research efforts and a favorable economic situation. This would allow for new renewable families to be found and developed, thereby meeting the demand. Obviously, those data are only one possible

PE, Polyethylene; PET, polyethylene terephthalate.

Table 12.3 Examples of Forecast Capacity Shares by Region. Share Forecast (%) Asia

50 70

South America

20 50

Europe

5 10

North America

5

Middle East and Africa

Negligible

Total

100

scenario among many others and could be totally false. They cannot be used to build economic predictions. Other different data can be found elsewhere.

12.2.1.4 Bioplastic Capacities by Region Please note that capacity and consumption can be quite different. Table 12.3 displays the global production capacity shares at mid-term for biopolymers based on renewable raw materials. Data are inconsistent for some regions, but unquestionably Asia and South America are the leaders. Obviously, these data are only a possible scenario among others that cannot be used to make economic predictions. Other data can be found elsewhere.

12.2.1.5 Bioplastic Capacities by Market Table 12.4 proposes a mid-term forecast of global production capacities by shares (out of textiles) for biopolymers based on renewable raw materials. Obviously, these data are only a possible

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Table 12.4 Examples of Forecast Capacity Shares by Application Sectors.

12.2.3.1 Crude Oil: Shortage or Not?

According to market research reports, the global plastics composite market is estimated to be worth between US$60 and US$300 billion by 2030. It is expected to increase at a CAGR of between 4% and 8%. Increased use of natural fiber to replace glass fiber is on the way, but the replacement of fossil carbon fiber by natural-sourced carbon fiber (CF) is not so advanced.

Oil shortages have been predicted or denied over the past few decades according to the considered significance (structural or temporary shortage), admissible price level, production and demand models, evolution of energy sources, political decisions, among others. As already said in Chapter 8, Economics Relating to Fossil and Renewable Plastics, at the current consumption levels, known recoverable crude oil reserves would be dried up in some tens of years for relatively easy extractable sources and 100 years or more if petroleum from sand is recovered. Potentially, this would lead to a global energy crisis in the medium term. For another example, according to BP (https:// www.bp.com/en/global/corporate/energy-economics/ statistical-review-of-world-energy/oil/oil-reserves. html) global proved oil reserves in 2017 fell slightly by 0.5 billion barrels ( 2 0.03%) to 1696.6 billion barrels. That is equivalent to about 50 years of 2017 global production. According to some hypotheses, oil consumption will reach a peak and then will decline, which could delay the structural oil shortage. Oil shortages are a controversial topic and many other predictions may be found in the technical and economic literature. As a result, it is essential to foresee the replacement of polymers based on crude oil by renewable polymers.

12.2.2 Bio-additives Consumption

12.2.3.2 Bioplastics Costs

% Packaging

45 60

Building and construction

10 20

Auto and transport

5 10

Electrical and electronics

5 10

Consumer goods

5 10

Agriculture

2

Others

2 5

Total

100

scenario among others and cannot be used to make economic predictions. Other data can be found elsewhere. Packaging is the unchallenged leader with a market share higher than 45%.

12.2.1.6 Composites Consumption

According to market research reports, the global plastics additive market is estimated to be worth between US$45 and US$100 billion by 2030. It is expected to increase at a CAGR of about 4% to reach between US$70 and US$170 billion by 2040. At the same time, to assure a sturdy progression in terms of sustainability, bio-additives should increase by some tens of percent, which seems a difficult goal.

12.2.3 Bio-material Costs Generally speaking, bio-materials related to plastics applications are more expensive than similar fossil materials. The availability of crude oil in the mid-term is a major parameter for the development of bio-materials.

Price is an obstacle to the spreading of bioplastics confirmed, for example, by a poll conducted by Brilliant Little Planet, a bioplastics supplier, and Adapt Low Carbon Group, a management consultancy, which found that while 8 out of 10 respondents said they used biodegradable products, more than half felt that the cost was too high. Generally speaking, according to various global market studies, the average price of bioplastics was valued on the order of US$2.2 US$2.9/kg, that is to say, 1.4- to 1.6-times the average price of commodity thermoplastics. More optimistic forecasters value the premium at 25%. Table 8.12 and Fig. 8.8 display a statistical analysis of expected prices for bio- and fossil-sourced plastics as well as prices versus market shares. Of

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

course, these data cannot be used to make economic predictions. Other different figures can be found elsewhere.

12.2.3.3 Long-term Costs of Bioplastics Compared to Fossil Plastics The high cost of virgin plastics boosts the use of recycled fossil plastics and natural-sourced polymers. For numerous virgin fossil plastics, crude oil is used both as a feedstock and as the energy source for the production, which doubles the consequences of oil prices. For recycled polymers, the crude oil used as a feedstock for virgin polymers is saved and crude oil is only used for energy production. Simply put, if crude oil cost was doubled:

• The cost of the virgin fossil polymer is expected to become about 34% 50% higher.

• Taking into account the actual discount for recyclates, the acceptable cost of the recycling treatment could be significantly increased, which would allow for new possibilities for the waste collection, sorting, cleaning, and recycling steps.

607

7

(A)

6 5 4 3 2 1 0 2025

2055

10 (B) 9 8 7 6 5 4 3 2 1 0 2025

2055

10

(C)

9 8 7

For natural-sourced polymers, figures are different, but trends are similar. Of course, many other predictions may be found in the technical and economic literature, but trends are generally on the same order. Modeling may be based on numerous assumptions, among which, we chose two as examples, one that is based on the history of prices and the another based on the forecast of the crude oil price. Renewable polymers are emerging materials without a history and we identify their cost in relation to that of a panel of agricultural products. Modelling is a game of the mind based on factual and mathematical hypotheses. Often the real world can evolve differently making that the use of models is more or less hazardous. Modeling From Historical Prices

First, we study the price evolutions of fossil PP as an example of fossil commodities (see Fig. 12.3A), and second, we model an index of prices for 10 agricultural products (World Bank data) representative of natural polymers or sources for renewable plastics (see Fig. 12.3B).

6 5 4 3 2 1 0 2025

2055 Maxi renewable price

Mini PP price

Maxi PP price

Mini renewable price

Figure 12.3 (A) PP historical price (US$/kg) forecast. (B) Theoretical PP price (US$/kg) forecast based on agricultural models. (C) Comparison of theoretical PP price (US$/kg) forecasts. PP, Polypropylene.

Third, we apply the model to the price evolution of a theoretical renewable plastic with an initial price higher than that of PP (see Fig. 12.3C). Concerning the agricultural index there is some problems with the reference period, the nature of agricultural products and high yearly variations of prices.

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Fig. 12.3,B shows two hypotheses:

400 350

• One based on FAO’s model (dashed line) with modeled prices of maize during more than 100 years. Data show a continuous trend of longterm decline.

• The other (continuous line) is based on an agricultural model taking into account 10 agricultural products (World Bank data) during a shorter period (about 20 years). Modeled prices are corrected data taking into account beneficial parameters for renewable plastic: • The mass effect for a material produced in fast growing volumes. According to several cases, it can be estimated to be about 20%. • A growing efficiency of production methods for fast developing emerging materials. First, it must be pointed out the negative slope for the first model, while contradictorily, the second model leads to a positive slope. This results in a broad range of prices for 2050 on the order of h1.6 h7/kg. In addition, please note that these estimations relate to cultivated natural resources. For renewable plastics originating from waste, the raw material purchase cost may be much lower or even negative when considering the cost of environment-friendly disposal of wastes if they had not been usefully recovered. Fig. 12.3C compares the various hypotheses of forecast price ranges (see Fig. 12.3A and B) showing the high degree of uncertainty. According to these scenarios, it is hazardous to draw conclusions. Perhaps the price of the theoretical renewable plastic can reach that of the PP price by 2035 2040 or later at best. Of course, modeling is just a mathematical exercise and, for example, independently of time, being more immediate than previously examined parameters, the increase of crude oil prices would be the decisive factor of the relative costs of fossil and renewable plastics. Crude Oil Price Expectations

The crude oil price depends on many unknown parameters such as, for example, global oil demand, healthy global economy, financial crisis, recession, demography, way of life, high or low economic growth, production of shale oil, alternative fuels, success of e-mobility, wars, and so

300 250

Low

200

High Mean

150 100 50 0 2020

2060

Figure 12.4 Crude oil price hypotheses.

forth. Obviously, the crude oil price range is as broad as the combination of the expected ranges of all these unknown parameters. Without any guarantees, Fig. 12.4 presents an example of envelopes of around 20 forecast curves, but despite the width of the range other data can be found outside of this envelope. Modeling Plastics Prices Thanks to Crude Oil Prices

We study these hypotheses for the crude oil price increasing up to US$200/bbl (mean of the 2050 forecast).

• Fossil PP feedstock is issued from crude oil and production needs energy.

• Renewable plastics feedstocks are issued from biomass and production energy is at its worst the same as that used for fossil plastics. Consequently, renewable plastics would be less sensitive to the crude oil price. First, we study the price evolutions versus crude oil prices of PP as an example of the fossil commodities (see Fig. 12.5A), and second, we model an index of prices for 10 agricultural products (World Bank data) representative of natural polymers or sources of renewable plastics (see Fig. 12.5B). Third, we apply the model to the price evolution of a theoretical renewable plastic with a price higher than that of fossil PP for a crude oil at US$80/ bbl. Fig. 12.5C (be aware: the x-scale is in years making comparison feasible with previous forecasts, but it is an additional hypothesis) compares the price with that of fossil PP, pointing out an equality for approximately 2030 (about US$110/bbl for crude oil price).

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3.5

609

Please note that these forecasts differ from previous ones because assumptions are different in that they are based on the historical prices of plastics or crude oil prices. This confirms the weakness of all these conjectures that are intellectual constructs and cannot guarantee the actual future. The use of these data leads to a real risk.

(A)

3 2.5 2 1.5 1 0.5 0 50

200

12.3 Sustainability: The Problem Is at a System Level

4 (B) 3.5 3 2.5 2 1.5 1 0.5 0 50.00

The problem lies on two levels:

• Partial change: what can be done without causing a negative impact at the system level? 200.00

• Examples of ways, but check the risks of individual changes

3.5 (C)

1.5 2020

12.3.1 Sustainability Game Changers: Smart Factories, Circularity, and Environmental Compliance

2025

2030

2035

Renewable

2040

2045

2050

Fossil

Figure 12.5 (A) Fossil PP price (US$/kg) versus crude oil price (US$/bbl). (B) Agricultural prices (US $/kg) versus crude oil price (US$/bbl). (C) Forecast of fossil and renewable commodity plastics versus crude oil price. PP, Polypropylene.

Concluding remarks:

• Fossil PP price clearly depends on crude oil price while agricultural prices are less affected for the studied model, but we have previously seen that two models can lead to contradictory results.

• Agricultural prices are broadly scattered according to weather hazards and global economic conjuncture.

• Probably, the price of renewable commodity plastics should compete with fossil commodity plastics in the more or less far future.

According to a survey (https://www.ibm.com/ downloads/cas/JD71Q7RK) of global manufacturers using all types of materials, cognitive manufacturing can improve all the steps of manufacturing and business with:

• 64% gain on decision making and planning • 58% on productivity and efficiency • 54% on security and compliance with reduced risks

• 52% on customer service • 49% on learning experience Cognitive manufacturing is already a reality in the world. For example, the ratio of used energy (index) to industrial production (index) for an industrialized nation is slowly declining (on average) for the period 1980 2020. The smart factory and business represent a flexible system that can self-optimize performance across a broader network, self-adapt to and learn from new conditions in real or near-real time, and autonomously run entire production processes.

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Of course, a smart factory uses a multitude of hardware and software solutions. Among others, there are, for example:

• Better and cheaper quality due to early

• Hyper-connectivity within the walls and

resources, supply chain management, and quality control

externally

• Hyper-sophisticated and omnipresent sensors • Big data collection, storing, and treatment • Collection and processing of structured and unstructured data to generate new understandings

• Real-time data analysis and processing • Sophisticated software solutions, modeling,

detection and treatment of dysfunctions

• Leverage advanced analytics to optimize • • • • • •

Lower production cost Lower pollution, lower environmental cost Increased worker safety and well-being Increased asset uptime Quick and consistent changes Autonomously optimize, adapt, and run production processes

eco-design, virtual testing, AI, block chains, big data analysis, etc.

• Forecast issues, estimate causes of failure and

• Use of autonomous and connected robots,

lifetime, and draw useful conclusions to improve operational efficiency and decision making

cobots, and cognitive bots for automated routine processes at minimal cost with high accuracy

• Collaborative work within the walls, upstream and downstream throughout the entire supply chain

• Process automation and automated alerts, automated tracking, self-adaptive processes, selfrepairing, smart manufacturing

• Augmented reality, artificial vision, powered exoskeleton to assist personnel

• In-line quality testing, constructive testing, virtual testing Benefits of smart manufacturing and business can include, but are not limited, to the reliability, availability, and performance improvements that would come from:

• Optimization of design and resources depletion • Minimization of waste and cycle times • Optimized, responsive, agile, and adaptable planning: timeous, quantitative, efficient production and delivery, etc.

• • • •

Safety and sustainability gains Real-time decisions Accurate forecasts continuously updated Real-time collaboration within the walls, upstream and downstream throughout the entire supply chain. Real-time linkages to staff and other stakeholders.

• Predictive downward slide, early identification of deviations, abnormalities, dysfunctions, issues; autonomous troubleshooting

• Automated management • Real-time testing and real-time adaptation of the process avoiding waste and hors-spec

• Transform processes and operational performance through continuous machine and human learning

• More efficient and cheaper maintenance and repairing of equipment

• Environmental, health, and safety gains, for example, sensors allow operation of equipment in close proximity to personnel or sensors on personnel monitor environmental conditions, lack of movement, etc. These few examples cannot cover all the cases so the reader must search and do experiments in coordination with other stakeholders. Also please remember that this endless digitization is not possible without the human brain for creative thinking. A circular economy and environmental behavior are essential for a better sustainability and must gain ground by the incorporation of additional requirements such as, for example, without claiming to be exhaustive:

• Create and make viable an effective postuse of plastics. Repair, reuse, and closed-loop recycling must become the rule.

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611

• Decouple plastics from fossil feedstocks.

• Autonomous processes thanks to prescriptive

Renewable resources shall be used efficiently and their consumption at long term should not exceed their natural regeneration.

analysis. Of course, current feedback is the most constructive.

• Nonrenewable resource use must be limited to

Descriptive analytics show historical insights regarding production, quality, sustainability, wastes, sales, finance, inventory, providers, and customers. Predictive analytics forecast probable (not certain) scenarios for the future. They combine historical data found in enterprise resource planning, customer relationship management, historical technology data, human resource management, historical sales systems, and many other reports to identify patterns in data and apply statistical models and algorithms to formulate relationships between various datasets. Prescriptive analytics provide different possible actions, advice, and guidance toward possible (not certain) solutions. Prescriptive analytics use techniques and tools such algorithms, AI, machine learning, modeling, big data, and others. Suitable and wellapplied prescriptive analytics can successfully be used to optimize production and logistics, for example, to make sure that an organization delivers the right products at the right time in the right quantity.

levels compatible with their forecasted substitution by renewable resources.

• Use

the best compromise resources/actual properties).

(amount

of

• Reduce the leakage of plastics into natural systems and other externalities.

• Ban accumulation of substances of concern, particularly when closing the plastic material loops.

• Release of hazardous or polluting substances to the environment should not exceed their assimilative capacity; pollutant concentrations must be below the known critical levels of preservation of human health and the environment.

• For hazardous substances, persistent and/or bio-accumulative, a zero release is required to avoid their accumulation in the environment.

• More generally, irreversible adverse effects of human activities on ecosystems and the environment must be banned.

12.3.2 Emergence and Rapid Advance of Prescriptive Techniques Historical data are an underutilized treasure that can be better valued by using the latest analytical techniques. Advances in data collection and processing are paving the way for new methods of data exploration that facilitate the transition from description to forecasting and then prescriptive analysis of data in a new stage.

• Descriptive analytics provide insights into the past.

• Predictive analytics provide insights into the

12.3.3 Examples of Strategies Aiming at a Better Sustainability To achieve a better sustainability, all stakeholders must focus on multiple key areas of circular economy, increase efforts along the value chain to include eco-design aspects, encourage users to favor more sustainable use, and organize, favor, and ease reusability and recyclability. The term “recyclable” demands attention. Two associations “The Association of Plastic Recyclers” and “Plastics Recycling Europe” say that plastics must meet four conditions for a product to be considered recyclable: 1. The product must be made with a plastic that is collected for recycling, has a market value, and/or is supported by a legislatively mandated program.

future using statistical models and forecasting techniques.

2. The product must be sorted and aggregated into defined streams for recycling processes.

• Prescriptive analytics propose hypotheses on

3. The product can be processed and reclaimed/ recycled with commercial recycling processes.

suitable actions leading to optimal results thanks to optimization and simulation algorithms.

4. The recycled plastic becomes a raw material that is used in the production of new products.

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Only actual facts are taken into consideration and theoretical possibilities and other vain wishes are not taken into account. Key points concerning sustainability include, but are not limited to: New design strategy:

• • • • • • •

avoiding or banning single-use products designing new products for greater efficiency using recycled materials designing long-lasting products designing for repairing and reuse easing dismantling

advantages and drawbacks. Differences include the collection rate, but also the end pollution, recycling rate, end costs, among others. All the steps involved must be taken into account including the integration of new polymers not compatible with existing streams. Worldwide, the recycling rate of packaging waste is between 0% and 50% for most nations. On the other hand, other solutions such as landfilling and burning increase soil, air, and water pollution. To complete the whole picture, the volume of nonbiodegradable plastics is increasing every day. Some collection strategies include, but are not limited to:

• Single stream or comingled collection strategy

designing for recycling

involving the collection of all dry recyclable materials into a single container.

Efficiently manage end-of-life (EOL):

• developing new technologies and systems for collecting, sorting, and recycling

• developing effective use of recycled plastics • ease access to recycling programs • expanding the types of recycled plastics Keep in touch with markets:

• Separating mixed MSW collection strategy, where waste is separated into multiple streams, that is, general wastes, organic wastes (garden wastes, food, etc.), and other material wastes (plastics, metals, etc.).

• Separating biowaste and other dry wastes. • Separating organic waste (including biowaste,

• aligning plastics product performances with actual

paper, cardboard, and wood) and inorganic waste (including plastics, metals, and others) and glass.

applications, for example, a 50-year lifetime is unnecessary if the actual use time is 5 10 years

• Multiple stream collection strategy involving

• aligning

recycled requirements

products

with

market

• improve quality of recycled plastics

12.4 Wastes: Collection and Financing Schemes The amount of waste is exploding, which worsens the issues concerning collection and financing of their treatment. New incompatible naturalsourced polymers or fossil plastics make the issue harder and cannot be integrated into existing streams requiring the opening of new channels.

12.4.1 Collection Systems: Separate or Commingled Waste Separate, partially, or totally (including glass) comingled collection systems are used with

the separation of biowaste, paper, and other mixed dry waste, which includes plastic waste, into separate fractions. Many other scenarios are used including mixed scenarios. Collection systems include:

• Curbside collection systems • Bring in systems • Deposit-and-return systems The collection efficiencies (capture rate) for plastic collection are roughly estimated to 10% (or less) for comingled waste, 75% for presorted wastes, and even 90% for PET bottles coming from deposit programs with low levels of contamination. Shehu (2017) studies and models several scenarios for the recycling of plastics in Finland, hypothesizing recycling rates of 1%, 18%, 31%, 44%, 52% according to the used collection conditions.

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12.4.2 “Polluter Pays” Principle This principle states that, directly or indirectly, the polluter must pay for the collection, sorting, processing, and decontamination of the produced or consumed product, device, and so forth. There are not common rules and only a few examples are given, showing their diversity. Many other systems may be set up by some nations. For example, household wastes collection and processing may be paid for by a fixed tax or by bin or may be taxed with pay-per-bag fees. For a different case, car pollution may be compensated for by a tax varying with the consumption, the power, the type of fuel, among others. Those taxes are included in the final cost of the car. For electronic and electrical equipment many solutions coexist, for example:

• An advance recovery fee, advance recycling fee, or advance disposal fee is paid by the consumer at the point of sale when purchasing a new product and is used to finance some part or all of the recycling process.

• General tax base funding where an additional tax would be imposed at the state or national level to fund state or national electronics recycling efforts.

• EOL fees are defined as a cost paid by the end-user at the point of discard for the electronic device. The fees provide immediate funding for a recycling system.

• Deposit and refund are where the consumer makes a deposit at the time of purchase of a new product and receives a refund upon returning the used container. This financial mechanism is popular for products such as bottles and cans. The carbon tax: Carbon is present in every hydrocarbon fuel (coal, petroleum, and natural gas) and is converted into CO2 and other products upon burning. CO2 is a GHG expected to be responsible of the climate warming. A number of countries have implemented carbon taxes or energy taxes that are related to carbon content or equivalent CO2 emissions. These taxes are often applied to combustible energy products and motor vehicles. In contrast, non-combustion energy sources— wind, sunlight, geothermal, hydropower, and nuclear—do not convert hydrocarbons into CO2. They can be supported by carbon credits.

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12.4.3 Polymers Incompatible With Existing Recycling Streams Even for traditional fossil polymers, combinations of materials such as polyvinyl chloride (PVC) and PET are particularly hazardous. If incompatible plastics are mixed in the same waste stream, the consequences can be disastrous. Sorting existing recycling streams must be efficient enough to avoid processing issues of compounds partially or totally based on recyclates. For example, a low level of PVC in a PET is harmful for the recycled PET. For mechanical recycling, the acceptable PVC level in a PET stream may be as low as 0.25%. Obviously, compatibilization technologies which allow multimaterial and particularly multilayer packaging materials to be recycled into new products cause a lot of scientific work. Natural-sourced polymers, “biodegradable” naturalsourced or fossil plastics, and, more generally, plastics polluting traditional plastics streams must be avoided or easily collected and sorted or must give rise to a new viable stream. For example, the incompatibility of polylactic acid (PLA) compounds with most other resins creates issues for recycling and also for the running of the processing machinery and lines that must be properly cleaned before feeding and purged to prevent any cross contamination. Recycling of bio-based plastics must be organized and planned by all stakeholders and should be effectively applied by all players including those that reuse recycled plastics. Of course, the recycling must be economically viable.

12.5 Recycling Management The global recycled plastics market (see Chapter 9: Recycling of Plastics, Advantages and Limitation of Use) was estimated, in US$, to be at tens of billions in 2017 and is projected to reach about US$50 billion by 2022 at a CAGR of 6.4% between 2017 and 2022. To support the management of millions of tons of plastics waste, new rules must enter into force including clearer obligations for all stakeholders, most notably:

• For authorities to step up separate collection, encourage investment in recycling capacity and quality, minimize or ban less sustainable practices (e.g., incineration, landfilling), and more closely harmonize rules.

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• For other stakeholders to smartly and fully A few examples have already been seen such as:

According to a study (http://www.plasticsmarkets.org/jsfcode/srvyfiles/endusedemand_report_ v8_1.pdf), the most commonly-cited barriers to recyclate use are:

• Coca-Cola launching its innovative PlantBottle

• Not enough of a price advantage over virgin

apply edited rules, directives, guidance, etc.

packaging technology based on recyclable PET beverage bottles made from up to 30% recycled resin in the first step.

• Toyota Motor Corporation announcing plans to make vehicle liner material and other interior surfaces from an ecological PET consisting of 70% terephthalic acid and 30% biological raw material derived from sugar cane replacing monoethylene glycol. For another example, Sony has reduced the use of nonrenewable resources by developing SORPLAS, a fire-retardant recycled plastic comprising polycarbonate that offers both sustainability and high performance, making it useful for new products. Instead of a typical 30% use of recycled plastics in electrical and electronic products, SORPLAS allows for an up to 99% recycled content due to a specific flame-retardant solution. SORPLAS is claimed to be recyclable several times over with an admissible loss of performance. This initiative could help to reduce manufacturing emissions by nearly 80% during its production as compared to virgin resin. The various steps of the recycling scheme controlled by Sony include:

• Collection of wastes: incorporating waste optical discs and leftover film from Sony and other factories as well as postconsumer materials such as plastic water bottles.

• Formulation and production. • Actual reuse: taking advantage of the combination of structural strength and flame retardancy, SORPLAS can be used for end products as diverse as lighting devices, handheld cameras and camcorders, business office elements, industrial wastewater purifiers, and TVs. Many other structured projects are emerging combining all the steps of a circular economy including design, waste collection, sorting, recycling treatments, and market outlets.

resins

• Not enough recyclate available to match the required specifications

• • • •

Variability of supply Contamination FDA restrictions Lack of demand

More generally, it is necessary to create a virtuous spiral leading to a better quality of recyclates at affordable prices so as to arouse the interest of designers and plastics converters. A few examples of private or corporate initiatives are given here.

12.5.1 Examples of Direct Involvement of Plastics Producers As already said, various plastics producers offer grades partly made out of recyclate or bio-based polymers. New projects are continuously launched involving several players of the value chain including producers, which ensure a steadier quality and a defined level of reuse and mitigate the bad image of recyclate. For example:

• Clean Site Circular Project by Total and several partners

• Borcycle by Borealis for polyolefins • Chemical recycling solution for polystyrene by INEOS Styrolution

• Certified circular polymers by SABIC • Neste Bioplastics Solution to produce biobased plastics

• Carbon renewal technology by Eastman for nonpolyester plastics and mixed plastics that cannot be recycled with conventional recycling technologies

12.5.2 Example of Associations of Plastics Industry FKS, association of the Dutch plastic pipes industry, has organized a national collection

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

scheme for plastic pipes in the Netherlands. The objective of the industry was to offer a complete environment-friendly service for pipe users, from the factory to the grave, through a voluntary commitment. PVC is recycled into new multilayer pipes (core of recycled PVC and external layer of virgin PVC), which are marked with a FKS logo. This FKS logo is a certificate of guarantee that certifies that the pipes adhere to the technical European norms and are made with recycled materials. For PVC pipes, the associated costs of the FKS system are expected as:

• h0.10/kg for collection • h0.35/kg for sorting and recycling (in this case, flake production)

• h0.15/kg for micronization (reducing flakes into a fine powder) The total costs of the FKS recycling scheme can be estimated to be h0.60/kg.

12.5.3 Example of Difficult-toRecycle Hi-Tech Carbon Fiber Reinforced Plastic Composite for Aeronautics Boeing and Airbus including the entire supply chain are generating as much as about 1000 t of cured and uncured carbon fiber prepreg waste each year. There are now many companies that offer composite recycling services and are able to reprocess these wastes, but there is a general technical problem. The fibers are discontinuous and almost always chopped, which limits the range of products, applications, and processes. Several strategies are to be investigated:

• Find new application fields using short carbon fibers such as interior panels for aeronautics.

• Use uncured composites in less demanding applications such as automobile applications. For example, ELG Carbon Fibre Ltd. will introduce the CARBISO range of recycled carbon fiber products for high volume, lightweighting solutions in automotive applications.

• Develop new recycling processes that preserve the fiber length.

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12.5.4 Example of Industrial-Scale PS Recycling Channel MarketsandMarkets (https://www.marketsandmarkets.com/Market-Reports/polystyrene-market148308682.html) expects the worldwide polystyrene market to be worth about US$28 billion by 2019. A producer of polystyrene (Total), a user of PS (Saint-Gobain), a promoter of recycling (Citeo) and the French Union of Fresh Dairy Product Manufacturers (Syndifrais) are joining forces to help lay the groundwork for an industrial-scale polystyrene recycling channel and to validate its technical and cost feasibility. Targeted goals involve collecting the packaging, finding the right technical solutions for recycling, and identifying uses for the recycled polystyrene. It is estimated that the major applications are in construction and packaging. Citeo will contribute to the emergence of a recycling channel for polystyrene packaging. Total has the objective to validate all the aspects of its large-scale recycling technology. Saint-Gobain is involved in initiatives related to the circular economy, particularly in the construction domain via its subsidiary Placoplatre. These cases are only examples and many others may be found in the literature. They show the essential roles of:

• the will of several stakeholders • the need for a clear road map for all the steps of the defined project

• the need to be in touch with the market • the effective collaboration between collecting channels, recyclers, and users of recycled materials Among many other examples, end-of-life vehicles (ELV) and waste electrical and electronic equipment (WEEE) are well known.

12.5.5 Better Reliability and Availability of Recycled Plastic Are Unavoidable Issues The European Plastics Converters Association (https://www.plasticsconverters.eu/) conducted a European survey in 2018 on the use of recycled

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Table 12.5 Issues Restraining the Rising Use of Recycled Plastics. Poor Opinions (%) of Main Barriers to the Use of Recycled Plastics The specifications of products do not allow for the use of rPlastics

49

Insufficient quality of rPlastics

40

Regulatory requirements/insecurities prevent using rPlastics

30

Limited quantitative availability

12

Insufficient demand/acceptance from the market

12

Prices are not competitive

10

Other

16 Qualitative Problems

Insufficient reproducibility of properties from lot to lot

47

Insufficient quality to meet market requirements and regulation

39

Color of rPlastics

39

Insufficient mechanical properties

36

Visual aspects in finished products

36

Smell/odor of the finished goods

31

Functionalities

20

Smell/odor of rPlastics during the production process

11

No qualitative problems

6

Other

6

• For new applications, recycling must be thought since the design step by applying some design guidelines reminded Chapter 9.

• For EOL products, the reliability of recycling mainly results from better sorting and efficient upgrading.

160 140 120 100 80 60 40 20

Insufficient supply

R PU

A M

PC

PM

PS

C PV

PP

PA

PE

PE D H

LD

T

0 PE

plastics materials (rPlastics) in Europe during which 376 companies from 21 different countries filled in an online questionnaire, pointing out some barriers to the increased use of recyclates. Table 12.5 displays the main barriers and qualitative problems quoted by the respondents. Fig. 12.6 shows negative opinions concerning the quality of 9 out of 10 families of recycled plastics. The best rated, rPET, reaps about one-fourth of the bad opinions. The basic answer to the claimed poor reliability of recycled plastics is the correct sorting of waste. This issue can be mitigated or solved by two ways adapted to the products and their stages of life:

Insufficient quality

Figure 12.6 Recyclates: poor opinion (%) for quality and supply.

12.6 Waste Sorting Sorting is a key step in the recycling of waste. Effective sorting is a primary step that enables the production of secondary raw materials of a similar quality

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

617

to virgin materials. Leading-edge technology solutions improve the identification, separation, and preparation of materials in order to optimize their reuse. Please note, the selected method may be:

• Positive sorting that focuses on identifying and removing a desired fraction from the input waste stream.

• Negative sorting that focuses on identifying and removing the undesired fraction (i.e., eliminating plastic bottles without the specific polymer properties required). Sorting techniques are constantly improved with automated detection of the type of waste and its constituents. Tools include sophisticated analyzers and automated sorting equipment as diverse as:

• Optical

separators definition scanners

equipped

with

technology (National Recovery https://19january2017snapshot. Technologies; epa.gov/sites/production/files/2015-06/documents/ highspeed.pdf)

• Delft University Kinetic: Gravity Separator • Holma Wilfley (http://www.holmanwilfley.co. uk/) wet shaking table

• Allmineral

(http://allmineral.com/en/homepage/) markets its “Allflux” upflow classifier

• Trommels and ballistic screens to separate mixed waste

• LMU

(Ludwig-Maximilians-Universita¨t Munich) researchers (http://www.en.unimuenchen.de/news/newsarchiv/2014/langhals_plastikmuell.html) have developed automated recognition of polymers taking advantage of the polymer-specific nature of the intrinsic fluorescence induced by photoexcitation

high-

• Sensors based separators • Shape and density separators • Near infrared (NIR) spectroscopy used to sort different colored polymers, for example, Sesotec WEEE-SORT N polymer separators (https:// www.sesotec.com/emea/en/industries/sub/plastics) are using NIR sorting systems for the identification and recovery of plastics such as acrylonitrilebutadiene-styrene (ABS) and polycarbonate

• Short-wave infrared spectroscopy for sorting plastics in the waste stream (http://www.sensorsinc.com/applications/machine-vision/plastic-sorting)

• High-definition infrared detection technology can be optimized for enhanced plastic detection, for example, Sortex (https://www.buhlergroup.com/global/en/products/sortex-polarvision.htm)

• Laser sensing technology (IDEC Co., LTD. and Photonics Advanced Research Center; http://www.idec.com/home/products/technology.html#IT_link) distinguishes between various kinds of plastics by the reflectivity of lasers of five wave lengths. The laser sensor is coupled with the robot technology of Mitsubishi Electric Engineering (MEE) Co.

• Visys Spyder laser sorting machine (http:// www.key.net/products/spyder)

• X-ray

• InGaAsHD camera technology • Sorting robots • Automatic control, etc. This list brings together some examples. The quoted company names, trademarks, and websites are provided “as they are” and do not constitute any legal or professional advice. Of course, the reader is the decision-maker responsible for the choice of the appropriate solution to their own problem. Sorting techniques must be adapted to the actual sorting issue. For example, sorting device manufacturers such as Buhler (http://www.buhlergroup.com/ global/en/process-technologies/optical-sorting/) can offer solutions for:

• • • • • • •

High-density PE (HDPE) sorting Pellet sorting PET sorting uPVC sorting WEEE/ELV sorting Recycled and virgin sorting Proprietary solutions, etc.

AI also emerges in sorting operations. For example, Max-AI technology (http://www.nrtsorters. com/max-ai-aqc-selected-apr-plastics-recyclingshowcase/) is an AI software that contributes to

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

identify recyclables and other items for recovery. Through deep learning technology, Max-AI employs both multilayered neural networks and a vision system to see and identify objects. In plastic recovery facility design, technology is driving improvements in recovery, purity, system optimization, and more. The Max-AI Autonomous Quality Control (AQC) system combines this intelligent technology with a robotic sorter to pick and place up to six different material types in one location. The AQC outperforms manual sorting in this role, consistently making smart decisions at a rate of 65 picks per minute over multiple shifts. As seen in Chapter 9, Recycling of Plastics, Advantages and Limitation of Use, the main issues to recyclate uses include reliability of supply, variations and limited performances, risks of polluting substances, and cost. Better waste management and advanced technologies of waste sorting may solve or mitigate these issues. Some methods are already opened and are promising, but must be more deeply investigated. Other paths are emerging and margins for processing costs could increase with the increase of oil prices leading to more expensive virgin plastics. New technologies may also drive lower recycling costs. Accuracy of sorting depends on many parameters:

• • • • • • • •

Waste origin Waste composition Object sorters or flake-sorting Polymers to be sorted Color sorting Pollutants Output Running costs, etc.

That being said, data from plastics recycling players show interesting potentials for accuracy improvement:

• For a given plant (see Table 9.3) Fig. 12.7 displays the accuracy (%) of fair sorted plastics made out of fair polymer of fair color. 39% of batches are fairly sorted, but about 5% of batches include about 10% of pollutants. Technological advances and probable price increases of virgin and recycled polymers allow for an improvement of well-sorted batches.

0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0

Frequency (%)

89.5-

91.5

93.5 % Fair resin

95.5

97.5 ou plus...

Figure 12.7 Fair sorted resin: accuracy frequency.

Following another way, for 24 different pieces of sorting equipment, their designers claim accuracy between 80% and 99.9% depending on:

• • • • • • •

Waste origin Waste composition Polymers to be sorted Color sorting Pollutants Method combination Number of runs on the same line or use of multiple lines

• Throughput • Running costs. etc. Table 12.6 displays a statistical analysis of the accuracy data (% well-sorted) for all technologies and by technology. Of course, previous data are examples that do not take into account the context. They demonstrate that high accuracy can be reached when high-tech means are used and higher recycling costs are agreed on by customers. It is likely that virgin costs will increase with crude oil prices and inevitably recyclate costs will increase allowing new investments and research efforts for better performing methods. Collection and sorting technologies must be adapted to the actual context. Of course, these facts and figures cannot be used for technical design and economic considerations. For instance, an advanced waste processing facility in Italy processes 150,000 t of postconsumer plastic packaging waste every year, allowing a reduction of about 200,000 t/year in CO2 emissions.

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

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Table 12.6 Statistical Analysis of the Well-Sorted Levels. All Technologies Accuracy (%)

Lowest Data

Highest Data

Mean

93

98

Median

93

99

Standard deviation

5

2

Mean 2 2SD

83

94

Minimum

80

90

Maximum

99

99.99

Mean 1 2SD

.100

.100

By Technology Accuracy (%)

Mean

Lowest Data

Highest Data

Camera

95.5

90

99

NIR

94.4

80

99.9

Vis

95

95

95

NIR Vis

97.7

92

99.99

X-ray

99

99

99

NIR, Near infrared.

The automatic system sorts postconsumer plastic containers for liquids including:

• • • •

clear PET blue PET colored PET HDPE

thanks to 40 AUTOSORT machines (https:// www.tomra.com/en/sorting/recycling/) using spectrometry and combining NIR and VIS (visible) sensors. NIR technology is used for sorting polymers and VIS sensors for sorting colors. The extracted secondary raw material is then separated into:

• flakes of PET from beverage bottles • granules of HDPE from bottles for liquids such as detergents

• granules of LDPE (low-density PE) and mixed polyolefins from carrier bags and film-type packaging The secondary raw materials are then sold to produce new wrapping and packaging materials,

objects, containers, building materials, vases, and other plastic items such as geomembranes used as insulating layers in the construction industry. At this facility:

• 80% of plastic is transformed into secondary raw materials

• 20% is transformed into secondary solid fuel used in cement works and blast furnaces

• Nothing is sent to landfills

12.7 Suppress the Pitfall of Waste Sorting: Process Plastics Waste Without Sophisticated Sorting The way is open for the recycling of plastics without sophisticated sorting, for example, due to enzymes or to microwaves.

12.7.1 Depolymerization by Enzymes For example, CARBIOS (https://carbios.fr/) developed a new approach of polymer recycling based on

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highly specific biological enzymes enabling the specific depolymerization of a single polymer (e.g., PET) without a sophisticated sorting process. At the end of this stage, the monomer(s) resulting from the depolymerization process are purified, with the objective to repolymerize them, thus, enabling an infinite recycling process. Eventually, the plastic residues not degraded during the first stage can be depolymerized in the same way in a second stage by applying a second different specific enzyme that depolymerizes the second polymer, etc. If monomer purification is efficient, the recycled materials have the same level of performance displayed by the original materials. Among plastic waste, CARBIOS is particularly interested in polyesters (PET, PLA, etc.) and polyamides that are easier to depolymerize by specific enzymes. In June 2019, CARBIOS announced that the United States Patent and Trademark Office (USPTO) has issued a Notice of Allowance for an additional US patent for CARBIOS’ proprietary process of recycling PET plastic waste. Following the enzyme route, a research team from the University of Greifswald and the Helmholtz-Zentrum Berlin (HZB) have solved the molecular structure of an important enzyme— MHETase (mono-hydroxyethyl terephthalate)—discovered in bacteria. Together with a second enzyme, PETase, MHETase is able to break down PET into its basic building blocks. The researchers produced a MHETase variant with optimized activity that can be used, together with PETase, for a sustainable recycling of PET. The results have been published in the research journal Nature Communications, DOI 10.1038/s41467-019-09326-3. The REnescience process by Orsted is another example of recovering plastics and metals from MSW without sorting using enzymes, mechanical sorting, recycled water, and anaerobic digestion. The REnescience process (http://www.renescience.com/en/) separates household waste into recyclables (metal, plastics, and other organics). Plastics can be recycled by traditional methods and liquefied organics are turned into green energy. The first plant opened in 2017.

12.7.2 Depolymerization by Microwaves ReVital Polymers, Pyrowave, and INEOS Styrolution announced a strategic partnership to

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

recycle polystyrene packaging collected in consumer curbside and depot recycling systems as well as other sources such as restaurants, offices, schools, and universities.

• ReVital Polymers recovers and recycles product packaging including rPET, rPE, and rPP.

• Pyrowave leases small modular recycling machines to depolymerize on-site mixed plastic waste using a proprietary technology defined as Catalytic Microwave Depolymerization. The equipment converts mixed plastics with or without food contamination into predominantly oil containing valuable waxes and monomers. The products are sold to chemical companies that reuse the monomers and waxes for FDA compliant applications.

• INEOS Styrolution is a global leader for styrene monomer, polystyrene, ABS standard, and styrenic specialties.

12.7.3 Other Methods Pyrolysis, thermochemical, selective depolymerization in supercritical fluids, and solvent recycling are also alternative recycling methods less demanding from a sorting point of view. Thanks to continuous research efforts, new processes are announced that can improve the performance and make them viable in a more or less near future.

12.8 Municipal Solid Waste: A Mine of Plastics (and Other Materials) or an Environmental Calamity? Only a small fraction of plastic recovered from consumers is actually recycled; most of the collected material is dirty and so mixed up that most recovered plastic is simply burned or dumped on land, in rivers, or even directly in oceans. Collection and recycling depend on the willingness of stakeholders, the general economy, bans and regulations, and technical advances. Large differences may be observed in recycling rates between countries of the same continent, Europe for example. Recovery rates may range from more than 60% in Germany to 1% in Serbia in round figures. For the six most performing

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

countries, recycling levels are equal or higher than 50%. At the opposite, the five less performing countries recycle less than 20% of their plastics wastes. This proves the broad margins of improvement, at least for the lesser performing countries. Increasingly abundant MSW lead to economic and environmental problems. On the one hand, costly disposal of mountains of useless, bulky, and polluting used materials, and on the other hand, cost, habits, and willingness to recycle, and the actual use of the recycled materials with most of the benefits of sustainable solutions. The global waste generation rate is unclear, but it is sure that wastes are unavoidably rising depending on the country and location. As in 2012, the World Bank estimates that the cities of the world generate 1.3 billion tons of solid waste per year. With rapid population growth and urbanization, municipal waste generation is expected to rise to 2.2 billion tons by 2025. Of course, extra urban population also generates wastes. In low and middle-income countries, waste is often disposed of in unregulated dumps or openly burned. These practices create serious health, safety, and environmental consequences such as global climate change. Managing waste properly is essential for building sustainable and livable cities, but it remains a challenge for many developing countries and cities. More specifically, concerning plastics, the percentage of plastic waste in the MSW stream is also unclear with a broad range varying according to a factor of 2 in round figures. For the global urban population, an estimate among others reaches 200 million tons of plastics wastes, that is to say, about 80% of the plastics consumption during the same year. Of course, all the waste cannot be recycled, but MSWs are a promising source. Data are given without any guarantee, but may give a rough idea of the interest of MSW as a source of recycled plastics. As an example, Europe processes waste:

• First by incineration (about 60% in round figures), but this is not the best solution from a sustainability point of view.

• Second by landfilling (about 30% in round figures), but this is the worst solution from a sustainability point of view. It takes 300 500 years to for plastic items decompose in landfills.

• Third by recycling (about 10% in round figures).

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The United States, according to the environmental protection agency (EPA), processes waste:

• First by landfilling (about 75% in round figures), the worst solution from a sustainability point of view.

• Second by incineration (about 15% in round figures).

• Thirdly by recycling (about 10% in round figures).

• Currently, due to the lack of infrastructure, the widely varying municipal recycling programs, and the low awareness of proper recycling practices, more than half of the material that could be recycled from US households is lost. Plastics sustainability may be improved by collection and sorting enhancement. Fig. 12.8 represents a scheme that is already applied and that can be generalized and perfected to improve the quantity and quality of recycled plastics.

12.9 Ocean Litter: Calamity or Untapped Feedstock? It is estimated that globally, 5 13 million tons of plastics (or 1.5% 4% of global plastics production) end up in the oceans every year and their accumulation represents more than 150 million tons for all oceans. Commingled with other solids they form marine litter “islands,” which are particularly shocking from a visual point of view. It is estimated that plastic accounts for over 80% of marine litter. UNEP (United Nations Environment Programme) estimates that damage to marine environments is at least US$8 billion per year globally. Marine litter can cause serious environmental, health, and economic damages including losses for coastal communities, tourism, shipping, and fishing. The smallest plastics items, often referred to as microplastics (usually less than 5 mm), can be ingested by aquatic wildlife leading to potential risks, injuries, poisoning, and other damages. Additives may be dissolved by water that is polluted and release pollution all along the food chain. Litter pollutes beaches and damages the environment.

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A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

MSW

Plastics

Mixed plastics

Monomaterial

Commodity

Engineering

PE

ABS

PP

PA

PET

PC

PVC

PMMA

Paper

Metal and other materials

Metal

Glass

Other materials

Residue

Residue

Reprocessing

PS

Figure 12.8 Example of scheme of MSW processing. MSW, Municipal solid waste.

Of course, marine litter is also synonymous with the loss of useful matter that needs to be fought by such measures as:

• Preventing leakage of plastics • Cleaning up the oceans • Recycling and reuse Leakages come from poor solid waste management, wastewater collection and treatment, and the lack of awareness of the public and companies at large about the consequences of their actions. Main sources of marine litter include:

• Land-based activities such as landfilling, industrial outfalls, untreated municipal sewerage, littering on beaches and other coastal areas.

• Sea-based activities such as fishing and aquaculture, shipping (e.g., transport, tourism), yachting, offshore mining and extraction, illegal dumping at sea. Currently, cleaning up the oceans is not a realistic option from an economic point of view.

However, a lot of efforts are underway to solve this problem. The potential cost across the European Union for coastal and beach cleaning was assessed at almost h630 million per year. Mandatory rules might be necessary to speed up the cleaning of the marine environment. Ocean litter damages are to such an extent that the issue cannot be tackled by a single entity and some organizations have created dedicated platforms. For example:

• The Global Plastics Alliance, a collaboration of plastics producers and manufacturers worldwide have signed the “Global Declaration for Solutions on Marine Litter” (https://www.marinelittersolutions.com/about-us/) including six key objectives: • Raising more marine litter awareness • Research for facts to quantify marine litter evolution • Promoting best policies • Spreading knowledge • Enhanced recovery • Preventing pellet losses during transportation, distribution, and manufacturing

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

• The

New Plastics Economy Global Commitment is led by the Ellen MacArthur Foundation, in collaboration with UN Environment, and is signed by many of the world’s largest packaging producers, brands, retailers, and recyclers as well as governments and NGOs (https://www.ellenmacarthurfoundation.org/news/a-line-in-the-sandellen-macarthur-foundation-launch-global-commitment-to-eliminate-plastic-pollution-at-thesource).

• The Ocean Legacy Foundation (https://oceanlegacy.ca/) is an international nonprofit organization that develops the world “Marine Debris Solutions” program. This dynamic and integrative approach combines sustainable technologies with education and skills training to give all plastic wastes economic value.

• Waste Free Oceans is a nonprofit organization that mobilizes fishermen, recyclers, brand owners, and the plastic industry to remove floating plastic from the ocean and then upcycles it into meaningful products.

• Parley

(http://www.parley.tv/#fortheoceans) has been created to accelerate the process of change that is already in progress concerning environmental issues of ocean litter by gathering in the same platform fishermen, recyclers, brand owners, plastic industry, designers, journalists, architects, inventors, scientists, etc.

• The members of the Trash Free Seas Alliance (https://oceanconservancy.org/trash-free-seas/ plastics-in-the-ocean/trash-free-seas-alliance/) pledge to work toward solutions that will eliminate ocean trash. The Alliance provides a constructive forum focused on identifying opportunities for cross-sector solutions that drive action and foster innovation.

• The “Ocean Cleanup” is a nonprofit organization developing advanced technologies to rid the world’s oceans of plastic. “Ocean Cleanup” launched in September, 2018, its “System 001” that takes advantage of the ocean currents. This passive drifting system is expected to clean up half the Great Pacific Garbage Patch in 5 years. Marine waste collection is a specific problem needing a special economic scheme and adapted

623

technologies such as trawling. Collection trawls can be towed by boats of varying sizes. For rivers, trawls can be placed within the body of water needing no human action until the net needs to be emptied. The recycling of plastics recovered from marine litter meets the same problems and finds the same solutions as the recycling of EOL waste (if the collection step is effective). Cleaning of waste can be more difficult because of marine microorganisms and other deposits. Chemical attack may also be more damaging, requiring efficient upgrading. Outlets are the same as for other recycled plastics, needing new efforts to find broader applications. Currently, a few actions and projects are on the way bringing together representative members of all stakeholders, that is fishermen and other marine players, recyclers, plastics industry converters, customers using plastics, associations, among others. The goal is generally to demonstrate the theoretical feasibility without taking into account the economics. By 2017, the “Global Plastics Alliance” launched more than 355 projects around the world focusing on six key areas.

• • • • • •

Education: 136 Recycling/recovery: 91 Public policy: 42 Best practices: 41 Research: 38 Plastic pellet containment: 9

For another example, the initiative “Let’s Clean Up the Danube Together” is an action coordinated by the Waste Free Oceans Foundation and is jointly implemented with the help of Plastix, Bulgaria Cap Project, Henkel, and Eco Partners, among others. Henkel will remove plastic waste from oceans and rivers and transform it into over a million bottles used for its Lovables laundry brand. The collaboration will run for at least 3 years and aim to remove enough plastic from rivers, lakes, seas, and oceans to produce 100 MT of usable recycled material each year. Volunteers will gather plastic waste from the Danube banks and beaches, while teams of fishermen will trawl

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the river using a special device that removes floating plastic waste from the water. The trawlers are able to collect between 2 and 8 MT of marine litter on each journey. The collections along the Danube will be followed by activities at several locations in the Mediterranean Sea. Once recycled, the plastic will be included in bottles for the Lovables laundry brand. The brand also aims to include recycled marine plastic litter from Waste Free Oceans (https://www.wastefreeoceans.org/) in over a million bottles. Furthermore, Henkel’s packaging follows other principles of circular economy preventing marine litter growing:

• Less packaging • Less waste • Better packaging For a third example, Adidas has launched the UltraBOOST Uncaged Parley produced from recycled ocean plastic waste recovered from the sea. Adidas created the running shoe using a combination of 95% plastics recovered from the Indian Ocean near the Maldives and 5% recycled polyester. The shoe laces and lining are also produced using recycled materials. The Parley Global Cleanup Network and Remote Island Interception operations are responsible for capturing and repurposing plastic waste. Orca Sound Project (http://www.orcasoundproject.com/) is a platform for collaboration, consultation, and activation that actively sources, collects, and treats ocean plastic ready for production. Orca Sound Project subsidies global fisheries to trawl for plastic instead of fish. Ecover has launched its Ocean Bottle made from 50% ocean plastic collected from the Rio and other beaches. Ecover will introduce 100% recycled plastic across packaging of all its products by 2020. Several government agencies of India fund social associations and fishermen to harvest all of the plastic found at sea while the women of the association wash and sort the collected waste. The system is not completely self-sufficient and most waste is too damaged and eroded to be recycled in traditional ways. Instead, it is shredded and sold to local construction crews who use it to strengthen asphalt for paving roads.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

12.10 Examples of Sustainable Renewable Sources Used or Proposed by Resin Producers Resin producers propose plastics grades partially made out of plant-derived, waste-sourced polymers or postconsumer recycled plastics such as, for example, Rnew, Bio, Eco, iQ, resound grades, among others. Regarding plant-derived polymers, several examples have already been quoted such as PLA, starchbased, among others. Continuing research efforts should open new channels. Waste-derived polymers from the by-products of all sorts of industries, for instance, food, energy, or chemical industry. Among others quoted, there is the example of methane captured in palm oil mills and waste fats used for PE production leading to more or less depletion of carbon footprint. In a cradle-to-gate carbon footprint comparison (https:// www.iscc-system.org/wp-content/uploads/2017/04/ Kaptijn_Sabic_ISCC_Sustainability_Conference_040215.pdf):

• Palm oil fatty acid based PE production (100% methane capture in palm oil mills) emits: 21.23 kg CO2 equiv./kg PE

• Palm oil fatty acid based PE production (5% methane capture in palm oil mills) emits: 11.03 kg CO2 equiv./kg PE

• Conventional petroleum naphtha based PE production emits: 11.86 kg CO2 equiv./kg PE

• Waste fats based PE production (SABIC route for renewable PE production) emits: 22.31 kg CO2 equiv./kg PE Postconsumer waste recyclates can be incorporated into virgin resins for environmental and economic benefits. Commodity and engineering resins are concerned such as PE, PP, PVC, styrenics, PET, polyamide (PA), polycarbonate (PC), ABS, polytetrafluoroethylene (PTFE), and so forth.

• Postconsumer plastic waste from household and industrial consumers are recycled into high-quality LDPE and HDPE.

• Neste and IKEA will produce PP plastic from fossil-free, bio-based raw materials at commercial scale.

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

625

It is expected to take 5 years to achieve commercial deployment. Biofuels and other biodiesels can be refined as petroleum and be used to replace it as feedstocks for plastics polymerization.

1.4 1.2 1 0.8 0.6 0.4 0.2 n

FE PT

c ni

yl o N

PC

yr e

St

Ac S ry lic s

E

AB

-P

PP U

H

M W

C PV

T PE

PE

0

Figure 12.9 Producers offer: percentage of grades including recyclate.

• Chemical recycling can create new outlets for plastic waste by enabling high end product qualities, thereby complementing traditional mechanical recycling. Taking into account plastics databases such as Matweb (http://www.matweb.com/search/ MaterialGroupSearch.aspx) or M-Base (https:// www.m-base.de/en/), it can be expected that plastics producers offer between less than 0.1% to more than 1% of grades containing recycled material (see Fig. 12.9). Trend is up and new research and collection growth must lead to the launch of new grades based on recycled material. Waste industrial CO2 as feedstock: for example, Covestro (http://www.covestro.com/en/), formerly Bayer MaterialScience, has developed a process for the production of polyether-polycarbonate-polyols, which uses the GHG CO2 as a building block. Following a successful test phase and promising market analysis, Covestro plans to invest h15 million in the construction of a production line to produce a precursor for premium polyurethane foam. The line will have an annual production capacity of 5000 MT. Covestro claims polyether-polycarbonate-polyols have at least the same level of quality (high) as conventionally manufactured materials and a more sustainable impact. The CO2 balance of the new process is far better than that of the conventional production method. Ford is working with Novomer to develop polyurethane foams formulated with up to 50% CO2based polyols meeting rigorous automotive test standards. The new polyurethanes aim to be used in seat cushions, seat backs, floor mats, and other components like side paneling and console features.

12.11 Supramolecular, Vitrimers, and Other Self-Healing Polymers Exposures to harsh environments easily lead to degradations of polymers, paints, and polymer composites and can significantly shorten structure lifetimes. Mimicking nature, self-healing polymers target the partial or total repair of these injuries allowing to assume a temporary or permanent functional usage. Multiple chemical or physical ways are investigated including in situ healing systems, self-healing polymers, embedded healing agents, extrinsic systems. The chemical methods through embedded reactive healing ingredients are the most often studied using two-part healing systems, microencapsulated or containment in hollow fibers or CNTs. The physical method using an encapsulated solvent is demonstrated for thermoplastics, but needs further study for industrialization. The physical method of intrinsic self-healing polymers is based on surface rearrangements, diffusion, wetting, reptation, and randomization of macromolecules ensuring the disappearance of cracking interfaces. Chemical methods for intrinsic self-healing polymers include reaction of unreacted species, broken molecule rebuilding, and the creation of labile bonds in lieu of chemical bonds. Among the industrialized breakthroughs, there are, for example, self-healing paints penetrating the automotive industry, self-healing silicone gels for electronics, the Reverlink range of products by Arkema based on the supramolecular chemistry. Bayer, Nissan, Lexus, HMG Paints, and others, develop, commercialize, or use self-healing twocomponent polyurethane topcoats for self-repairing scratches on painted car surfaces including scratches from car-washing machines, off-road driving, and fingernails. In supramolecular chemistry, the bonds holding together small or large molecules are reversible physical bonds.

626

Arkema’s research and development focuses on its application in the field of polymers, marketing the Reverlink range including semi-crystalline resins and elastomeric materials based on renewable sources. Cidetec (https://www.cidetec.es/en/top-achievements/self-healing-polymer) proposes self-healing polyurea-urethane elastomers, which could show quantitative healing efficiency at room temperature, without the need for any catalyst or external intervention. Advanced composites are a promising application field and promote a multitude of studies concerning, for the more sophisticated technologies, multiple-times self-healing composites mimicking the biological pervasive vascular network to supply the necessary healing components or highperformance composites for aerospace and defense combining the use of mendomer materials and magnetic microparticles and nanoparticles allowing a composite to be heated up to its glass transition temperature by the application of a magnetic field. Inherently thermally self-healing thermoset polymers open the way to endless recycling due to alternate Diels Alder (DA) and retro-DA reactions forming and subsequently breaking polymeric crosslinking. This is a new step toward the cradleto-cradle concept. For example, Mallinda (http://www.mallinda. com/about) makes reversible thermoset prepreg laminates for high-throughput composite part production. Mallinda’s patented resin system enables the compression molding of products in just seconds for high-throughput, high-volume production of structural composites. Mallinda’s prepreg resin is claimed to be a disruptive platform technology that allows rapid (,1 minute) compression molding of fully cured thermoset composite parts. In addition, Mallinda’s resin can be depolymerized in solution for a cradle-to-cradle, energy-neutral system for the recovery of resin and woven/full-length fiber. Resin is included in the vitrimer family consisting of molecular, covalent networks, which at high temperatures flow like viscoelastic liquids and at low temperatures can behave like classical thermosets. Besides epoxy resins based on diglycidyl ether of bisphenol A, other polymer networks have been used such as polylactic acid (polylactide), polyhydroxy-urethanes, epoxidized soybean oil with citric acid and polybutadiene.

A PRACTICAL GUIDE TO PLASTICS SUSTAINABILITY

12.12 Conclusion The tripod—environment-friendly, economic efficiency, social advancement—base of sustainability must be continually reviewed and optimized according to the actual situation, local requirements, technical advances, and competition with alternative materials. Plastics are often suspected of being a poor material from a sustainability point of view, but like many topics, the sustainability of plastics is a gray area. Sustainability being a fluctuating concept, that is false and true. That is false because the plastics industry already applies a significant batch of guidelines of sustainability. That is true because the plastics industry does not take full advantage of the many other ways emerging from the general transition of the world toward better sustainability. Of course, the future of the sustainability of plastics is closely related to the rational or irrational rejection or adoption of plastics and their comparison with alternative materials. Only some factors have been examined and many others can be more or less influential according to time, location, general world evolution, and innovative applications. Sustainability generates expenses, but also creates new jobs and businesses. Efforts regarding decarbonization create additional opportunities for growth. More plastic recycling helps to reduce dependence on imported fossil fuel and to cut CO2 emission. In all likelihood, in the long-term, sustainability is a survival condition that must be supported by regulations. That being said, some general guidelines include, but are not limited to:

• Eco-design • Objective consumer awareness • Transition from linear economy toward circular economy

• Minimization of waste generation • Effective waste recycling systems, etc. Poor recycling rates of plastics need special attention:

• Consumers must be alerted and convinced of the need and benefits of recycling and reuse,

12: PLASTICS SUSTAINABILITY: PROSPECTIVE

627

thus, contributing actively to the circular economy and the transition toward sustainability.

• Effective and realistic reuse of recyclates can minimize (or even solve) in the long term the issue of plastics waste. However, all stakeholders must keep in mind that recycling cannot save 100% of used materials. There is always a more or less high loss.

• Improve design and support innovation to

public procurement; legislative initiative on single-use plastics must reach a consensus; fiscal measures are desirable to boost the collection and recycling of plastics wastes.

• Recycling market must be stabilized in the long-term, giving the green light to high investment levels with admissible risks.

• Innovative materials and alternative feedstocks

make plastics and plastic products easier to recycle.

for plastics production must be developed and effectively used if they are more sustainable compared to the nonrenewable alternatives.

• All plastics products placed on the market

• Recycling, production of virgin plastics, and

must be either reusable or recycled in a costeffective manner.

processing must be optimized according to consumption locations, which would minimize transportation.

• Waste collection must be accessible to everyone.

• Waste collection systems of plastics must be adapted to local contexts and must reach high levels comparable with those of other materials.

• Authorities must issue new guidelines on the collection and sorting of waste.

• Plastics recycling capacity must be significantly extended, accessible.

modernized,

and

easily

• The plastics value chain must be far more integrated, and stakeholders must work together closely and find wider and higher value applications for recyclate output.

• The ocean litter issue must be solved by halting leakage of plastics to the ocean and taking remedial actions against existing litter. Prospective is a game of the mind based on numerous hypotheses related to the future. Obviously the real world can evolve differently introducing many discrepancies, errors, omissions, uncertainties, but it is also a benefiting brainstorming opening the door to innovative ways of thinking. Last, this book is not theoretical, but is intended to suggest concrete ways, some of which may be suitable for the own case of the reader. At the opposite end, some other suggested ways may be counterproductive concerning some contexts.

• Substances and design practices hampering recycling processes must be phased out.

• Create viable markets for recycled and renewable plastics.

• Develop quality standards for sorted plastic waste and recycled plastics.

• National governments must achieve a better sustainability through economic incentives and

Reference Shehu, S.I., 2017. Separation of Plastic Waste from Mixed Waste: Existing and Emerging Sorting Technologies Performance and Possibilities of Increased Recycling Rate with Finland as Case Study. Lappeenranta University of Technology.

Index Note: Page numbers followed by “f” and “t” refer to figures and tables, respectively.

A Aachen Center for Integrative Lightweight Production, 581 Accelerated aging, 173 Acidification, 97 Acidification potential (AP), 310 311, 311t Acoustic comfort, 79 Acrylics, renewable. See Renewable acrylics Acrylonitrile butadiene styrene (ABS), 464t, 480t Acrylonitrile styrene acrylate (ASA), 200 Additive costs, examples of, 372 Additives for aging protection, 443 444 recycled material upgrading by, 439 447 additives for aging protection, 443 444 compatibilizers, 442 impact modifiers, 442 plasticization, 443 purity enhancement, 446 447 recyclate upgrading, special additives and packages for, 445 446 sensorial property enhancers, 444 445 renewable. See Renewable additives Additives, compounding with, 51 66 aging protection: additives, films, 57 59 cost cutters, 64 66 nonblack fillers, 64 66 mechanical property upgrading and customization, 52 57 impact modifiers, 55 56 nanofillers, 54 55 plasticization, 56 57 reinforcement, 52 reinforcement and filling with mineral fillers, 53 54 reinforcement with fibers, 52 53 reinforcement with glass beads, 54 sensory properties, 59 64 additives for antifriction polymers, 63 antistatic specialties, 62 conductive carbon blacks, 62

conductive fibers, 62 conductive polymers, 62 fire behavior, 60 61 magnetic polymers, 63 64 metal powders or flakes, 62 odors, 60 polymers with high thermal conductivity, 63 scratch-resistance improvement, 60 structural foams, 66 use of recycled plastics, 66 Adidas, 598 599 Aeronautics, difficult-to-recycle hi-tech carbon fiber reinforced plasticcomposite for, 615 Aerospace industry, zero-defect manufacturing of composite parts in, 141 142 Aging, 76 77 Aging protection, 57 59 Akulon Ultraflow, 129 Alberdingk renewable PUR, 533 Algae and fossil polymer compounds, examples of, 550 Algix, 550 Aliphatic polyesters, 487 Aliphatic polyketones, 114 Alliance to End Plastic Waste (AEPW), 598 599 Alloying, plastic, 51 Alloys, 202 203, 549 554 algae and fossil polymer compounds, examples of, 550 of renewable and fossil polymers, 549 of renewable polymers, 549 renewable raw materials, various bioplastics derived from, 550 554 Altuglas/Plexiglas Rnew biopolymer resins, 543 544 Ambient humidity, 75 Ambient temperature, plastics behavior above, 171 174 accelerated aging, 173 average temperature, 172 continuous use temperature (CUT), 172 heat deflection temperature (HDT), 173 stabilizers and antioxidants, environmental cost of, 173 174

underwriter laboratories temperature index, 172 173 Vicat softening temperature (VST), 173 American Chemistry Council (ACC), 6 AMICO Supervision Software, 139 Aminolysis, 449 Amorim cork composites, 482 Amorphous polymers, 67 68 Amorphous transparent renewable polyamides, 526 527 Anaerobic biodegradation of biodegradable plastics with gas recovery, 452 Anisotropy, 72 73 Antiblocking agents, 482 Antifogging additives, 483 486 Antifriction polymers, additives for, 63 Antistatic additives, 482 Antistatic agents, examples of, 486t Antistatic specialties, 62 APIGO Bio, 550 property examples of, 551t APILON 52 BIO, 551 APINAT Bio, 550 APINAT F BIO, 551 Aramid fiber (AF), 168 ARBOBLEND grades, 543 ARBOFORM, 542 Arburg, 131 ARBURG, 152 Arc resistance, 179 Arkema, 626 Asian Lignin Manufacturing Pvt. Ltd., 545 Authoritarian restrictions, bans, and incentive actions, 597 600 Automotive industry, favorable example of, 160 161 Autonomous Quality Control (AQC) system, 617 618 Autonomous vehicles, 597, 601 Auto shredder residues (ASR), 413 AVA Biochem, 546 Avantium Renewable Polymers, 516 Average temperature, 172

B Bacterial fermentation, natural linear polyesters produced by, 499 503

629

630

Bacterial fermentation, natural linear polyesters produced by (Continued) application sectors, 502 503 environmental features, 502 processing, 502 producers and trademarks, examples of, 503 property tables, 503 Balancing the product durability and actual sustainable benefits, 156 157 Balsa, 479 481 BASF, 494, 518 Bcomp, 578 579 Best available techniques (BAT) in the production of polymers, 41 42 Bioadditives consumption, 387 389, 606 natural fiber composite market, 388 389 other bioadditives, 389 Biobased ethylene vinyl acetate copolymer, 513 Bioblocks, 586 Biochemical oxygen demand (BOD), 97 Biodegradable plastics, anaerobic biodegradation of with gas recovery, 452 Biofuels and other biofeedstocks from biomass, 36 38 Bioisocyanate crosslinker for polyurethanes, 532 533 BioLogiQ, 481 Bio-material costs, 390 391, 606 609 bioplastics costs, 390 391, 606 607 crude oil, 606 long-term costs of bioplastics compared to fossil plastics, 607 609 crude oil price expectations, 608 historical prices, modeling from, 607 608 modeling plastics prices, 608 609 natural fiber costs, 391 Bionolle, 487 Bioplastic capacities by market, 387, 605 606 by region, 387, 605 Bioplastic family market shares by, 385, 605 production capacities by, 385 386, 605 Bioplastics costs, 606 607 Bioplastics markets, survey of, 391 408 agriculture, 404 automotive and transportation, 392 399 building and construction, 399 404 consumer goods, 392 packaging, 392 Biopolyethylene and biosourced ethylene vinyl acetate, 507 513

INDEX

biobased ethylene vinyl acetate copolymer, 513 polyethylene application sectors, 510 512 polyethylene environmental features, 510 polyethylene property tables, 513 processing, 510 producers and trademarks, examples of, 512 513 traditional polyethylene reminder of advantages of, 510 reminder of drawbacks of, 510 Biopolymers, general behavior of, 187 Bio-polyols, 530 531 Biopolyurethane foams, 532 533 Biopolyurethane sprays, 533 BioRez resins, 549 Biosourced plastics consumption, 383 385, 604 605 Biosourced polycarbonates, 542 Biosourced polymers, 469 Biostrength 280 impact modifier, 488 Biotex Flax/PLA, 552 Biothermoplastic polyurethane, 533 Biovyn, 548 Bisphenol A (BPA), 538 Blow molding, 81 BMW, 456, 598 BOD (biochemical oxygen demand), 41 Boeing 787, 592 Boilermaking, 122 BOMcheck THINKSTEP, 105 Bottle recycling, 453 454 Bottles, collection of, 453 Bottle-to-bottle recycling, 454 Bottle to engineering thermoplastic polyester grades, 454 Brittle point, 174 175, 247 Building products recycling and reprocessing of, 456 457 Bulk modulus, 304 Burning, rate of, 182 183 BusinessWire, 411

C Cadmium, 26 Calendering, 81 CARBIOS, 619 620 Carbon dioxide, 19 20 -containing polyols, 531 532 emission, 458 460 gas warming potential (GWP), 96 Carbon fiber (CF), 168 170 Carbon footprint, 458 460 Carbon nanotubes (CNT) and graphene, 171 Cardolite, 545 Cargill, 113 Car sharing of autonomous vehicles, 597

Cashew nut shell liquid (CNSL), 489 Catalytic Microwave Depolymerization, 620 Cellulose, 469 470 Cellulose derivatives based on natural cellulose, 503 507 advantages, 506 application sectors, 506 507 drawbacks, 506 environmental features, 506 processing, 506 producers and trademarks, examples of, 507 property tables, 507 Cellulose nanofibers, 171 Cellulosics, 202, 470, 506 507, 508t CESA-natur light masterbatches (Clariant), 489 Chain Extender, 445 Chain Scissors, 445 Change, promoters of, 8 12 cautious forecast of major changes in the global environment, 12 examples of marketing strategy based on sustainability, 11 12 policies, directives and regulations, 10 11 standards and reporting, 8 10 Chemical oxygen demand (COD), 98 Chemical recycling, 447 449 polyurethanes, 449 thermoplastic polyesters, 448 449 Chemical Safety Report (CSR), 155 Chemolysis, 447 Chlorinated paraffins, 27, 154 Chlorinated polyethylene (CPE), 200 Chlorofluorocarbons (CFCs), 154 Chloroparaffins, 27, 154 Cidetec, 626 CIMV, 543 Circular economy, 1 3 Climate change, expected response to, 18 23 biological consequences, 23 climate warming and sea level rise: the major risks, 22 23 main greenhouse gases, 19 22 carbon dioxide, 19 20 halogenated gases, 21 methane, 20 21 nitrous oxide, 21 ozone, 21 22 sulfur hexafluoride, 22 urgency of decisions, 22 water vapor, 19 Climate warming and sea level rise, 22 23 Closed- and open-loop recycling auto, 455 456 electricity and electronics, 454 455

INDEX

Closed-loop recycling, 563 564 CMLCA, 101 CML-IA by CML, 100 Coca-Cola, 113 114, 454 COD (chemical oxygen demand), 41 Coefficient of friction (CoF), 368 Coinjection, 147 Colorants, collateral effects of from a sustainability standpoint, 191 195 colorants and pigments, 195 titanium oxide, 195 Colorants and pigments, 195 COMMISSION REGULATION (EU) 2015/1906 of October 22, 2015, 427 Compatibilizers, 442 Competence development, training, elearning, 157 Composites capability proposals for, 376 378 consumption, 606 expected cost of, 380 381 recycling of, 457 458 Compound annual growth rate (CAGR), 387 Compression modulus, 304 Conductive carbon blacks, 62 Conductive fibers, 62 Conductive polymers, 62, 179 180 Cone calorimeter, 182 Continuous use temperature (CUT), 172, 237 238, 238t Copolyester thermoplastic elastomers, 470 Copper, 26 Cority, 101 Cork, 482 Cost cutters, 64 66 nonblack fillers, 64 66 Cost estimator results, examples of, 378 380 agreement between different cost estimators, 378 379 check sensitivity and application window of variables of interest, 379 380 run size, example of effect of, 379 Cost estimator software, 378 380 examples of, 378 Costs, examples of, 380 381 expected cost of composites, 380 381 expected costs by market, 380 Covestro, 129, 531 533 Creep, 71 72, 332 346 Creep strength, 346t Crude oil, 606 Crude oil price expectations, 608 incentive effect of, 420

631

Crystalline and semicrystalline polymers, 68 71 crystallization, 71 glass transition temperature, 71 Crystallization test, 175, 249 Cyclic olefin copolymers (COC), 199

D Dairy Roadmap, 454 Danone, 454, 598 Data Distribution Centre (DDC), 101 DataXplorer, 139 Decision 2000/532/EC, 426 Demand and growth potential of plastics, 595 602 alternative fuels, 601 authoritarian restrictions, bans, and incentive actions, 597 600 dream of almost perfect polymers, 601 effects of demography and standard of living, 596 emerging technologies, 600 601 autonomous vehicles, 601 electric vehicles, 600 601 future global plastics industry, 595 596 plastics brand image, 601 602 specificities linked to sustainable plastics, 602 time management, rethinking, 597 Demolding agents. See Release agents Density, 249 260, 251t Depolymerization by enzymes, 619 620 by microwaves, 620 “Deposit and bill” approach, example of, 571 Dielectric loss factors, examples of, 354, 357t Dielectric strength, 179 examples, 354 Digitalization and software solutions, 130 142 enterprise resource planning software, 132 134 execution system software, manufacturing, 131 132 smart/intelligent machines, 130 131 software solutions integrated by plastics machinery providers, 135 141 energy monitoring, 136 Integrated Production, 139 Intelligent Machines, 138 139 interactive services, 139 141 troubleshooting, 136 138 zero-defect manufacturing (ZDM), 141 142 of composite parts in aerospace industry, 141 142 mass-produced molded parts, 141

Dimensional effects, 168 Dimensional stability, 75 76 design for, 176 178 aging, desorption, bleeding, releasing of organic components, 177 178 shrinkage, 177 thermal expansion/retraction, 176 177 warpage, 177 water or chemicals uptake, 177 organic additives, release of, 76 shrinkage, 76 warpage, 76 Diospyros peregrina, 490 DIRECTIVE 2002/96/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL, 428 434 Diverse indicators, 97 98 DOMO Engineering Plastics, 461 Domtar, 543 DOW ECOLIBRIUM bio-based plasticizers, 473 474 Due diligence, 91 DuPont, 517 DuPont Composite Recycle Technology, 461 DuPont Engineering Polymers, 129, 461 Dust/particulate matter, 311, 312t Dynamic fatigue, 167 168, 350t Dynamic torsion modulus, 247 249

E Eco-design, advanced environmental and engineering properties to support, 309 advanced indicators, examples of, 310 312 acidification potential, 310 311, 311t dust/particulate matter, 311, 312t ecotoxicity potential, 312, 313t eutrophication potential, 311, 312t ozone depletion potential, examples of, 310 photo-oxidant creation potential (POCP), 310, 311t electrical properties, 352 354 dielectric loss factors, examples of, 354, 357t dielectric strength examples, 354 resistivity examples, 354, 355t flammability, 355 364 fuel energy and feedstock energy, 309, 310t gas permeability, 365 367 gas warming potential (GWP), 309 natural-sourced versus fossil polymers, 312 314 optical properties, 365

632

Eco-design, advanced environmental and engineering properties to support (Continued) Poisson’s ratios, 349 352, 353t thermal dependency of mechanical properties, 314 321 long-term heat effect on oxidizing aging, 315 321 short-term effects of high and low temperatures, 314 315 time dependent mechanical properties, 321 349 creep, 332 346 fatigue, 347 349 relaxation, 346 347 tribological properties, 367 369 coefficient of friction (CoF), 368 limiting pressure velocity, 368 369 Eco-design, environmental and engineering data to support, 209 density, 249 260, 251t environmental indicators, 212 221 energy requirements, 214 216 examples of, 216 217 indicator per weight and indicator per functional unit, 220 221 net carbon footprint, CO2 and other greenhouse gases, 216 use of renewable materials instead of fossil resources, 214 variability and weakness of, 217 220 water footprint, 216 general boundaries of standards, 209 210 mechanical properties, 260 304 “compression modulus”, 304 hardness, 260 stress and strain under unidirectional loading, 260 304 mold shrinkage, examples of, 306 307 real sense of common terms, 211 212 statistical distribution of properties, 210 211 means as false friends, 210 211 standard deviation depending on multiple factors, 211 weak points and average properties, 210 thermal behavior, 221 249 above room temperature, 228 243 glass transition temperature, 222 228 low-temperature behavior, 243 249 water uptake, examples of, 304 305 Eco-design rules for plastics sustainability, 159 alloys, 202 203 cellulosics, 202

INDEX

dimensional stability, design for, 176 178 aging, desorption, bleeding, releasing of organic components, 177 178 shrinkage, 177 thermal expansion or retraction, 176 177 warpage, 177 water or chemicals uptake, 177 electrical properties, 178 180 arc resistance, 179 conductive polymers, 179 180 dielectric strength, 179 frequency, temperature, moisture, physical, and dynamic aging effects, 179 high voltage arc tracking rate (HVTR), 179 surface resistivity, 178 179 volume resistivity, 178 environmental traps, examples of, 160 162 automotive industry, favorable example of, 160 161 energy production method, selection of, 162 house building, counterexample of, 161 162 fire behavior, 180 187 biopolymers, general behavior of, 187 cone calorimeter, 182 fire resistant polymers, 183 186 general collateral effects from a sustainability standpoint, 186 187 glow wire test, 183 ignition temperature, 182 oxygen index, 182 rate of burning, 182 183 smoke opacity, toxicity, and corrosivity, 182 UL 94 fire ratings, 181 182 fluorinated thermoplastics, 202 lifetime and end-of-life criteria, 203 206 accelerated aging and modeling, 205 smart design and mitigation of aggressiveness of surroundings, 205 206 light and ultra violet resistance, 196 197 liquid crystal polymer (LCP), 202 low temperature behavior, 174 176 brittle point, 174 175 crystallization test, 175 environmental footprint of plasticizers, 175 176 low-temperature tests, 174 rigidity in torsion, 175 material sustainability impact, 163 165

impact of material selection on other parameters, 164 165 material impact, general pathway toward mitigation of, 164 overall view of sustainability, 165 mechanical loading, design to withstand, 165 171 combination with other parameters, 168 dimensional effects, 168 dynamic fatigue, 167 168 hardness, 167 impact behavior, 167 lifetime, 168 loading type effect, 166 reinforcements, environmental cost of, 168 171 strain rate/time effect, 166 167 temperature effect, 166 plastics behavior above ambient temperature, 171 174 accelerated aging, 173 average temperature, 172 continuous use temperature (CUT), 172 environmental cost of stabilizers and antioxidants, 173 174 heat deflection temperature (HDT), 173 underwriter laboratories temperature index, 172 173 Vicat softening temperature (VST), 173 polyacetals (POM), 202 polyamides, 200 201 polybenzimidazole, 202 polycarbonates (PCs), 201 polyetherimide, 202 polymethylmethacrylate, 201 polyolefins and derivatives, 199 polyphenylene ether (PPE), 202 polyphenylene sulfide (PPS), 202 polysulfone, 202 PVC and other chlorinated thermoplastics, 199 200 regulation, health, and safety requirements, 206 207 sensory issues, 187 195 colorants and pigments, 195 complementarity of instrumental measurements and sensory panel evaluations, 188 189 noise, vibration, harshness, 191 odor and taste properties and transfer, 191 physical aspect, 189 titanium oxide, 195 touch, 189 190 visual aspect, 189 specific plastics design issues, 163

INDEX

styrenics, 200 thermoplastic polyesters, 201 TPE and thermoplastic vulcanizate, 203 weathering appraisal, elements of, 197 198 anti-UV additives, effect of, 198 color, effect of, 198 Eco-design/sustainable design, incorporation of in the life cycle through ISO 14006, 87f, 88, 91 EcoImpact, 101 Ecological features boosting the growth of plastics, 574 587 functionality integration due to design freedom, 574 575 lightweighting, 575 585 automotive: a promising domain for traditional fossil plastics, 580 582 composites save weight and mitigate pollution, 582 583 environment-friendly structural solutions, 575 576 fully renewable solutions: natural fibers and biosourced polymers, 576 578 general plastics solutions, 575 hybrid solutions combine renewable and fossil components, 578 580 main potential boosters and brakes for natural fiber reinforced composites, 576 mobility solution examples, 583 585 sustainable solutions based on “unsustainable” composites, 580 take advantage of the unique insulation efficiency of plastics foams, 585 587 E-Commerce, 597 EconCore, 582 Economic involvements, 4 5 Economy, 8 EcoPaXX, 524 EcoPoxy, 539 Eco-profiling system (EPS), 100 EcoTechnilin Products, 554 Ecotoxicity potential, 312, 313t Ecover, 624 Efficient machines, investing in, 125 129 injection machines, 125 126 peripherals and retrofitting solutions, 126 129 EHS SmartStart, 102 Elastic limit, 261 Elastic modulus, 261 Electrical and electronic equipment, 428 435 Electrical properties, 178 180, 352 354 arc resistance, 179 conductive polymers, 179 180

633

dielectric loss factors, examples of, 354, 357t dielectric strength, 179 dielectric strength examples, 354 frequency, temperature, moisture, physical, and dynamic aging effects, 179 high voltage arc tracking rate (HVTR), 179 resistivity examples, 354, 355t surface resistivity, 178 179 volume resistivity, 178 Electricity sources, share examples of, 38 Electric vehicles, 600 601 Elemental composition, 66 EMS-GRIVORY, 518 End-of-life, optimizing, 157 Energy, 32 38 energy demand forecast, 32 33 potential energy sources for the future, 33 38 electricity sources, share examples of, 38 fossil energy, 34 renewable energy resources, 34 38 versus gross domestic product, 32 Energy consumption, 95 Energy demand forecast, 32 33 Energy monitoring, 136 Energy Monitoring Module, 138 Energy production method, selection of, 162 Energy recovery, 451 Energy requirements, 214 216 ENGEL, 130, 137, 152 Engineering thermoplastics (ETPs), 419 Enterprise Resource Planning (ERP) Software, 132 134, 134t Entropy resins epoxy, examples of, 539t Envirofoam Sustain range of formulated polyols, 585 586 Environmental assessment of sites and organizations (EASO), 91 Environmental footprint of plasticizers, 175 176 Environmental indicators, 95 98, 212 221 acidification, 97 CO2 and other greenhouse gases, gas warming potential, 96 diverse indicators, 97 98 energy consumption, 95 energy requirements, 214 216 eutrophication, 97 examples of, 98, 216 217 indicator per weight and indicator per functional unit, 220 221 net carbon footprint, CO2 and other greenhouse gases, 216

ozone depletion, photochemical oxidation, 97 photochemical smog, 97 toxicity, unwanted emissions, 97 use of renewable materials instead of fossil resources, 214 variability and weakness of, 217 220 water footprint, 96 97, 216 Environmental issues from a plastics point of view, 26 32 high lifetimes of plastics, 32 marine litter, 29 30 microplastics, microbeads, microfibers, 30 31 potential pollutants, 26 28 single-use products, 31 32 Environmental labels and declarations, 92 Environmentally conscious design (ECD), 209 Environmental management, 89 91 databases and software help in, 100 105 software leading to some discrepancies, 105 software solutions, examples of, 101 105 Environmental performance evaluation, 92 Environmental product declaration, 94 95 Environmental Protection Agency (EPA), 101, 581 Environmental requirements, in the framework of plastics industry, 3 Environmental stress cracking (ESC), 77 78 Environmental traps, examples of, 160 162 automotive industry, favorable example of, 160 161 energy production method, selection of, 162 house building, counterexample of, 161 162 Environment damages, sustainability to mitigate, 17 24 biological consequences, 23 climate warming and sea level rise: the major risks, 22 23 main greenhouse gases overview, 19 22 carbon dioxide, 19 20 halogenated gases, 21 methane, 20 21 nitrous oxide, 21 ozone, 21 22 sulfur hexafluoride, 22 urgency of decisions, 22 water vapor, 19 natural and artificial sinks, 23 24

634

Environment damages, sustainability to mitigate (Continued) population and gross domestic product growths, general consequences of, 18 population growth, 17 18 standard of living, 18 Environment management systems (EMS), 85 Enzymatic depolymerization of polylactic acid, 452 Enzymes, depolymerization by, 619 620 Epichlorohydrin, 538 Epoxidized natural rubber (ENR), 487 Epoxy resins, 471, 538 general properties of, 541 542 applications, 542 general advantages, 541 general drawbacks, 541 special grades, 541 renewable. See Renewable epoxy resins eQuick Change system, 129 Ethylene-methacrylate ionomers (EMA), 199 Ethylene-vinylacetate copolymers (EVAs), 199, 507 Ethylene-vinyl alcohol copolymers (EVOH), 199 Europe, plastic wastes in, 417 European Commission Regulation No (EC) 282/2008, 427 European Food Safety Agency (EFSA), 427 European Union information agency for Occupational Safety and Health Administration (EU-OSHA), 588 589 Eutrophication, 97 Eutrophication potential, 311, 312t EU waste legislation examples, 426 427 EVerdEE, 102 Execution system software, manufacturing, 131 132 Exposure without constraint, 77 Extended producer responsibility (EPR), 569 Extrusion and connected processes, 81

F Fatigue, 347 349 Fibers, 168 171 carbon fibers, 169 170 natural fibers, 170 171 FibriBoard, 554 FibriMat, 554 FibriPlast, 554 FibriPreg, 507 Film insert molding (FIM), 148 149 Fire behavior, 60 61, 180 187, 587 588

INDEX

biopolymers, general behavior of, 187 cone calorimeter, 182 fire resistant polymers, 183 186 FR additive solutions, 184 186 halogenated flame retardant and fire, smoke, and toxicity grades, 186 inherently FR polymers, 183 184 general collateral effects from a sustainability standpoint, 186 187 glow wire test, 183 ignition temperature, 182 oxygen index, 182 rate of burning, 182 183 smoke opacity, toxicity, and corrosivity, 182 UL 94 fire ratings, 181 182 Fire resistant (FR) polymers, 183 186 FR additive solutions, 184 186 halogenated flame retardant and fire, smoke, and toxicity grades, 186 inherently FR polymers, 183 184 Flammability, 355 364 Flexible PVC, 548 Fluid-assisted injection molding, 147 148 Fluorinated thermoplastics, 202 Fogging, 79 Ford Motor Company, 399, 456, 579, 581 Fossil and renewable plastics, economics relating to, 371 capability proposals, 376 378 for composites, 376 378 for thermoplastics, 376 cost estimator results, examples of, 378 380 agreement between different cost estimators, 378 379 check sensitivity and application window of variables of interest, 379 380 run size, example of effect of, 379 cost estimator software, 378 380 examples of, 378 costs, examples of, 380 381 composites, expected cost of, 380 381 market, expected costs by, 380 main bioplastics markets, survey of, 391 408 agriculture, 404 automotive and transportation, 392 399 building and construction, 399 404 consumer goods, 392 packaging, 392 raw plastics material cost, 371 374 actual consumption of plastic compared to weight of the part, 373 374 additive costs, examples of, 372

reinforcement costs, examples of, 372 373 sophisticated raw materials, cost of, 372 usual physical types of plastics raw materials, 371 renewable materials, economics of, 381 391 bioadditives consumption, 387 389 bioplastic capacities by market, 387 bioplastic capacities by region, 387 bioplastic family, market shares by, 385 bioplastic family, production capacities by, 385 386 bioplastics costs, 390 391 biosourced plastics consumption, 383 385 natural fiber costs, 391 plastics recycling, 383 wood plastic composite (WPC) and natural fiber composite markets, 389 390 Fossil energy, 34 Fossil energy demand of end products, 566 567 Fossil energy gains, examples of due to the use of recycled resins, 565 566 Fossil polyesters, 519t Fossil polymer foams, 585 Franklin Associates, 415 Fraunhofer, 582 Friction, coefficient of, 368 Frisella Design, 152 Fudow Company, 545 546 Fuel energy and feedstock energy, 309, 310t Functionality integration due to design freedom, 574 575 Furfural, 549 Furolite resins, 549 Future global plastics industry, 595 596

G GaBi Database, 104 Gas permeability, 365 367 Gas warming potential (GWP), 309 GDP, 18 Gensuite, 103 Geothermal energy, 36 Gevo, Inc., 516 Glass and carbon fibers, and highperformance polymers recycling of, 458 Glass fibers (GFs), 168 Glass transition temperature, 71, 222t Global emissions model for integrated systems (GEMIS), 102 103 Global Plastics Alliance, 622 623

INDEX

Global warming potential (GWP), 19, 96, 118, 216 of end products incorporating recycled polymers, 565 of specific recycled polymers, 564 565 Gloss modifiers, 483 486 Glow wire test, 183 Glycerol, 474 Glycolysis, 449 Granta, 103 Graphene, 171 Green electricity, 1 GreenGran, 477 Greenhouse effect, 458 460 Greenhouse gases (GHGs), 19 22, 96, 413, 414t carbon dioxide, 19 20 halogenated gases, 21 methane, 20 21 nitrous oxide, 21 ozone, 21 22 sulfur hexafluoride, 22 urgency of decisions, 22 water vapor, 19 GRI (Global Reporting Initiative), 9 Gross domestic product, energy versus, 32 Gross world product (GWP), 18 Growth rate, of plastics, 25 26 Gurit Balsaflex, 479

H Hallgreen IM-8830, 487 Hallgreen R-3020, 487 Hallstar, 486 487 Halogenated gases, 21 Halogen-containing FR (HCFR) solutions, 183 Halogen-free FR (HFFR) solutions, 183 Hardeners, 491 Hardness, 167, 260 Hazardous materials, avoiding/ minimizing/banning, 115 116 Heat deflection temperature (HDT), 173, 228 237, 229t High-density polyethylene bottles, 454 High-performance materials, recycling of, 564 High-tech repairs, 559 560 High thermal conductivity, polymers with, 63 High voltage arc tracking rate (HVTR), 179 House building, counterexample of, 161 162 Husky, 137, 152 Hybrid alloys of renewable and fossil polymers, 549 Hybrid materials, 49 50 Hydrochlorofluorocarbons, 154 Hydrofluorocarbons, 154

635

Hydrolysis, 449 Hydropower, 34 35

J Jomar injection blow-molding machines, 138

I Ignition temperature, 182 ILLIG, 151 Immersion/contact, chemical resistance by, 77 78 environmental stress cracking (ESC), 77 78 exposure without constraint, 77 Impact behavior, 167 Impact modifiers, 55 56, 442, 486 489 examples of, 488t Imperial Chemical Industries, 113 Impranil eco, 533 Incentive legislation example, 569 Index, 98 Industrially recycled polyamides, 461 Industrial-scale PS recycling channel, 615 Industry 4.0, 561 562 INEOS Styrolution, 620 Injection machines, 125 126 In-line decoration, 148 149 In-mold assembly (IMA), 151 In mold coating (IMC) process, 149 In-mold decoration (IMD), 148 In-mold flocking, 149 In-mold graining, 149 In mold labeling (IML), 149 Inorganic renewable natural fillers, 482 Integrated compounding, 146 147 Integrated Production, 139 Integration of subparts and reduction of raw material diversity, 153 Integrum, 103 104 Intelligent Machines, 138 139 Interactive services, 139 141 Intertek, 104 Intumescent flame retardant (IFR), 185 Intumescent materials, 185 IPCC (Integrated Pollution Prevention and Control), 101 ISO 14000 family of standards, 89 91 ISO 14006 incorporation of eco-design/sustainable design in the life cycle through, 87f, 88 incorporation of eco-design/sustainable design in the life cycle through, 91 ISO 14020 series of standards, 92 ISO 14030, 92 ISO 14031, 92 ISO 14040 series, 92 93 ISO 9000 family, 94 Isosorbide diesters, 472 473 ISO/TC 61/SC 4 Secretariat, 587 588 Isotropy, 72 73

K Kautex, 138 Kautex Control Easy, 138 KraussMaffei Berstorff, 139 KraussMaffei database, 152

L Lapol bioplasticizer, 474 Laser Direct Structuring (LDS) technology, 150 Laser marking, 150 Laser sensing technology, 617 Laser structuring, 151 Lead, 26 Lexan PC automotive glazing, 581 Life cycle, 86 87, 86f, 87f Life cycle accounts, 86 88 incorporation of eco-design or sustainable design in the life cycle through ISO 14006, 87f, 88 life cycle assessment (LCA), 87 life cycle costing (LCC), 88 life cycle impact assessment (LCIA), 88 life cycle inventory (LCI), 87 Life cycle analysis, 105. See also Life cycle assessment (LCA) Life cycle assessment, 87, 101, 105, 118, 216, 565, 576 ISO 14040 series, 92 93 Life cycle costing (LCC), 88 Life cycle impact assessment (LCIA), 88 ISO 14040 series, 92 93 Life cycle inventory (LCI), 87, 105 ISO 14040 series, 92 93 Lifetime, 168 Lifetime and end-of-life criteria, 203 206 accelerated aging and modeling, 205 smart design and mitigation of aggressiveness of surroundings, 205 206 Lifocork, 482 Light and ultra violet resistance, 196 197 Light stabilizers, 445 Lightweighting, 575 585 automotive, 580 582 composites save weight and mitigate pollution, 582 583 organosandwich, 582 traditional composites, 582 583 environment-friendly structural solutions, 575 576 fully renewable solutions: natural fibers and biosourced polymers, 576 578 general plastics solutions, 575

636

Lightweighting (Continued) hybrid solutions combine renewable and fossil components, 578 580 main potential boosters and brakes for natural fiber reinforced composites, 576 mobility solution examples, 583 585 aircraft, 583 marine, 584 585 railway, 585 road transportation, 583 584 sustainable solutions based on “unsustainable” composites, 580 Lignin, 470 derivatives of, 542 543 Limiting oxygen index (LOI), 185, 355 364 Liquid crystal polymer (LCP), 202 Liquid depolymerized natural rubber, 474 Liquid wood, 542 Loading type effect, 166 Long-fiber injection (LFI) process, 146 147 Long fiber-reinforced thermoplastics (LFRT), 466 Low-density polyethylene (LDPE), 491 Low temperature behavior, 174 176 brittle point, 174 175 crystallization test, 175 environmental footprint of plasticizers, 175 176 low-temperature tests, 174 rigidity in torsion, 175 Lubricant, 482 Lumicene M3427, 129

M Magna International, 581 Magnetic polymers, 63 64 Mallinda, 626 Manufacturing and environmental impact, 124 156 digitalization and software solutions, 130 142 enterprise resource planning software, 132 134 manufacturing execution system (MES) software, 131 132 smart or intelligent machines, 130 131 software solutions integrated by plastics machinery providers, 135 141 zero-defect manufacturing (ZDM), 141 142 efficient machines, investing in, 125 129 injection machines, 125 126 peripherals and retrofitting solutions, 126 129

INDEX

integration of subparts and reduction of raw material diversity, 153 less energy-demanding compounds, favoring, 129 130 manufacturing steps, integrating, 146 153 alternative processing methods, example of, 151 coprocessing, 147 fluid-assisted injection molding, 147 148 in-line decoration, 148 149 in-mold assembly (IMA), 151 integrated compounding, 146 147 laser marking, 150 laser structuring, 151 printing, 149 150 workcells, 152 153 minimizing waste, 144 potentially hazardous releases possibly emitted by plastics, 153 155 preventive and predictive maintenance, 143 promoting efficient real-time quality control, 142 143 renewable energy, using, 144 146 retrofitting of machinery, 155 156 Manufacturing execution system (MES) software, 131 132, 132t Manufacturing steps, integrating, 146 153 alternative processing methods, example of, 151 coprocessing, 147 fluid-assisted injection molding, 147 148 in-line decoration, 148 149 in-mold assembly (IMA), 151 integrated compounding, 146 147 laser marking, 150 laser structuring, 151 printing, 149 150 workcells, 152 153 Marine litter, 29 30 Market, expected costs by, 380 Marketing strategy, examples of based on sustainability, 11 12 MarketsandMarkets, 411 Mater-Bi Wave foam sheet, 494, 586 Material consumption optimization using simulation and modeling tools, 116 118 Material sustainability impact, 163 165 impact of material selection on other parameters, 164 165 material impact, general pathway toward mitigation of, 164 overall view of sustainability, 165 Max-AI technology, 617 618

Mechanical loading, design to withstand, 165 171 combination with other parameters, 168 dimensional effects, 168 dynamic fatigue, 167 168 environmental cost of reinforcements, 168 171 carbon fibers, 169 170 carbon nanotubes (CNT) and graphene, 171 cellulose nanofibers, 171 natural fibers, 170 171 natural mineral fillers, 171 hardness, 167 impact behavior, 167 lifetime, 168 loading type effect, 166 strain rate/time effect, 166 167 temperature effect, 166 Mechanical properties, 260 304 “compression modulus”, 304 hardness, 260 stress and strain under unidirectional loading, 260 304 Mechanical property upgrading and customization, 52 57 impact modifiers, 55 56 nanofillers, 54 55 plasticization, 56 57 reinforcement, 52 reinforcement and filling with mineral fillers, 53 54 reinforcement with fibers, 52 53 reinforcement with glass beads, 54 MEGOL bio, 551 Mercedes, 456, 598 Mercury, 26 Metal hydroxides, 185 Metal powders/flakes, 62 Methane, 20 21 Methanolysis, 449 Method Products, Inc, 454 Methylmethacrylate-acrylonitrilebutadienestyrene (MABS), 200 Metrics of sustainability in plastics, 85 clarification concerning some terms, 105 databases and software help in environmental management, 100 105 software leading to some discrepancies, 105 software solutions, examples of, 101 105 detailed accounts of LCA, LCI, LCIA, 92 93 eco-design/sustainable design in the life cycle through ISO 14006, 91 environmental assessment of sites and organizations (EASO), 91

INDEX

environmental indicators, 95 98 acidification, 97 CO2 and other greenhouse gases, gas warming potential, 96 diverse indicators, 97 98 energy consumption, 95 eutrophication, 97 examples of indicators, 98 ozone depletion, photochemical oxidation, 97 photochemical smog, 97 toxicity, unwanted emissions, 97 water footprint, 96 97 environmental labels and declarations, 92 environmental management ISO 14000 family and a few related standards, 89 91 environmental performance evaluation, 92 environmental product declaration, 94 95 environment management systems (EMS), 85 life cycle accounts, 86 88 incorporation of eco-design/ sustainable design in life cycle through ISO 14006, 87f, 88 life cycle, 86 87, 86f, 87f life cycle assessment (LCA), 87 life cycle costing (LCC), 88 life cycle impact assessment (LCIA), 88 life cycle inventory (LCI), 87 quality management systems, 94 risk management, 93 94 synthetic indices resulting from environmental indicator integration, 98 100 CML-IA by CML, 100 eco-profiling system (EPS), 100 Microbead-Free Waters Act of 2015, 598 Microbeads, 30 31 Microfibers, 30 31 Microplastics, 30 31 Microwaves, depolymerization by, 620 Milk Roadmap. See Dairy Roadmap Minger, 458 Mitsubishi Chemicals, 544 Molding liquid thermoplastics, 81 82 Molding solid thermoplastics, 80 81 Mold shrinkage, examples of, 306 307 Molecular weight and chain architecture, 66 Monoethylene glycol (MEG), 513 Municipal solid wastes (MSWs), 413, 620 621

N Nanofillers, 54 55

637

Nanomaterials, 588 589 National Highway Traffic Safety Administration (NHTSA), 581 Natural alcohol, replacement of the fossil alcohol by, 513 515 paraxylene for 100% biopolyester, 515 516 plant-based mono ethylene glycol, 513 515 polyethylene-furanoate, 516 Natural and artificial sinks, 23 24 Natural and seminatural additive, 472t Natural cellulose, cellulose derivatives based on. See Cellulose derivatives based on natural cellulose Natural fiber composite market, 388 389 Natural fiber costs, 391 Natural fibers (NF), 168, 170 171, 477 479 Natural linear polyesters examples of, 504t produced by bacterial fermentation. See Bacterial fermentation, natural linear polyesters produced by Natural mineral fillers, 171 Natural oil polyols (NOPs), 530 531 Natural reinforcements, 474 482 balsa, 479 481 inorganic renewable natural fillers, 482 natural fibers, 477 479 organic natural fillers, 481 482 Natural rubber, 470 Natural-sourced epoxidized oils and epichlorhydrin, 538 541 Natural-sourced versus fossil polymers, 312 314 Near infrared (NIR) spectroscopy, 617 Negri Bossi, 139 Negri Bossi AMICO Network, 139 140 Nestle´ Waters, 454 Net carbon footprint, CO2 and other greenhouse gases, 216 Netstal, 131, 152 New Plastics Economy Global Commitment, 623 Nextek, 454 Nissei, 140 Nitrogen-based FRs, 185 Nitrous oxide, 21 Noise, vibration, harshness, 191 Nonblack fillers, 64 66 Nonwater soluble amino acids, 489 Novamont, 113

O Oak Ridge National Laboratory, 574 Ocean Cleanup, 623 Ocean Legacy Foundation, 623 Ocean litter, 621 624

Odor and taste properties and transfer, 191 Odors, 60 openLCA, 104 Optical properties, 365 Optical property modifiers, 483 486 examples of, 487t Orca Sound Project, 624 Organic additives, release of, 76 Organic components aging, desorption, bleeding, releasing of, 177 178 Organic natural fillers, 481 482 OrganoClick, 554 Organosandwich, 582 Overmolding, 147 Oxygen index (OI), 182, 355, 358t Ozone, 21 22 Ozone depletion, photochemical oxidation, 97 Ozone depletion potential, examples of, 310, 311t

P Paraxylene for 100% biopolyester, 515 516 Parley, 623 Parley Global Cleanup Network and Remote Island Interception, 624 Partially renewable thermoplastic elastomer ester, 517 PE furanoate (PEF), 574 Pentamethylene diisocyanate (PDI), 532 PepsiCo, 114, 516 517, 568 569 Perception of plastics sustainability, 5 8 plastics concern details, 8 applications, 8 economy, 8 environment, 8 technical features, 8 plastics concern overview, 6 7 plastics sector players, opinions of, 5 6 Perfluorocarbons, 154 Perillon, 104 Peripherals and retrofitting solutions, 126 129 Phenol formaldehyde resins, 471 renewable. See Renewable phenol formaldehyde resins Photochemical smog, 97 Photo-oxidant creation potential (POCP), 97, 105, 310, 311t Piovan, 129 Plant-based mono ethylene glycol, 513 515 PlantBottle technology, 113 114 Plastic boilermaking, 122 Plastic bottles, sorting of, 453 Plasticization, 56 57, 443 Plastic recycling, impediments to, 435f

638

Plastics field, sustainability in, 3 5 economic involvements, 4 5 renewable polymers, 4 sustainable design, 3 sustainable processes or sustainable manufacturing, 4 sustainable use phase, 4 waste management, repair, reuse, recycling, 4 Plastics industry, pace of change in, 113 115 Plastics waste market, 417t Plastic waste recovery, breakdown of, 418t Plastic wastes for the United States in 2003, 417t Plastisols, 548 PMMA, 544 Poisson’s ratios, 349 352, 353t Pollutants, effect of, 438 439 “Polluter pays” principle, 613 Poly(methyl methacrylate), 543 544 general advantages, 544 general drawbacks, 544 Polyacetals (POM), 202 Polyamides (PAs), 200 201, 463t, 470 alternating long and short hydrocarbon segments, 526 industrially recycled polyamides, 461 with long hydrocarbon segments, 524 525 renewable. See Renewable polyamides with short hydrocarbon segments, 526 Polybenzimidazole, 202 Polybrominated biphenyls (PBBs), 17, 154 Polybrominated diphenyl ethers (PBDEs), 17, 154 Polybutylene succinate (PBS), 517, 524t Polybutylene succinate-adipate (PBSA), 524t Polycarbonate (PC), 201, 579 580 biosourced, 542 Polycarbonate, PC/ABS, and PC/PBT alloys examples of, 461 462 Polychlorinated biphenyls (PCBs), 27 28, 154 155 Polyether block amides (PEBAs), renewable, 528 530, 530t property tables, 530 Polyetherimide, 202 examples of, 462 465 Polyethylene (PE), 199, 470, 511t Polyethylene application sectors, 510 512 Polyethylene bottles, high-density, 454 Polyethylene environmental features, 510 Polyethylene-furanoate, 516 Polyethylene property tables, 513

INDEX

Polyethylene terephthalate (PET) bottles, 453 454 bottle recycling, 453 454 bottle-to-bottle recycling, 454 bottle to engineering thermoplastic polyester grades, 454 collection of bottles, 453 sorting of plastic bottles, 453 PolyFibra by FuturaMat, 477 Polyhydroxyalkanoates (PHA), 470, 499 503, 574 application sectors, 502 503 environmental features, 502 processing, 502 producers and trademarks, examples of, 503 property tables, 503 Polyhydroxybutyrate (PHB), 470 Polylactic acid (PLA), 309, 469, 574 enzymatic depolymerization of, 452 property examples of, 500t Polylactic acid (PLA) polymerized from a natural monomer, 495 499 application sectors, 498 environmental features, 497 498 processing, 497 producers and trademarks, examples of, 498 property tables, 499 heat stabilization, 499 melt strength enhancement, 499 Polylactides and polylactic acid (PLA) plastics, 469 Polymer composites, 49 Polymer foams, 585 Polymers best available techniques in the production of, 41 42 with high thermal conductivity, 63 incompatible with existing recycling streams, 613 from natural sources, 42 renewable. See Renewable polymers Polymethylmethacrylate, 201 Polymethylpentene (PMP), 199 Polynt Composites, 535 Polyolefins and derivatives, 199 PolyOne, 473, 486, 489 Polyphenylene ether (PPE), 202 Polyphenylene sulfide (PPS), 183, 202 Polyphthalamide, 528, 529t Polypropylene (PP), 461, 470, 477, 480t, 566 Polystyrene (PS), 214, 464t, 469 470 and acrylonitrile butadiene styrene examples, 461 Polysulfone, 202 Polytrimethyleneterephthalate, 517, 522t Polyurethane players, examples of, 534 Polyurethanes, 449

renewable. See Renewable polyurethanes Polyvel, 488 Polyvinyl chloride (PVC), 470 and other chlorinated thermoplastics, 199 200 renewable. See Renewable polyvinyl chloride Population and gross domestic product, 24 general consequences of, 18 Population growth, 17 18 Postconsumer products, treatment of, 14 17 cost savings, 16 environment advantages, 15 16 regulations and limitations, 16 17 Potential energy sources for the future, 33 38 electricity sources, share examples of, 38 fossil energy, 34 renewable energy resources, 34 38 biofuels and other biofeedstocks from biomass, 36 38 geothermal energy, 36 hydropower, 34 35 solar power, 36 wind power turbine, 35 Potential heterogeneity of properties, 73 75 local and bulk properties, 75 molecular and filler orientation, 73 75 water uptake plasticizes certain polymers, 73 Potentially hazardous releases possibly emitted by plastics, 153 155 Potential pollutants, 26 28 PowerRibs, 579 Pressure velocity (PV), 367 368 limiting, 368 369 Printing, 149 150 Processing aids, 482 examples of, 483t Production wastes, recycling of, 13 14 Product sustainability, decreasing the material impact on, 115 124 avoiding renewable material competing with food or causing deforestation, 120 121 design to facilitate maintenance, repair, reuse, refurbishment, 121 124 hazardous materials, avoiding/ minimizing/banning, 115 116 material consumption optimization using simulation and modeling tools, 116 118 recycled materials and waste, using, 118 120

INDEX

renewable materials, avoiding nonrenewable natural resource depletion using, 118 using reliable materials and trustworthy providers, 124 Proportional limit, 261 Protective agents, 489 490 examples of, 490t Publicly Available Specification (PAS), 427 Purity enhancement, 446 447 Pyrowave, 620

Q Quality management systems, 94

R Raven Lining Systems, 540 Raw plastics material cost, 371 374 actual consumption of plastic compared to weight of the part, 373 374 additive costs, examples of, 372 reinforcement costs, examples of, 372 373 sophisticated raw materials, cost of, 372 usual physical types of plastics raw materials, 371 REACH, 155 Reaction injection molding (RIM), 149 Ready-to-use thermoplastic blends derived from starch, 491 495 application sectors, 494 495 environmental features, 494 processing, 491 494 producers and trademarks, examples of, 495 property tables, 495 Real-time quality control, promoting, 142 143 Recovery volume, 603 604 Recyclate property examples, 461 465 polyamides examples, 461 industrially recycled polyamides, 461 polycarbonate, PC/ABS, and PC/PBT alloys examples of, 461 462 polyetherimide, examples of, 462 465 polypropylene examples, 461 polystyrene and acrylonitrile butadiene styrene examples, 461 Recyclate upgrading, special additives and packages for, 445 446 Recycled materials and waste, using, 118 120 Recycled materials in cost saving, 466 Recycled material use, limitations to, 466 producer recommendations, 466 underwriters laboratories’s recommendations on the use of regrind, 466

639

Recycled PE (rPE), 564 Recycled PET (rPET) recipe, 455 Recycled plastics, use of, 66 Recycled plastics limitations, example of, 571 Recycled polyethylene terephthalate, 516 517 Recycled resin use, environmental benefits of, 416t Recycling, 411 435, 452 458 advantages, 458 460 some real facts and figures, 460 statistical analyses of some real examples, 460 automotive, 427 428 schedule, 428 of building products, 456 457 closed- and open-loop recycling auto, 455 456 electricity and electronics, 454 455 of composites, 457 458 economics of, 416 420 plastic wastes in Europe, 417 plastic wastes in United States, 416 417 recovery costs, 417 420 electrical and electronic equipment, 428 435 environmental benefits of, 414 415 EU waste legislation examples, 426 427 of glass and carbon fibers, and highperformance polymers, 458 high-density polyethylene bottles, 454 packaging, 428 performances, recycling loop effects on, 423 425 of plastics, 383 reliability of, 420 423 of thermosets, 457 used polyethylene terephthalate bottles, 453 454 bottle recycling, 453 454 bottle-to-bottle recycling, 454 bottle to engineering thermoplastic polyester grades, 454 collection of bottles, 453 sorting of plastic bottles, 453 Recycling and actual reuse, 562 569 closed-loop recycling, 563 564 environmental benefits of recycling, 562 563 example of environmental benefits of recycling a commodity plastic, 568 example of inconsistency between indicators relating to a recycled polymer family, 567 568 examples of cost savings due to recycling, 568

examples of fossil energy gains due to the use of recycled resins, 565 566 fossil energy demand of end products based on reused materials and/or recycled polymers, 566 567 global warming potential of end products incorporating recycled polymers, 565 of specific recycled polymers, 564 565 high-performance materials, recycling of, 564 recycling, reuse, or use virgin polymer, 568 569 Recycling management, 613 616 better reliability and availability of recycled plastic, 615 616 difficult-to-recycle hi-tech carbon fiber reinforced plastic composite for aeronautics, 615 industrial-scale PS recycling channel, 615 plastics industry, associations of, 614 615 plastics producers, direct involvement of, 614 Recycling methods, 435 452 anaerobic biodegradation of biodegradable plastics with gas recovery, 452 chemical recycling, 447 449 polyurethanes, 449 thermoplastic polyesters, 448 449 energy recovery, 451 polylactic acid, enzymatic depolymerization of, 452 recycled material upgrading by additives, 439 447 aging protection, additives for, 443 444 compatibilizers, 442 impact modifiers, 442 plasticization, 443 purity enhancement, 446 447 recyclate upgrading, special additives and packages for, 445 446 sensorial property enhancers, 444 445 REnescience process, 452 reprocessing of processing scraps and mechanical recycling, 437 439 pollutants, effect of, 438 439 solvent recycling, 449 450 pretreatment, 450 selective dissolution, 450 separation, 450 thermal recycling, 450 451 Refillable bottles, 560

640

Refurbishing and upgrading machinery, 562 563 Industry 4.0, 561 562 Regulation boosting recycling, example of, 570 Reinforced thermoplastic (RTP), 579 Reinforcement, 52 with fibers, 52 53 and filling with mineral fillers, 53 54 with glass beads, 54 reinforcement costs, examples of, 372 373 Reinforcements, environmental cost of, 168 171 carbon nanotubes (CNT) and graphene, 171 cellulose nanofibers, 171 fibers, 168 171 carbon fibers, 169 170 natural fibers, 170 171 natural mineral fillers, 171 Relative temperature index (RTI), 241t, 242t Relaxation, 72, 346 347 Release agents, 482 examples of, 485t Renault, 456 REnescience process, 452 Renewable acrylics, 543 544, 545t general advantages, 544 general drawbacks, 544 Renewable additives, 471 491 antistatic additives, 482 fire retardants, tackifiers, nucleating agent, waxes, hardeners, foaming agents, etc, 490 491 natural reinforcements, 474 482 balsa, 479 481 natural fibers, 477 479 organic natural fillers, 481 482 other inorganic renewable natural fillers, 482 optical property modifiers, 483 486 processing aids, 482 protective agents, stabilizers, thermal, and antiaging additives, light stabilizers, 489 490 release agents, 482 renewable colorants, 483 486 renewable impact modifiers and tougheners, 486 489 renewable masterbatches based on renewable matrix or renewable additive, 491 renewable plasticizers, 472 474 surface friction modifiers, 482 Renewable and fossil polymers, hybrid alloys of, 549 Renewable colorants, 483 486 Renewable energy, using, 144 146

INDEX

Renewable energy resources, 34 38 biofuels and other biofeedstocks from biomass, 36 38 geothermal energy, 36 hydropower, 34 35 solar power, 36 wind power turbine, 35 Renewable energy sources (RES), 33 Renewable epoxy resins, 538 542 epoxy resins, general properties of, 541 542 applications, 542 general advantages, 541 general drawbacks, 541 special grades, 541 natural-sourced epoxidized oils and epichlorhydrin, 538 541 Renewable impact modifiers and tougheners, 486 489 Renewable masterbatches based on renewable matrix or renewable additive, 491 Renewable materials, 571 574 avoiding nonrenewable natural resource depletion using, 118 avoiding renewable material competing with food or causing deforestation, 120 121 questionable case, 573 replacement of ABS for LEGO bricks, 573 574 drop-in solutions for green ABS, 573 574 substitute biobased polymers for ABS, 574 success story examples, 572 573 use of, 214 Renewable materials, economics of, 381 391 bioadditives consumption, 387 389 natural fiber composite market, 388 389 other bioadditives, 389 biomaterial costs, 390 391 bioplastics costs, 390 391 natural fiber costs, 391 bioplastic capacities by market, 387 bioplastic capacities by region, 387 biosourced plastics consumption, 383 385 market shares by bioplastic family, 385 production capacities by bioplastic family, 385 386 recycling, of plastics, 383 wood plastic composite (WPC) and natural fiber composite markets, 389 390 Renewable PET, PBT, PEF, PTT, 513 518

natural alcohol, replacement of the fossil alcohol by, 513 515 paraxylene for 100% biopolyester, 515 516 plant-based mono ethylene glycol, 513 515 polyethylene-furanoate, 516 partially renewable thermoplastic elastomer ester, 517 polybutylene succinate (PBS), 517 polytrimethyleneterephthalate, 517, 522t property examples, 518 recycled polyethylene terephthalate, 516 517 Renewable phenol formaldehyde resins, 544 546 general advantages, 546 general drawbacks, 546 Renewable plastics consumption, 603 606 at mid- and long-term, 603 605 bio-sourced plastics consumption, 604 605 recovery volume, 603 604 bioplastic capacities by market, 605 606 bioplastic capacities by region, 605 composites consumption, 606 market shares by bioplastic family, 605 production capacities by bioplastic family, 605 Renewable polyamides, 518 530 amorphous transparent renewable polyamides, 526 527 polyamides alternating long and short hydrocarbon segments, 526 polyamides with long hydrocarbon segments, 524 525 polyamides with short hydrocarbon segments, 526 polyphthalamide, 528, 529t renewable polyether block amides, 528 530, 530t property tables, 530 Renewable polyether block amides, 528 530, 530t property tables, 530 Renewable polyethylene (PE), 1 Renewable polymers, 4, 469 471 alloys of, 549 Renewable polypropylene, 547 Renewable polyurethanes, 530 534 applications, 532 533 biopolyurethane foams, 532 533 biopolyurethane sprays, 533 biothermoplastic polyurethane, 533 coatings and adhesives, 533 bioisocyanate crosslinker for polyurethanes, 532 533

INDEX

CO2-containing polyols, 531 532 environmental advantages, examples of, 533 534 natural and renewable oil polyols, 530 531 polyurethane players, examples of, 534 Renewable polyvinyl chloride, 548 general advantages, 548 general drawbacks, 548 Renewable raw materials, various bioplastics derived from, 550 554 Renewable unsaturated polyesters, 535 538, 536t applications, 537 general advantages, 537 538 general drawbacks, 538 general properties, 537 538 special grades, 538 Repsol, 532 Resistivity examples, 354, 355t Retrofitting of machinery, 155 156 Reused drums, benefits of, 560 ReVital Polymers, 620 Rexam Prescription Products, 454 Rigidity in torsion, 175 Rigid PVC, 548 Risk management, 93 94 R.M. SUFFIELD and All, 489 RoHS (Restriction of Hazardous Substances), 155 ROMI, 140 RTP Company, 477 Run size, example of effect of, 379

S Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR), 588 589 Scratch-resistance improvement, 60, 78 Sea level rise, 22 23 Secant modulus, 261 262 Secondary energy, 105 Secondary processing, 82 Self-healing polymers, 625 626 Self-reinforced composite, example of produced from cereals, 543 Sensorial property enhancers, 444 445 Sensory issues, 187 195 collateral effects of colorants from a sustainability standpoint, 191 195 colorants and pigments, 195 titanium oxide, 195 complementarity of instrumental measurements and sensory panel evaluations, 188 189 noise, vibration, harshness, 191 odor and taste properties and transfer, 191 physical aspect, 189 touch, 189 190

641

visual aspect, 189 Sensory properties of plastics, 78 79 acoustic comfort, 79 fogging, 79 odors, 60, 79 optical properties, 78 scratch-resistance improvement, 59 60, 78 taste, 79 touch, 78 SGL Automotive Carbon Fibers, 458 Sheet molding compound (SMC), 457 SHOTSCOPE NX, 137 138 Shrinkage, 76, 177 Sicomin, 540 Sicomin PB 360 GS, 541 Sidel, 140 141 Siloxanes, 185 SimaPro, 104 Single-use products, 31 32 Skinform technology, 151 Slipping agents, 482 Smart factory, 609 Smart/intelligent machines, 130 131 Smoke opacity, toxicity, and corrosivity, 182 SoFi software, 104 Software leading to some discrepancies, 105 Software solutions, examples of, 101 105 Software solutions integrated by plastics machinery providers, 135 141 energy monitoring, 136 Integrated Production, 139 Intelligent Machines, 138 139 interactive services, 139 141 troubleshooting, 136 138 Solar power, 36 Solvay, 524 Solvay Advanced Polymers, 129 Solvent recycling, 449 450 pretreatment, 450 selective dissolution, 450 separation, 450 Solvolysis Process, 457 Sony’s televisions, 455 Sophisticated raw materials, cost of, 372 Sorona, 470, 517 SoRPlas by Sony, 462 463, 563 Stabilizers and antioxidants, environmental cost of, 173 174 Standard deviation depending on multiple factors, 211 Standard of living, 18 Standards and reporting, 8 10 Starch, 469 Starch-based films and sheets, 494 Strain rate/time effect, 166 167 Stratasys, 141 Stress and strain at yield, 261

Stress and strain under unidirectional loading, 260 304 Structural foams, 66 Styrene acrylonitrile (SAN), 200 Styrenics, 200 Succinity, 532 SUKANO, 489 Sulfur hexafluoride, 22 Supply and distribution chains, reducing the impact of, 156 Supramolecular chemistry, 625 Surface friction modifiers, 482 examples of, 484t Surface resistivity, 178 179 Sustainability, 1, 557, 609 612 “deposit and bill” approach, example of, 571 ecological features boosting the growth of plastics, 574 587 functionality integration due to design freedom, 574 575 lightweighting, 575 585 unique insulation efficiency of plastics foams, 585 587 emergence and rapid advance of prescriptive techniques, 611 example of regulation restraining the use of plastics, 569 570 examples of bottlenecks for the growth of plastics, 587 589 3D printing and other additive manufacturing techniques, 589 fire behavior, 587 588 nanomaterials, 588 589 examples of strategies aiming at better sustainability, 611 612 extended producer responsibility, 569 global, regional, sectorial inequalities, 589 592 brief jumble of facts and figures, 592 global landscape, 589 590 plastics waste treatment, 590 591 recycled plastics limitations, example of, 571 recycling and actual reuse, 562 569 closed-loop recycling overview, 563 564 environmental benefits of recycling, 562 563 example of environmental benefits of recycling a commodity plastic, 568 example of inconsistency between indicators relating to a recycled polymer family, 567 568 examples of cost savings due to recycling, 568 examples of fossil energy gains due to the use of recycled resins, 565 566

642

Sustainability (Continued) fossil energy demand of end products based on reused materials and/or recycled polymers, 566 567 global warming potential of end products incorporating recycled polymers, 565 global warming potential of specific recycled polymers, 564 565 high-performance materials, recycling of, 564 recycling, reuse, or use virgin polymer, 568 569 regulation boosting recycling, example of, 570 renewable materials, 571 574 drop-in solutions for green ABS, 573 574 questionable case, 573 substitute biobased polymers for ABS, 574 success story examples, 572 573 repair and reuse, 558 562 high-tech repairs, 559 560 refillable bottles, 560 refurbishing and upgrading machinery, 562 563 reused drums, benefits of, 560 sustainability game changers, 609 611 waste minimization, 558 waste strategies, vast range of, 557 558 Sustainable design, 3 Sustainable materials management (SMM), 11 13 Sustainable processes or sustainable manufacturing, 4 Sustainable renewable sources, examples of used or proposed by resin producers, 624 625 Sustainable use phase, 4 Sustainable waste management. See Waste management, sustainable Suzhou HiPro Polymers, 524 SwingChutes, 151 Synbra Group, 586 Synthetic indices resulting from environmental indicator integration, 98 100 CML-IA by CML, 100 eco-profiling system (EPS), 100

T Tackifiers, 491 Technical and economic possibilities of processing, 79 84 blow molding, 81 calendering, 81

INDEX

economic comparison of some processing costs, 83 84 extrusion and connected processes, 81 molding liquid thermoplastics, 81 82 molding solid thermoplastics, 80 81 repair possibilities: a significant thermoplastic advantage for large parts, 84 secondary processing, 82 three-dimensional printing and other additive manufacturing methods, 82 83 Teknor Apex, 580 Teleworking, 597 Temperature dependency, 72 Temperature effect, 166 TENAX-E COMPOUND rPEEK CF30, 458 Tensile modulus, 286t Terraloy, 580 Terraloy 9000 Series masterbatches, 488 Thermal behavior, 221 249 above room temperature, 228 243 general assessments concerning continuous use temperature, 237 238 heat deflection temperature or deflection temperature under load, 228 237 impact strength above room temperature, examples of, 242 243 UL relative temperature index, examples of, 238 241 glass transition temperature, 222 228 low-temperature behavior, 243 249 brittle point, 247 crystallization test, 249 dynamic torsion modulus, 247 249 expected minimum service temperatures, 243 standardized impact tests processed at low temperatures, 247 Thermal dependency of mechanical properties, 314 321 long-term heat effect on oxidizing aging, 315 321 short-term effects of high and low temperatures, 314 315 behavior above room temperature, 315 behavior below room temperature, 315 Thermal expansion/retraction, 176 177 Thermal gravimetric analysis (TGA), 185 Thermal recycling, 450 451, 451f ThermHex Waben, 582 Thermoplastic elastomers (TPEs), 46 48, 203 schematic structure of, 47f

Thermoplastic polyesters, 201, 448 449 Thermoplastic polyolefin (TPO) foam foil, 149 Thermoplastics, 45 46, 122 advantages, 45 capability proposals for, 376 disadvantages, 45 46 Thermoplastic starch, property examples of, 496t Thermoplastic vulcanizate, 203 Thermosets, 48 49, 48f advantages, 48 disadvantages, 48 49 recycling of, 457 Thermosetting cyanate ester resins, 548 549 Thermosetting furanic resins, 549 ThinkStep, 104 105 Three-dimensional printing and other additive manufacturing methods, 82 83, 589 Time dependency, 71 72 Time dependent mechanical properties, 321 349 creep, 332 346 fatigue, 347 349 relaxation, 346 347 Time management, 597 Titanium oxide, 195 Touch, 78, 189 190 Toxicity, unwanted emissions, 97 Toyota Motor Corporation, 513 515 Toyota Tsusho Corp., 513 Traditional composites, 582 583 Traditional polyethylene reminder of advantages of, 510 reminder of drawbacks of, 510 TransFurans Chemicals (TMC), 549 Transparency MarketResearch, 411 Transparent/translucent thermoplastics, 366t Trash Free Seas Alliance, 623 TRB Lightweight Structures Ltd, 582 583 Triacetin TP LXS 51035, 474 Tribological properties, 367 369 friction, coefficient of, 368 limiting pressure velocity, 368 369 Troubleshooting, 136 138

U UL 94 fire ratings, 181 182 Ultimate stress and strain, 261 UltraBOOST Uncaged Parley, 624 Ultradur High Speed, 129 130 Umberto, 105 Underwriter laboratories temperature index, 172 173

INDEX

Underwriters laboratories’s recommendations on the use of regrind, 466 Unimoll AGF, 474 United States, plastic wastes in, 416 417 Unsaturated polyesters (UPs), 471 renewable. See Renewable unsaturated polyesters UPM, 537 Use phase impacts, reduction of, 156

V Valox iQ resin, 454 Vegeplast markets, 543 Viba, 489 Vicat softening temperature (VST), 173, 242 243, 243t Virent Cy, 515 516 Viscoelasticity, creep, relaxation, 71 72 temperature dependency, 72 time dependency, 71 72 ViscoSensor Online Rheometer, 142 143 Vitamin E, 489 Vitrimers, 626 Volatile organic compounds (VOCs), 97, 105, 154 Volume resistivity, 178 Volvo Cars, 455 456 Vyncolit Sumitomo Bakelite Co, 457

W Warpage, 76, 177 Waste & Resources Action Programme (WRAP), 415

643

Waste Framework Directive, 426 Waste Free Oceans, 623 Waste management, repair, reuse, recycling, 4 Waste management, sustainable, 13 17 postconsumer products, treatment of, 14 17 cost savings, 16 environment advantages, 15 16 regulations and limitations, 16 17 production wastes, recycling of, 13 14 Waste minimization, 558 Wastes, 612 613 collection systems, 612 “polluter pays” principle, 613 polymers incompatible with existing recycling streams, 613 Waste sorting, 616 619 suppressing the pitfall of, 619 620 depolymerization by enzymes, 619 620 depolymerization by microwaves, 620 Waste strategies, vast range of, 557 558 Waste water treatments (WWT), 41 Water footprint, 39, 96 97, 216 of plastics industry and water stress, 39 42, 40f best available techniques in the production of polymers, 41 42 plastics production, water consumption for, 39 41 polymers from natural sources, 42 Water or chemicals uptake, 177

Water uptake, examples of, 304 305 Water vapor, 19 Waxes, 491 Weak points and average properties, 210 Wear factor, 367 Weathering appraisal, elements of, 197 198 anti-UV additives, effect of, 198 color, effect of, 198 WEEE (Waste Electrical and Electronic Equipment), 155 Wind power turbine, 35 Wittmann 4.0, 141 Wittmann Battenfeld, 143 Wood plastics composite (WPC), 389, 470 and natural fiber composite markets, 389 390 Workcells, 152 153 Worldwide plastics demand at a glance, 24 25

Y Yield10 Bioscience, 487 Yield point, 261 Young’s modulus, 261

Z Zero-defect manufacturing (ZDM), 141 142 of composite parts in aerospace industry, 141 142 mass-produced molded parts, 141 Zinc, 26