Polymer Nanocomposite-Based Smart Materials: From Synthesis to Application [1 ed.] 0081030134, 9780081030134

Table of contents :
Cover
Polymer Nanocomposite-
Based Smart Materials:
From Synthesis to Application
Copyright
Dedication
Contributors
About the editors
Preface
1 - Introduction: different types of smart materials and their practical applications
Abstract
Keywords
1 Introduction to smart materials
2 Smart materials: definition and fundamental characteristics
3 Types of smart materials
3.1 Piezoelectric materials
3.2 Magnetostrictive materials
3.3 Shape-memory alloys
3.4 Chromic materials
3.5 Thermoresponsive materials
4 Application of smart materials
5 Conclusion
References
2 - Role of characterization techniques in evaluating the material properties of nanoparticle-based polymer materials
1 Introduction
2 Crystallographic properties
3 Morphological properties
4 Thermal properties
5 Antimicrobial properties
6 Conclusion
References
3 - Self-healing based on composites and nanocomposites materials: from synthesis to application and modeling
1 - Introduction
1.1 Types of healing process in polymers
1.1.1 - Intrinsic self-healing polymers
1.1.2 - Extrinsic self-healing polymers
1.1.2.1 - Vascular self-healing materials
1.1.2.2 - Microcapsules-based self-healing materials
1.2 - Practical applications of self-healing polymers
1.2.1 - Self-healing coating systems
1.2.2 - Healing in presence of structural reinforcements
1.3 - Evaluation of healing efficiency
1.3.1 - Quasi-static fracture
1.3.2 - Fatigue
1.3.3 - Impact damage/indentation
1.4 - Theoretical models of healing mechanisms
2 - Conclusion
References
4 - Thermochromic composite materials: synthesis, properties and applications
1 Introduction
2 Thermochromic materials classification
2.1 Inorganic reversible thermochromic materials
2.1.1 Crystal water gain/loss mechanism
2.1.2 Crystal transfer mechanism
2.2 Liquid crystal
2.3 Organic reversible thermochromic materials
2.3.1 Structural change in the molecule
2.3.1.1 Crystal transition mechanism
2.3.1.2 Dimensional structure change
2.3.1.3 Intermolecular proton transfer
2.4.1 Intermolecular electron transfer
3 Thermochromic material synthesis
3.1 Liquid phase deposition
3.2 Solid phase deposition
3.3 Vapor deposition
4 Properties of thermochromic composite materials
5 Thermochromic material applications
5.1 Textile field
5.2 Thermochromic smart window
5.3 Anticounterfeiting field
5.4 Sensors
5.5 Temperature indicators
6 Conclusion
References
5 - Piezoelectric polymer films: synthesis, applications, and modeling
1 Introduction
2 Piezoelectric polymers: types, fabrication, and applications
2.1 Bulk polymers
2.2 Piezocomposites
2.3 Charged cellular polymer films (ferroelectrets)
2.3.1 Most used cellular polymers
2.3.2 Case study: development of cellular polyethylene ferroelectrets
3 Modeling of the piezoelectric coefficient d33
3.1 Modeling of the elastic stiffness (c33)
4 Conclusion and future directions
References
Chapter Shape memory based on composites and nanocomposites materials: from synthesis to application
1 Introduction
2 Shape-memory materials
3 Shape-memory polymers
3.1 Background and definition
3.2 Classification of shape-memory polymers
3.3 Comparison between thermoplastic and thermoset SMPs
3.4 Architecture of shape-memory polymers
3.5 Stimulus methods of shape-memory polymers
Shape-memory polymers composites
4.1 Why use SMPCs instead of SMPs?
4.2 Reinforced shape-memory polymers composites (SMPCs)
4.2.1 Particle-filled shape-memory polymer composites
4.2.2 Fiber-reinforced shape-memory polymers
4.3 Shape-memory effects in polymer composites
4.4 Applications of SMPs and their composites
4.4.1 Biomedical applications
4.4.2 Other applications (deployable structures and actuators)
5 Conclusion
References
7 - Self-assembling smart materials for biomaterials applications
1 Introduction
2 Self-assembly of materials
2.1 The importance of self-assembly
2.2 Nanoscale building blocks for self-assemble smart biomaterials
2.2.1 Inorganic and organic nanostructures in smart biomaterials
2.3 Self-assembly of materials and biomolecules under internal interaction
2.4 Self-assembly of materials and biomolecules under external stimuli
2.4.1 pH-responsive self-assembly
2.4.2 Temperature-responsive self-assembly
2.4.3 Ionic strength-responsive self-assembly
2.4.4 Photo-responsive self-assembly
3 Self-assemble polymeric nanostructures in smart biomaterials
3.1 Micelles
3.2 Hybrid hydrogels
3.2.1 Polymeric hydrogels
3.2.2 Self-assembling DNA hydrogels
3.2.3 Hybrid hydrogels-based DNA self-assembly
3.2.4 Self-assembling poly polypeptide-based hydrogels
3.3 Dendrimers
3.3.1 Polypeptide dendrimers
3.3.2 Polyester dendrimers
3.3.3 Polyacetal dendrimers
4 Biomolecules as self-assemble smart biomaterials
4.1 Self-assemble DNA as a smart biomaterial
4.2 Self-assemble protein as a smart biomaterial
4.3 Self-assemble peptides as a smart biomaterial
Conclusion and future directions
References
8 - Electroactive polymer composites and applications
1 Introduction
2 Mechanism
3 Applications of electroactive polymers
3.1 Used in aerospace applications
3.2 Used in biomedical applications
3.3 Used in space applications
3.4 Used in automotive applications
4 Conclusions
References
9 - Polymer nanocomposites smart materials for energy applications
1 Introduction
1.1 Application on polymer nanocomposites-based smart materials in energy generation
2 Application on polymer nanocomposites based smart materials for energy storage
3 Challenges in polymer nanocomposites for energy application
4 Conclusion
References
10 - Smart materials for medical applications
1 Introduction
2 Silk: an excellent smart material
3 Silk smart materials based on structures
3.1 3D structures
3.2 Particle structures
3.3 Film structures
4 Smart silk material in medical applications
4.1 Drug delivery applications
4.2 Tissue engineering
4.3 Sutures
4.4 Wound dressing
4.5 Dentistry
4.6 Electronic applications
4.6.1 Biosensing devices
4.6.2 Optical devices
4.6.3 Switching memory devices
5 Conclusion and future directions
Acknowledgment
References
11 - Smart composite materials for civil engineering applications
1 Introduction
2 Applications of composite materials in civil engineering
2.1 Concrete
2.2 Road construction
2.3 Sensors
2.4 Repair and rehabilitation of historical monuments
3 Conclusion
Acknowledgment
References
12 - Molecularly imprinted polymer for water contaminants
1 Introduction
2 Adsorbent technology on water contaminants
3 The principle of molecularly imprinted polymer
3.1 Factors affecting the molecular imprinting process
3.1.1 Functional monomer
3.1.2 Cross-linking agents
3.1.3 Porogen
3.1.4 Initiator
3.1.5 Methods of preparation for molecularly imprinted polymer
4 Applications of MIP on water pollution
4.1 Heavy metals
4.2 Dyes
4.3 Polycyclic aromatic hydrocarbons (PAHs)
4.4 Micropollution
5 Conclusion
References
Index
Back Cover

Citation preview

Woodhead Publishing Series in Composites Science and Engineering

Polymer NanocompositeBased Smart Materials From Synthesis to Application

Edited by

Rachid Bouhfid Abou el Kacem Qaiss Mohammad Jawaid

Woodhead Publishing is an imprint of Elsevier The Officers’ Mess Business Centre, Royston Road, Duxford, CB22 4QH, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States The Boulevard, Langford Lane, Kidlington, OX5 1GB, United Kingdom 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. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-08-103013-4 (print) ISBN: 978-0-08-103014-1 (online) For information on all Woodhead publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Susan Dennis Acquisitions Editor: Gwen Jones Editorial Project Manager: Ana Claudia Garcia Production Project Manager: Vignesh Tamil Designer: Victoria Pearson Typeset by Thomson Digital

Editors are honored to dedicate this book to Research Collaboration between Composites and Nanocomposites Center, at Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Morocco and Laboratory of Biocomposite Technology, Institute of Tropical Forestry and Forest Products (NTROP), Universiti Putra Malaysia, Malaysia

Contributors Hind Abdellaoui  Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco Mohd Zaid. Akop  Center for Advanced Research on Energy, Universiti Teknikal Malaysia Melaka, Durian Tunggal, Melaka, Malaysia Prithvi C. Asapur  Central University of Gujarat, Gandhinagar, Gujarat, India Indrani Banerjee  Central University of Gujarat, Gandhinagar, Gujarat, India Mohammed-ouadi Bensalah  University Mohammed V—Rabat, Faculty of Science, Rabat, Morocco Anuradha Biswal  Department of Chemistry, Veer Surendra Sai University of Technology, Sambalpur, India Rachid Bouhfid  Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco Jorold John Britto  Department of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, Tamil Nadu, India Hind Chakchak  The Technical Support Units for Scientific Research (UATRS)/ The National Center for Scientific and Technical Research (CNRST), Rabat, Morocco Mounir El Achaby  Materials Science and Nanoengineering Department (MSN), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco Hamid Essabir  Moroccan Foundation for Advanced Science, Innovation and Research, Rabat, Morocco; Ibn Zohr University—Agadir, National School of Applied Sciences, Agadir, Morocco K. Ganesh  Department of Mechanical Engineering, Eritrea Institute of Technology, Mai-Nefhi, Asmara, Eritrea Ouassim Hamdi  Department of Chemical Engineering, Université Laval, Quebec, Canada Mohammad Jawaid  Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, Serdang, Malaysia Naveen Jusuarockiam  Department of Mechanical and Manufacturing Engineering, Universiti Putra Malaysia, Serdang, Malaysia Nor Ain Shahera Khairi  Institute of Advanced Technology, Universiti Putra Malaysia, Serdang, Selangor, Malaysia

xii Contributors

Anish Khan  Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, Saudi Arabia Senthil kumar Krishnasamy Department of Mechanical Engineering, Kalasalingam Academy of Research and Education, Krishnankoil, Tamil Nadu, India; Department of Mechanical and Process Engineering, The Sirindhorn International Thai-German Graduate School of Engineering (TGGS), King Mongkut’s University of Technology North Bangkok, Bangkok, Thailand; Centre for Composite Materials, International Research Centre, Kalasalingam Academy of Research and Education, Krishnankoil, Tamil Nadu, India R. Kumar  Department of Mechanical Engineering, Eritrea Institute of Technology, Mai-Nefhi, Asmara, Eritrea Muhd Ridzuan. Mansor  Center for Advanced Research on Energy, Universiti Teknikal Malaysia Melaka, Durian Tunggal, Melaka, Malaysia Mohamed El Mehdi Mekhzoum  Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco Frej Mighri  Department of Chemical Engineering, Université Laval, Quebec, Canada Chandrasekar Muthukumar  School of Aeronautical Sciences, Hindustan Institute of Technology & Science, Chennai, Tamil Nadu, India Souad Nekhlaoui  University Mohammed V—Rabat, Faculty of Science, Rabat, Morocco Abou el kacem Qaiss  Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco Siti Khadijah Ab. Rahman  Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, Serdang, Selangor, Malaysia Rajapaksha Dewage Asanka Amith Rajapaksha  Institute of Nano Electronic Engineering, Universiti Malaysia Perlis, Kangar, Perlis, Malaysia; College of Chemistry, Central China Normal University, Wuhan Hubei, P.R. China Marya Raji  Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco Ishak Mohd Ridwan  Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, Serdang, Malaysia; Department of Aerospace Engineering, Universiti Putra Malaysia, Serdang, Malaysia Denis Rodrigue  Department of Chemical Engineering, Université Laval, Quebec, Canada

Contributors

xiii

S.S. Saravanakumar  Department of Mechanical Engineering, Kamaraj College of Engineering and Technology, Virudhunagar, Tamil Nadu, India P. Senthamaraikannan  Department of Mechanical Engineering, Kamaraj College of Engineering and Technology, Virudhunagar, Tamil Nadu, India Sarat K. Swain  Department of Chemistry, Veer Surendra Sai University of Technology, Sambalpur, India Senthil Muthu Kumar T  Department of Mechanical Engineering, Kalasalingam Academy of Research and Education, Krishnankoil, Tamil Nadu, India; Centre for Composite Materials, International Research Centre, Kalasalingam Academy of Research and Education, Krishnankoil, Tamil Nadu, India S. Vijay Ananth  Department of Mechanical Engineering, Vels Institute of Science, Technology & Advanced Studies, Chennai, India Nor Azah Yusof  Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, Serdang, Selangor, Malaysia; Institute of Advanced Technology, Universiti Putra Malaysia, Serdang, Selangor, Malaysia

About the editors Dr. Rachid Bouhfid is a senior researcher at Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center (CNC), Rabat, Morocco. He obtained his PhD in Organic Chemistry from Mohammed V University, Morocco. Following his PhD, he joined Artois University, France as ATER, and then became Assistant Professor. Dr. Rachid Bouhfid’s research are mainly in the field of organic synthesis of functional molecules to use them as modifiers of inorganic fillers and the development of new polymeric nanocomposites based on clay and nanoclay, graphene, and cellulose nanocrystalline. So far, he has published two books, 25 chapters and more than 150 international journal papers with inventions of 18 patents to his credits. Dr. Bouhfid is the regular reviewers of different international journals published by RSC, Elsevier, Wiley, Springer, Bentham, etc. There are six scholars who are successfully awarded PhD degree with active supervisions of Dr. Bouhfid. He has handled several research grants from the MAScIR Foundation and Minister of National Education, Vocational Training, Higher Education and Scientific Research of Morocco. He has co-organized several international conferences in the field of heterocyclic chemistry (Trans Mediterranean Colloquium on Heterocyclic Chemistry TRAMECH-7, Rabat, 2013) and polymer processing (The International Polymer Processing Society Meeting PPS-27, Marrakech, 2011). Dr. Abou el kacem Qaiss is currently working as Director of Composites and Nanocomposites Center, at Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR). He received his PhD from Université Laval, Québec, Canada. He has more than 20 years of experience in teaching, research, and industries. His area of research interests includes Hybrid Reinforced/Filled Polymer Composites, Advance and Smart Materials: Graphene/Nanoclay, Lignocellulosic Reinforced/ Filled Polymer Composites, Modification and Treatment of Lignocellulosic Fibres, Nano Composites and cellulose Nanofibril and Nanocrystals, Polymer blends. So far he has published more than 25 book chapters, and more than 100 International journal papers during 2011–2019. He is also reviewer of several high impact ISI journals of Elsevier, Springer, Wiley, etc., publishers. Presently, he is supervising 4 PhD students in the field of Hybrid composites, Green composites, Nanocomposites, Natural fiber reinforced composites, etc. 8 PhD students graduated under his Supervision in 2012– 19. He has Research grant at MAScIR and Minister of Higher Education, Scientific Research and Training, Morocco (MESRSFC) of around USD 690000. He was a cochair of The International Polymer Processing Society Meeting (PPS-27) that hold for the first time in Africa and in the MENA region (Middle East and North Africa), in the City of Marrakech, Morocco, May 10–14th, 2011. Dr. Mohammad Jawaid is currently working as High-Flyer Fellow (Professor) at Biocomposite Technology Laboratory, Institute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia (UPM), Serdang, Selangor, Malaysia,

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About the editors

and also has been Visiting Professor at the Department of Chemical Engineering, College of Engineering, King Saud University, Riyadh, Saudi Arabia since June 2013. He has more than 14 years of experience in teaching, research, and industries. His area of research interests includes hybrid composites, lignocellulosic reinforced/filled polymer composites, advance materials: graphene/nanoclay/fire retardant, modification and treatment of lignocellulosic fibers and solid wood, biopolymers and biopolymers for packaging applications, nanocomposites and nanocellulose fibers, and polymer blends. So far, he has published 37 books, 65 book chapters, more than 350 peer-reviewed international journal papers, and several published review papers under top 25 hot articles in science direct during 2013–2018. He also obtained 2 Patents and 3 Copyrights. H-index and citation in Scopus are 46 and 9237 and in Google scholar, H-index and citation are 53 and 12665. He is founding Series Editor of Composite Science and Technology Book Series from Springer-Nature, and also Series Editor of Proceeding in Material Science, Springer-Nature. He worked as guest editor of special issues of SN Applied Science, Current Organic Synthesis and Current Analytical Chemistry, International Journal of Polymer Science, IOP Conference Proceeding. He also in Editorial Board Member of Journal of Polymers and The Environment, Journal of Plastics Technology, Applied Science and Engineering Progress Journal, Journal of Asian Science, Technology and Innovation and the Recent Innovations in Chemical Engineering. He is also a life member of Asian Polymer Association, and Malaysian Society for Engineering and Technology; Professional Member of Society for polymers Engineers, American Chemical Society, International Association of Advanced Materials, and Universal Association of Mechanical and Aeronautical Engineers (UAMAE), The IRED. Besides that, he is also reviewer of several highimpact international peer-reviewed journals of Elsevier, Springer, Wiley, Saga, ACS, RSC, Frontiers, etc. Presently, he is supervising 16 PhD students (5 PhD as Chairman, and 11 PhD as Member) and 8 Master’s students (2 Master as Chairman, and 6 Master as Member) in the fields of hybrid composites, green composites, nanocomposites, natural fiber-reinforced composites, nanocellulose, etc. 20 PhD and 11 Master’s students graduated under his supervision in 2014–2020. He has several research grants at university, national, and international levels on polymer composites of around 3 million Malaysian ringgits (USD 700,000). He also delivered plenary and invited talks in international conferences related to composites in India, Turkey, Malaysia, Thailand, the United Kingdom, France, Saudi Arabia, Egypt, and China. Besides that, he is also a member of technical committees of several national and international conferences on composites and material science. Recently Dr. Mohammad Jawaid received Excellent Academic Award in Category of International Grant-Universiti Putra Malaysia-2018 and also Excellent Academic Staff Award in industry High Impact Network (ICAN 2019) Award. Beside that Gold Medal-Community and Industry Network (JINM Showcase) at Universiti Putra Malaysia. He also Received Publons Peer Review Awards 2017, and 2018 (Materials Science), Certified Sentinel of science Award Receipient-2016 (Materials Science) and 2019 (Materials Science and Cross field). He is also Winner of Newton-Ungku Omar Coordination Fund: UK-Malaysia Research and Innovation Bridges Competition 2015.

Preface The editors are pleased to present the book Polymer Nanocomposite-Based Smart Materials: From Synthesis to Application under the book series Composites Science and Engineering. Over the past 25 years, the smart polymeric materials have attracted the attention of both scientists’ researchers and industries for a diverse range of applications, from automotive and construction, consumer electronics, marine, to aeronautics or biomedical and agriculture fields, for example, in drug delivery systems, tissue generation/ repair, sensing, optical materials, smart coatings, moreover in artificial muscles or biomimetic actuators. Smart polymeric materials built of the responsive polymers that are eligible to alter one or more chemical and/or physical properties upon exposure to external stimuli factors, including changes in temperature, light, pH, mechanical force, enzyme, moisture, electric, or magnetic field, chemical composition, etc. There are different kind of smart polymeric materials as piezoelectric, pyroelectric, electrochromic, magnetostrictive, shape memory, photochromic, thermochromic, self-healing based on composites and nanocomposites materials, which generally depending in of the observable micro- and/or nanoscale changes, such as color, shape, temperature, and functionality, etc. This book gives a broad updated survey and information of the major categories of smart materials and their preparation routes, providing also the main applications fields and properties for these diverse types of smart polymer based on composites and nanocomposites materials. On the other hand, some of the modeling methods and simulation is presented to summarize the physical changes response introduced by the effect of changing in the environmental conditions. We are highly grateful to all authors who contributed to this book and made our idea reality. In addition, we are also grateful to the Elsevier UK support team, for helping us during completion of this book. Abou el kacem Qaiss, Morocco Mohammad Jawaid, Malaysia Rachid Bouhfid, Morocco

Introduction: different types of smart materials and their practical applications

1

Mohamed El Mehdi Mekhzoum, Abou el kacem Qaiss, Rachid Bouhfid Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco

1  Introduction to smart materials Over the last decade, the design of new materials that are smarter or intelligent, multifunctional, more survivable, customizable, as well as environmentally compatible has received considerable attention and becomes a key research focus for all scientific from diverse technological and engineering disciplines [1–4]. Back in mid-1980s, the idea of smart, intelligent, and adaptive structures has emerged as newly era of the most exciting class of functional materials with large-scale systems [5–9]. These smart materials exhibit different properties and behavior such as self-alterable dynamic properties, self-healing, self-sensing, self-adaptability, and are highly sensitive to any external stimuli in their environments, namely moisture, temperature, stress, light, pressure, electric, or magnetic field [10–15]. Nowadays, smart materials, which have the ability to be active, sharp, fashionable, clever, as well as sophisticated, can be applied in all human life and technology. In addition, a number of researchers have investigated the use of their potential in various engineering applications which may prove useful for us [16,17]. Smart or intelligent material systems are often hybrid composite or integrated systems of materials with several advantages and capabilities than the existing conventional functional materials [18,19]. These performances include lighter weight, no corrosion, as well as increase in duration of the structures that use them. They can also modify their dimensions, their form, and their mechanical properties. They have an important role to play in building technology development in the world and perform as a living system [20]. Interestingly, several smart materials have been provided by nature, for instance, Chameleons change color according to environmental situations, sunflowers turn toward the sun [21], and cuttlefish change their body patterns and colors depending on their surrounding environment [22]. There are a lot other examples where nature applied time-control efficiently in switching critical properties [23]. Recently, several cases of smart materials have been reported including gels that change color due to external stimuli, namely pressure, temperature, humidity [24], self-healing polymers that deliver healing agents during structural damage [25,26], as well as electronic paper displays, whose ink disappears or appears depending on electrical charge [27,28]. Taking into account the wide range of uses in science and nature, smart materials have numerous potential applications and broadly implemented in a Polymer Nanocomposite-Based Smart Materials. http://dx.doi.org/10.1016/B978-0-08-103013-4.00001-7 Copyright © 2020 Elsevier Ltd. All rights reserved.

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Polymer Nanocomposite-Based Smart Materials

variety of industries including automotive, aerospace, military, mechanical and biomedical engineering, energy, electronics and chemical, nanomedicine, cell recovery, disease therapy, and civil engineering [29–32]. Furthermore, there are so many commercial and industrial applications and new ones that are being investigated by a several range of organizations. The objective of this chapter is to review the state of the art of smart material, and their different types including piezoelectric, magnetostrictive, shape-memory alloy (SMA), chromic materials, and thermoresponsive materials. This chapter concludes with some practical applications of smart materials.

2  Smart materials: definition and fundamental characteristics McCabe Zrinyi [33] defined intelligent materials as those which may be altered by stimuli and then transform back to the original state after removing the stimuli. These stimuli (input) can be temperature changes, pH, movement, moisture, deformation, stress, electricity, chemical or biomedical agents, and magnetic fields, whereas the output can be changes in deformation, stress temperature, viscosity, or electrical resistance [34] (Fig. 1.1). In addition, smart materials are also known as responsive materials which have high capacity to respond to any environmental change. Therefore, a key characteristic of smart materials includes the ability to return to the original state after the stimulus has been removed [35]. In addition, five common fundamental characteristics were defined as distinguishing a smart material from the more traditional materials such as transiency, immediacy, self-actuation, directness, and selectivity [36]. Furthermore, smart materials are either active or passive; the active ones have the intrinsic ability to transduce energy, whereas the passive do not. Piezoelectric materials are active smart materials, while fiber optic is passive. Besides, passive materials can be applied as sensors but not as actuators [37]. Generally speaking, sensor and actuator are fundamental functions of smart structures for sensing and controlling purposes. These components are usually combined using different materials in combination with a control unit. These combinations can be called hybrid composites connected with a control unit [38–40]. Some advantages of smart materials sensors as well as actuators include fast response, few moving parts, and compact size, while their disadvantages are mainly high cost, limited strain outputs, limited blocking forces, and sensitivity to harsh environmental conditions [41]. Table 1.1 illustrated the smart materials actuators and sensors, and their associated “stimulus” and “response.”

Figure 1.1  Basic functioning of smart materials.

Introduction: different types of smart materials and their practical applications

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Table 1.1  Sensor and actuator of some smart material classes. Variables

Material class

Stimulus

Response

Sensors

Pyroelectrics Electrostrictors Magnetostrictors Electrochromic Piezoelectrics Shape-memory alloys Magnetostrictors Electrorheological fluids

Temperature change Mechanical strain Mechanical strain Electric field Electric current Temperature change Magnetic field Electric field

Electric polarization Electric polarization Change in magnetic field Color change Mechanical strain Mechanical strain Mechanical strain Viscosity change

Actuators

3  Types of smart materials There are many types of smart material. Each type exhibits different characteristics that can be changed as well as different interest for designers and users. To understand the variety of potential uses, a classification is required. In the following section, the most mature intelligent materials are shortly described [42,43]. The other materials, which include electrostrictive, elastorestrictive, electrorheological, magnetorheological, pH-sensitive materials, smart polymers, smart (intelligent) gels (hydrogels), smart catalysts, are usually rather less well known and have limited academic curiosities. Smart materials are generally classified into the following types (Scheme 1.1).

3.1  Piezoelectric materials The Greek term piezoelectricity is composed of piezo which means to press and electron refers to amber. The piezoelectric materials have the ability to produce an electric potential as a response to an input in the form of an applied mechanical stress. When an electric potential is applied to the surface of the piezoelectric material, a mechanical

Scheme 1.1  Types of smart materials.

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Polymer Nanocomposite-Based Smart Materials

Figure 1.2  General milestone map for piezoelectric materials [54].

strain is generated. Therefore, the structure made with this material can bend, expand, and compress [44]. Piezoelectric materials are lightweight and compact. They are high energy density materials that scale very favorably upon miniaturization and used in several application, namely optics, medicine, biology, microelectronics, and mechanical engineering. These materials exhibit simultaneous actuator/sensor behavior and can act as transducers between electric potential and frequency [45,46]. Historically, the phenomenon of piezoelectricity was first reported by Curie in 1880 and was demonstrated in a-SiO2 crystal (quartz) [47]. Several piezoelectric materials have been reported synthesized [48–50]. Also, new piezoelectric devices, for instance, actuators and transducers, have been invented and used in a variety of engineering applications and systems [51,52]. Fig. 1.2 summarizes a general milestone map for piezoelectric material as a function of their performance since 1880–2014. Many synthetic and natural materials show piezoelectric properties [53], which can be classified into four classes: natural crystals, liquid crystals, noncrystalline materials textures, and synthetic piezoelectric materials (Table 1.2). Table 1.2  Some synthetic and natural piezoelectric materials. Natural crystals Liquid crystals Noncrystalline materials Textures Synthetic piezoelectric materials

Quartz, Rochelle salt, ammonium phosphate Glass rubber, paraffin Bone, wood 1. Piezoceramics: lead zirconate titanate, barium titanate, lead niobate, lead lanthanum zirconate titanate 2. Crystallines: ammonium dihydrogen phosphate 3. Piezoelectric polymer: polyvinylidene fluoride

Introduction: different types of smart materials and their practical applications

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3.2  Magnetostrictive materials These materials exhibit changes in the shape under the influence of the magnetic field and also the change of magnetization under the influence of the mechanical stress. The magnetostrictive materials can convert magnetic energy into kinetic energy, or the reverse [55]. In 1842, the magnetostrictive effect was first discovered by an English physicist James Joule. He reported that a sample of ferromagnetic material changes its length in the presence of a magnetic field. Generally, magnetostrictive actuator materials are similar to piezoelectric ones, but respond to magnetic, relatively than electric, fields [56]. Ni was the first known magnetostrictive material that showed strains of 50 ppm in a 1-m rod, usually called micro-strain. After that, Alstad and Rhyne reported that the rare earth element iron combined with terbium had much larger strains (1000 ppm) than nickel one. The giant magnetostrictive material or Terfenol-D represents the best-known example of magnetostrictive materials and the difference in strain can be as much as 1500–1700 ppm owing to alignment of its magnetic domains [57,58]. The magnetostrictive materials are very expensive. They contain one of the rarest of the rare earth material, they can achieve high elastic modulus (E = 200 GPa), and they have also fine hysteresis loop and thus low loss [59,60]. Several magnetostrictive actuator and sensor materials have been reported and used in various applications such as magnetostrictive clamps [61], self-biased modular drivers [62], omnidirectional loudspeakers, and helical line hydrophones [63]. Fig. 1.3 shows a typical configuration of a magnetostrictive actuator.

3.3  Shape-memory alloys They are group of metallic materials such as NiTi, NiTiCu, and CuAlNi that can recover from a deformation and return to its original shape when subjected to heat [65]. In 1932, Ölander was first reported shape memory like behavior in a sample of

Figure 1.3  Magnetostrictive actuator [64].

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Figure 1.4  Schematic illustration of shape-memory effect [70].

gold cadmium (AuCd) [66]. A full shape memory effect was then observed in a series of nickel–titanium alloys by Buehler, Gilfrich, and Wiley in 1963 [67]. The most commercially attractive known SMA is nickel–titanium (NiTi) also called Nitinol which is developed at the Naval Ordnance Laboratory in the early 1960s. Moreover, some polymers as well as ceramics materials also show the shape-memory effect. The Nitinol material possesses the best shape-memory properties (shape-memory strain of 8%) with variable transformation temperature and the ability to change its chemistry or composition. Fig. 1.4 represents the principal of SMA [68,69]. Moreover, copper-based SMA, namely Cu-Al-Ni as well as Cu-Zn-Al, has 4% and 5% of shape-memory strain, respectively. The NiTi SMA displays excellent fatigue behavior and high corrosion resistance. In addition, Nitinol material can be used in variety of industrial application, namely in medical applications [71–76]. Recent examples of SMAs have been reported, for instance, tiny actuators that eject discs from computers machines and amazing bendable eyeglass frames. Thus, the fascinating behaviors of these devices depend on a phenomenon called the “shape-memory effect” [77,78]. There are two different temperature-dependent crystalline states: the higher temperature is defined as austenite state and the lower one is called martensite state. In the austenite state, the physical properties of the material are strong and hard, whereas in the martensite phase, it’s soft and ductile. In addition, the crystal structure of austenite and martensite materials is simple body-centered cubic as well as a complex rhombic structure, respectively [79–81]. SMAs are already used in aerospace morphing structure, for examples, in an engine nozzle on a Boeing commercial airplane in order to reduce jet noise [82] (Fig. 1.5). In addition, some other uses of SMAs in jet engines, namely a morphing intake [83], a morphing nozzle [84], and morphing inlet internal wall [85]have been also reported.

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Figure 1.5  Boeing’s variable geometry chevron (VGC) [82].

3.4  Chromic materials Chromic materials are smart or intelligent materials that exhibit a distinct color change when subjected to an external stimulus (temperature, pressure, light, electric field), particularly when the change is controllable as well as reversible [86,87]. These color change phenomena can be irreversible or reversible. In this sense, when the original color/optical properties of the materials are regained once the external stimuli are removed, these materials possess reversible chromism. Some materials exhibit new color/optical properties even when the external impetus are removed and do not regain their old color/optical properties. Such materials possess irreversible chromism [88–90]. Interestingly, the reversible chromism materials are more useful than the irreversible ones due to the fact that the reversible chromic materials can be used multiple times. Furthermore, in the visible region from 400 to 800 nm, the color change of these materials can be observable by our naked eye. However, the photodetectors have replaced eye, and thus the color change can be infrared, ultraviolet, or visible regions. Numerous materials with chromic properties have been discovered and investigated in the course of recent decades and wide ranges of products have been introduced commercially [91,92]. Among them, many varieties of dyes and pigments are used as chromic materials [93–96]. Another example of chromic materials is photochromic sunglasses. These glass lenses change color when they are held under sunlight and regain their original color in shadow (Fig. 1.6). Chromic materials have been studied since before the 1900s and present a large possible input. Thus, they can be used in a wide variety of industrial applications, for instance, in thermometry, electronics, ophthalmics, and biomedicine. These materials can be classified into several types depending on the cause/stimuli. Table 1.3 enumerates a list of exhaustive chromism as well as their causes/stimuli involved. The most studied chromic materials are photochromic (color change with light), thermochromic (color change with heat), and electrochromic (color change by applying electric field), while the others materials listed have limited commercial exploitation [97–99].

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Figure 1.6  Optical images of temperature-dependent visual color changes of thermochromic materials [100]. Table 1.3  Important types of chromism and their causes/stimuli. No.

Chromism

Stimulis

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

Thermochromism Photochromism Ionochromism Electrochromism Solvatochromism Vapochromism Mechanochromism Chronochromism Radiochromism Magnetochromism Biochromism Tribochromism Humidochromism Halochromism Piezochromism

Change in temperature Illumination by light Due to ions Application of a voltage Solvents Due to vapor/gas contact and/or its concentration Mechanical action Time Ionizing radiation Magnetic field Biological sources Due to mechanical friction Change in humidity Due to change in pH Application of pressure/change in pressure applied

3.5  Thermoresponsive materials During the past decades, one of the main groups of “intelligent” materials is based on stimuli-responsive polymers. These materials have attracted considerable attention owing to their high potentiality in tailoring intelligent materials than metals or ceramics ones [101,102]. These responsive polymers can respond to stimuli, namely pH, temperature, ionic strength, light, humidity, electrical or magnetic field, chemical and biological stimuli. Among several environmental stimuli, temperature is most widely studied in the field of “intelligent” polymers. Thermoresponsive polymers, also termed as temperature responsive polymers, are polymers that have the ability

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Figure 1.7  Curves showing phase transition phenomenon. (A) Lower critical solution temperature (LCST) and (B) upper critical solution temperature (UCST) phase transition behaviors of thermo-responsive polymers in solution [105].

to respond to a change in temperature. Thermoresponsive polymers materials show a phase transition temperature in which a drastic change in the solubility occurs [103]. There are two main types of thermoresponsive polymers. The first type corresponds to the lower critical solution temperature (LCST) and the second one related to the upper critical solution temperature (UCST). LCST is defined as the temperature at which a thermoresponsive polymer upon heating changes reversibly its properties from watersoluble to water-insoluble, while the UCST upon cooling shows the opposite behavior to LCST. In this case, the polymer goes from hydrophobic to hydrophilic. However, UCST has much less documented compared to LCST owing to their high sensitivity to the environmental [104]. Fig. 1.7 illustrates the phase diagrams of polymer solution LCST and UCST behaviors. In the phase diagram, the minimum and maximum temperatures are indicated as being the LCST and UCST, respectively. Poly(N-alkyl-substituted acrylamides) are the first reported and most studied thermo-responsive polymers exhibiting an LCST in water [106]. Among these polymers, poly(N-isopropylacrylamide) (PNIPAM) shows a phase transition behavior across its LCST, which is generally around 32°C. This temperature is very close to the human physiological temperature and valuable for pharmaceutical and biomedical applications [7,8]. Additionally, the polymer consists of hydrophilic (amide) and hydrophobic (isopropyl) groups, and its solubility in water can be affected by environmental conditions including the nature of substituent groups, temperature, molar mass, cosolvent, ion concentration or salt concentration and surfactants [107,108]. As example, the PNIPAM solubility in water can be reduced or enhanced by introducing hydrophobic or hydrophilic comonomers, respectively. The properties of PNIPAM are applied in biosensors, thermally modulated drug delivery systems, thermoresponsive cell culture substrates, and thermoresponsive enzymes [109]. Several other polymers with thermoresponsive properties showing LCST behavior including poly(methyl vinyl ether) (PMVE) with an LCST of around 37°C, poly(N-vinylcaprolactam) (PVCL), which has an LCST between 25 and 35°C, poly(N,N-diethylacrylamide) (PDEAAM) with an LCST of 32°C, poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) with an LCST of 50°C, and poly(ethylene glycol) (PEG) with an LCST of 85°C have been widely investigated and have found numerous applications

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Scheme 1.2  Structures of some thermoresponsive polymers with LCST and UCST behaviors.

as intelligent materials [110–112]. On the contrary, only a few examples of thermoresponsive polymers showing UCST behavior in water have been reported, for example, zwitterionic polymers and poly(sulfobetaine)s [113,114]. Scheme 1.2 represents some thermoresponsive polymers with an LCST and a UCST. Moreover, various polymeric materials that exhibit thermoresponsive behavior, namely membranes of thermosensitive permeability, hydrogels with a temperature-depending swelling behavior, materials which change color or sharp upon reaching a certain temperature, have been reported in the literature [115–118]. In addition, few natural polymers have been investigated as thermoresponsive materials, namely derivatives of agarose and cellulose for examples (methyl cellulose (MC) has an LCST of 40°C and hydroxypropylmethyl cellulose (HPMC) has an LCST of 69°C) [119,120]. Due to their highly reversible responsive behavior, thermoresponsive materials have gained significant scientific interest and have been the subject of numerous publications dedicated to their potential applications including drug delivery system, rheological control additives, smart surface modification, gene therapy, microfluidics, thermal affinity separation, temperature sensing and nanotechnology, catalysis, bioengineering, oil industry, chromatography, mechanical transducers (artificial muscles), reversible adhesion, etc. [121–125].

4  Application of smart materials As stated before, the increasing demand for new generations of advanced products has fuelled research activities focused on smart materials. Smart materials have at least one or more characteristics that can be dynamically changed depending on specific

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conditions called external stimuli. In addition, each type of intelligent material has specific properties that can be altered, namely color, volume, shape, as well as conductivity. Therefore, these properties can affect on their types of applications in different areas [55,126]. Numerous commercial and industrial applications of smart materials technology have been reported in different field including aircraft or automobiles discussed by Boller [127], aerospace structures, robotic suites for entertainment, biomedicine and structural health monitoring reported by Sohn et al. [128], sensors or sensing devices, skin diagnostics, engineering, civil infrastructure, virtual reality systems for education, microelectronics, adaptive manufacturing tooling, marine structures, as well as other applications such as intelligent highways, smart antibodies, toxic waste processing, and high-speed railways. Moreover, most application of smart technology has focused especially on aerospace area evolving to control, noise, vibration, aeroelastic stability, shape and stress distribution vibration, as well as damping [128–135]. However, there are various barriers that restraint their space applications that include actuator stroke, nonexistent mathematical modeling of smart systems, and reliable database of smart material characteristics [136]. Fig. 1.8 presents a few potential locations for the use of smart materials and structures in aircraft. Figs. 1.9 and 1.10 show examples, for the use of smart materials for the deployment of airbags and antilock braking systems (ABS). Smart composite materials are also used in wind power generation due to their high stiffness, low density, and long fatigue life features [138]. In addition, smart materials offer new opportunities for application in nuclear sector, namely for personal exposure reduction, performance improvement, and life-cycle cost-reduction [139].

Figure 1.8  Locations of potential smart systems in an aircraft [137].

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Figure 1.9  Smart materials applications in the robotics domain [140].

Figure 1.10  A modern car with a large number of smart subsystems [141].

5 Conclusion Advanced materials that change their properties by an external condition have perennially attracted much scientific attention and industrial communities. These “smart” or “intelligent” materials are the next generation of new materials that have a potential

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to impact the technologies for lifetime efficiency and improved reliability. Therefore, the ultimate aim of research in this area is to understand as well as to control both the microstructure and composition of these materials which are vital to the development of several fields of science and technology. In this chapter, we reported a short overview about the smart materials technology, their types, their specific properties, as well as some general examples for applications of smart materials which may prove useful for us.

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[111] Ramos J, Imaz A, Forcada J. Temperature-sensitive nanogels: poly(N-Vinylcaprolactam) versus poly(N-isopropylacrylamide). Polym Chem 2012;3(4):852–6. [112] Webster M, et al. Tunable thermo-responsive poly(N-Vinylcaprolactam) cellulose nanofibers: synthesis, characterization, and fabrication. Macromolecular Mater Eng 2013;298(4):447–53. [113] Chen CY, Wang HL. Dual thermo- and PH-responsive Zwitterionic sulfobataine copolymers for oral delivery system. Macromolecular Rapid Commun 2014;35(17):1534–40. [114] Maji T, Banerjee S, Biswas Y, Mandal TK. Dual-stimuli-responsive l—serine-based Zwitterionic UCST-type polymer with tunable thermosensitivity. Macromolecules 2015;48(14):4957–66. [115] Garreau S, Leclerc M, Errien N, Louarn G. Planar-to-nonplanar conformational transition in thermochromic polythiophenes: a spectroscopic study. Macromolecules 2003;36(3):692–7. [116] Gong J-P, Osada Y. Soft and wet materials: polymer gels. Adv Mater 1998;10(11):827. [117] Rao G, Rama V, et al. Synthesis and characterization of silica-poly(N-isopropylacrylamide) hybrid membranes: switchable molecular filters. Chem Mater 2002;14(12):5075–80. [118] Schmidt AM. Thermoresponsive magnetic colloids. Colloid Polym Sci 2007;285(9):953–66. [119] Calejo MT, et al. In vitro cytotoxicity of a thermoresponsive gel system combining ethyl(hydroxyethyl) cellulose and lysine-based surfactants. Colloids Surf B Biointerf 2013;102:682–6. http://dx.doi.org/10.1016/j.colsurfb.2012.09.033. [120] Jeong B, Sung WK, Bae YH. Thermosensitive sol-gel reversible hydrogels. Adv Drug Delivery Rev 2012;64:154–62. http://dx.doi.org/10.1016/j.addr.2012.09.012. [121] Dilgimen AS, et al. Water-soluble covalent conjugates of bovine serum albumin with anionic poly(N-Isopropyl-Acrylamide) and their immunogenicity. Biomaterials 2001;22(17):2383–92. [122] Dinçer S, Tuncel A, Pis¸kin E. A potential gene delivery vector: N-isopropylacrylamideethyleneimine block copolymers. Macromolecular Chem Phys 2002;203(10–11):1460–5. [123] Kikuchi A, Okano T. Intelligent thermoresponsive polymeric stationary phases for aqueous chromatography of biological compounds. Progress Polym Sci (Oxford) 2002;27(6):1165–93. [124] Kondo A, Kaneko T, Higashitani K. Development and application of thermo-sensitive immunomicrospheres for antibody purification. Biotechnol Bioeng 1994;44(1):1–6. [125] Ngang HP, Ahmad AL, Low SC, Ooi BS. Preparation of thermoresponsive PVDF/SiO 2-PNIPAM mixed matrix membrane for saline oil emulsion separation and its cleaning efficiency. Desalination 2017;408:1–12. http://dx.doi.org/10.1016/j.desal.2017.01.005. [126] Measures RM, et al. Fiber optic sensors for smart structures. Optics Lasers Eng 1992;16(2–3):127–52. [127] Boller C. State of the art and trends in using smart materials and systems in transportation vehicles. Proc Institut Mech Eng Part I J Syst Control Eng 1998;212(3):149–58. [128] Sohn JW, Kim GW, Choi SB. A state-of-the-art review on robots and medical devices using smart fluids and shape memory alloys. Appl Sci (Switzerland) 2018;8(10):1928. [129] Bolshakov VI, et al. The usage of smart materials for skin-diagnostics of building structures while their monitoring. Procedia Eng 2017;172:119–26. http://dx.doi.org/10.1016/j. proeng.2017.02.033. [130] Chang G, Morreale P, Medicherla P. Applications of augmented reality systems in education. Technol Teacher Edu 2010;2010:1380–5. http://www.editlib.org/p/33549/. [131] Chong KP, Nicholas JC, Washer G. Health monitoring of civil infrastructures. Smart Mater Struct 2003;12(3):483–93.

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[132] Gray HN, Bergbreiter DE. Applications of polymeric smart materials to environmental problems. Environ Health Perspect 1997;105(Suppl. 1):55–63. [133] Kageyama K, et al. Smart marine structures: an approach to the monitoring of ship structures with fiber-optic sensors. Smart Mater Struct 1998;7(4):472–8. [134] Spencer BF, Ruiz-Sandoval ME, Kurata N. Smart sensing technology: opportunities and challenges. Struct Control Health Monitor 2004;11(4):349–68. [135] Varadan VK, Varadan VV. Microsensors, microelectromechanical systems (MEMS), and electronics for smart structures and systems. Smart Mater Struct 2000;9(6):953–72. [136] Straub FK, Merkley DJ. Design of a smart material actuator for rotor control. Smart Mater Struct 1997;6(3):223–34. [137] Akhras G. Smart materials and smart systems for the future. Canadian Military J 2000;1:25–32. [138] Nelson RC, et al. A smart wind turbine blade using distributed plasma actuators for improved performance. In: 46th AIAA aerospace sciences meeting and exhibit. Reno, NV, USA; 2008. [139] Giurgiutiu V, Zagrai AN. Use of smart materials technologies in radiation environments and nuclear industry. In: Proceedings of the SPIE 3985. Smart structures and materials 2000: smart structures and integrated systems; June 22, 2000. Doi: 10.1117/12.388812. [140] Subburaman R, et al. Human inspired fall prediction method for humanoid robots. Robot Auton Sys 2019;121:103257. https://doi.org/10.1016/j.robot.2019.103257. [141] Narayanan SN, Khanna K, Panigrahi BK, Joshi A. Smart cities cybersecurity and privacy. Security in Smart Cyber-Physical Systems: A Case Study on Smart Grids and Smart Cars. Elsevier Inc; 2019. http://dx.doi.org/10.1016/B978-0-12-815032-0.00011-1.

2

Role of characterization techniques in evaluating the material properties of nanoparticle-based polymer materials

Chandrasekar Muthukumara, Naveen Jusuarockiamb, Senthil kumar Krishnasamyc,d,e, Senthil Muthu Kumar T c,e, Mohammad Jawaidf, Ishak Mohd Ridwanf,g, Jorold John Brittoh a School of Aeronautical Sciences, Hindustan Institute of Technology & Science, Chennai, Tamil Nadu, India; bDepartment of Mechanical and Manufacturing Engineering, Universiti Putra Malaysia, Serdang, Malaysia; cDepartment of Mechanical Engineering, Kalasalingam Academy of Research and Education, Krishnankoil, Tamil Nadu, India; dDepartment of Mechanical and Process Engineering, The Sirindhorn International Thai-German Graduate School of Engineering (TGGS), King Mongkut’s University of Technology North Bangkok, Bangkok, Thailand; eCentre for Composite Materials, International Research Centre, Kalasalingam Academy of Research and Education, Krishnankoil, Tamil Nadu, India; fInstitute of Tropical Forestry and Forest Products (INTROP), Universiti Putra Malaysia, Serdang, Malaysia; gDepartment of Aerospace Engineering, Universiti Putra Malaysia, Serdang, Malaysia; hDepartment of Mechanical Engineering, Ramco Institute of Technology, Rajapalayam, Tamil Nadu, India

1 Introduction In recent years, remarkable development has been made in synthesizing and characterizing the materials to the size of nanoscale for tailoring the properties of materials where they are used as filler. The nano-sized materials play a vital role in many fields such as (1) environmental engineering, (2) medicine, (3) industries, and (4) electronics [1]. In general, the nanomaterials will have a size between 1 and 100 nm. Furthermore, the longest and shortest dimensions in x- and y-axes do not differ significantly. Nanoparticles are also called “ultrafine particles,” and these materials are opposed to fine particles (size between 100 and 2,500 nm) and coarse particles (ranged between 2,500 and 10,000 nm). The properties of nano-sized materials can significantly vary by altering their sizes, and it differs noticeably from the fine particles or bulk materials [2]. For example, the transition temperature of ferromagnetic particles (MgFe2O4, MnFe2O4) can be varied by changing their particle size. Similarly, the bulk ZnO particles have different adsorption range, different rate of reaction, and redox than the nano-sized ZnO particles [3,4]. Incorporation of nanoparticle into the polymers has shown improvement in various properties. The enhancement in properties of the nanocomposites depends on (1) Polymer Nanocomposite-Based Smart Materials. http://dx.doi.org/10.1016/B978-0-08-103013-4.00002-9 Copyright © 2020 Elsevier Ltd. All rights reserved.

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Figure 2.1  Three basic types of composite structures such as (A) phase-separated, (B) intercalated, and (C) exfoliated [16]. Source: Reproduced with the permission, License number 4684200083277.

the polymer matrix, (2) the type of nanofiller selected, (3) nanoparticle orientation, (4) particle aspect ratio, (5) particle concentration, etc. Some of the nanoparticles such as carbon nanotubes (CNTs) [5], clay [6,7], halloysite (HNT) [8], nanocellulose [9], calcium carbonate [10], metal-nanoparticles [11], graphene [12,13], and zeolite [14] were widely used as fillers to form the nanocomposites. Importantly, the dispersion of nanoparticles in the polymer matrix will be a key challenge in achieving the improved properties [15]. For example, Fig. 2.1 shows the different types of composite structures that arise due to the variation of dispersion of the nanoparticle in the polymer matrix. In Fig. 2.1A, silicate layers were not mixed properly with the polymer matrix, in which the properties of these composites were identical to the conventional matrix composites. In case of Fig. 2.1B, the polymers were intercalated between the silicate layers. It resulted in a well-structured multilayered morphology with mixed layers of polymer and clay. Fig. 2.1C revealed the uniform dispersion of silicate layers in the polymer matrix relative to Fig. 2.1A and B. Because of this uniform dispersion of silicate layers in matrix, an exfoliated structure is formed [16]. This exfoliated structure can provide an effective reinforcement due to the large surface area between the matrix and the nanofiller [17]. Knowledge of characterization techniques is the key to understand the variation in properties (i.e., physical, chemical, morphological, mechanical, thermal, etc.) of nanocomposites. Table 2.1 shows the characterization techniques for different types of studies. The polymer nanocomposites possess many advantages. Some of the advantages are: (1) enhanced barrier property than the neat polymer, (2) excellent in flame retardancy property, and (3) lighter than the conventional materials. However, it has a few disadvantages such as toxicity. Many researchers reported that reducing the size of nanoparticles possesses higher toxicity [24,25]. Though, some of them were reported that smaller-sized nanoparticles exhibit lesser toxicity [26,27]. Table 2.2 shows the potential applications of nanomaterials.

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Table 2.1  Commonly used characterization techniques. Characterization technique

Details of study

References

Wide-angle X-ray diffraction (WAXD) Small-angle X-ray scattering (SAXS) Scanning electron microscopy (SEM) Transmission electron microscopy (TEM) Atomic force microscope (AFM) Fourier-transform infrared spectroscopy (FTIR) Differential scanning calorimeter (DSC) Rheometry Dynamic modulus analysis (DMA) Thermomechanical analysis (TMA) Thermogravimetric analysis (TGA)

Structural and morphological

[17–21]

Mechanical, thermal, and rheological

[19,22,23]

Table 2.2  Essential applications of the nanofiller. Applications

Nanofiller

Automotive

Calcium carbonate, tungsten, clay, cobalt oxide, copper, diamond, calcium sulfonate Aluminum oxide, silver, clay, zirconium dioxide, carbon, gold Calcium hydroxide, carbon, aluminum oxide, silver, titanium Silicon dioxide, aluminum, and silver Zinc oxide, silver, clay, manganese Boron nitride, silicon dioxide, tungsten, carbon, silver Carbon, clay, silver, titanium

Medicine Construction Electronics Food Petroleum Sports

The characteristic of nanoparticles and behavior of the nanoparticle-incorporated polymer materials depends on many factors such as filler type, filler size, filler concentration, filler dispersion, etc. Various commercially characterization techniques can be utilized to understand how such factors influence the properties of polymer materials after the incorporation of nanoparticles. The primary objective of this chapter is to provide a comprehensive review on the characterization techniques used in determining the crystallographic, chemical, morphological, antimicrobial, and thermal properties of the nanocomposites.

2  Crystallographic properties Polymer nanocomposites were investigated for the last 3 decades. Various sized discontinuous fillers are reinforced in a continuous polymeric system to alleviate the limitations of polymers [28]. Nanoparticles of various shapes such as cylindrical, platelets, and spheroids were incorporated as filler in the polymer nanocomposites. The performance of the nanocomposites would be controlled by better dispersion of fillers and interfacial interactions. X-ray diffraction technique plays a vital role in optimizing these interactions. It is a most widely used technique to investigate the

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Figure 2.2  Different phases of polymeric nanocomposites (A) amorphous, (B) semicrystalline, and (C) highly crystalline [29]. Source: Reproduced with the permission, License number 4685810805790.

crystalline and amorphous nature of the fillers, polymers, and composites as shown in Fig. 2.2 [29]. Roy et al. [30] have developed a novel ZnO/PVA composite film. It has been reported that ZnO nanoparticles exhibited crystalline peaks at 36.61 (100), 39.55 (002), 41.45 (101), 52.70 (102), 61.56 (110), 67.98 (103), and 73.13 degrees (112). Similar peaks were observed in case of ZnO/PVA composites, which corroborate the fact that there was no significant change in the crystalline nature of ZnO nanoparticles when it was embedded with the polymeric matrix. The enhanced properties of polymeric nanocomposites are mainly due to the structural modification of polymers with the nanofillers. Nanoclay-based polymeric composites attracted the researchers in 1990s due to its exceptional performance in terms of fire resistant, electrical properties, thermal stability, and abrasion resistance [20]. The most widely used nanoclay is montmorillonite (MMT). The montmorillonite follows a sandwich crystal structure which contains a core layer of octahedral aluminum hydroxide sheet and outer layers of tetrahedral silicon oxide sheets. Monica et al. [31] studied the X-ray diffractogram of organically modified MMT/low-density polyethylene (LDPE) nanocomposites films. The intense peak at 2θ = 3.42 degree indicates the modification of MMT with alkyl group and provides a d-spacing of 25.8Å. XRD of organically modified montmorillonite (OMMT)/ LDPE nanocomposites shifted the peak to lower angle with d-spacing of 30.7Å. The reduction in the peak intensity was attributed to the intercalated/exfoliated morphology of the nanocomposites. Pramoda et al. [32] studied the effect of adding different wt.% of clay on the properties of polyvinylidene fluoride (PVDF)/clay nanocomposites. It was observed that the peak at 2θ = 3.9 degree disappeared in the MMT/PVDF composites with 1 and 2 wt.% which corroborates the uniform dispersion of MMT. On the other hand, the peak reappeared when the nanoclay loading was 5 wt.% which represents the nonuniform dispersion of the clay in the polymer. Silica-based polymer nanocomposites found potential applications in aerospace structures and in sensors [33]. Xu et al. [34] investigated the X-ray diffractogram of silica/PA6 nanocomposites and found the peaks at 2θ = 19 and 23 degrees is due to α crystalline while 2θ = 21 degree is due to γ crystalline (Fig. 2.3). Compared to PA6,

Role of characterization techniques

25

Figure 2.3  XRD pattern (A) PA6 and (B) Silica/PA6 nanocomposites [34].

the nanocomposites have shown weaker α crystalline and stronger γ crystalline. The increase in toughness was mainly attributed to the stronger γ crystalline. CNT has become potential nanofiller in the polymeric nanocomposites due to its flexibility, high modulus, thermomechanical, and electrical properties. Xu et al. [35] investigated the crystallization behavior of PVDF/CNT nanocomposites. PVDF showed peaks at 2θ = 17.8 (100), 18.6 (110), and 19.8 degrees (020). Also, it was observed that addition of CNT shifts the peak to lower angle which is due to the reduction in the intermolecular movement of the polymeric chain. Graphene nanoparticle (GNP) is one of the strongest recently discovered nanomaterials. The Young’s modulus and strength of monolayer graphene is 1 TPa and 125 GPa, respectively. It is a two-dimensional (2D) isotropic one atom thick sheet with a thickness of approximately 0.335 nm [36]. The structural changes occurred during the conversion of graphite to grapheme oxide (GO), Rgo, and GNP can be confirmed with XRD analysis. Morimune et al. [37] have developed and analyzed structural changes of GO/poly(vinyl alcohol) composites. From the analysis it was found that the diffraction peak of GO at 2θ = 11.1 degree disappeared in GO/PVA composites which indicates the homogeneous dispersion and exfoliation of GO. Small-angle X-ray scattering (SAXS) is another technique to investigate the crystallographic properties of polymer nanocomposites. In particular, it is used to study the structural changes of nanocomposites which does not follow a specific order and fails to produce a Bragg diffraction peak [29]. The degree of OMMT dispersion in the poly[(butylene succinate)-co-adipate] (PBSA) was studied by Bandyopadhyay and Ray [38]. The clay showed a peak at q = 3.14 nm − 1 with a d-spacing of 1.85 nm. The disappearance of this peak in the nanocomposites samples indicates that the ordered structure of the clay has been destroyed. Wang et al. [39] studied the structural changes of OMMT/epoxy composites with different dispersion methods (shearing and sonication). From the analysis, it was found that the morphologies were a mix of intercalated and exfoliated structures, depending on the dispersion technique.

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3  Morphological properties The morphological changes that occur in polymer-based materials due to the addition of nanoparticles in the matrix have traditionally been studied with micro- and nanolevel images of the composites reinforced with the nanoparticles. The techniques used to study the morphology of the nanoparticle-incorporated polymer materials such as scanning electron microscope (SEM), field emission scanning electron microscope (FESEM), atomic force microscope (AFM), scanning tunnel microscope (STM), and transmission electron microscope (TEM) are shown in Fig. 2.4. The morphological characteristics commonly assessed are (1) dispersion of nanoparticles in the matrix, (2) change in surface texture, (3) change in the failure characteristics due to the addition of nanoparticles, and (4) elemental distribution and mapping of nanoparticles and their composition on the surface. It can be noticed from literature that micrographs from SEM is the commonly used technique to assess the morphological changes on the polymer surface and failure characteristics. Fig. 2.5A–C shows the typical image of a composite made up of

Figure 2.4  Commonly used imaging techniques for characterization of the nanoparticle structure and their composites.

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27

Figure 2.5  SEM images of nanocomposite with halloysite nanotubes (HNT) (A) Sodium Alginate/HNT, (B) Methylcellulose/HNT, and (C) Chitosan/HNT [40]. Source: Reproduced with the permission, License number 4685810548361.

three different types of matrix and reinforced with halloysite nanotubes (HNT) [40]. The general observation reported from SEM micrographs is the change of surface texture from smooth to the rough texture [41]. Energy dispersive X-ray (EDX) when used along with SEM provides information on the elemental composition on the surface under investigation. However, in order to get high-quality images in nano level either AFM or TEM is preferred since they have atomic resolution while the SEM and FESEM have a resolution of several 100 nm [42]. In addition to the images in nano level (Fig. 2.6A), TEM can also provide elemental mapping or elemental distribution of the constituents of the material as shown in Fig. 2.6B. Furthermore, the presence of nanoparticles in the polymer and their distribution can be distinguished through the bright field images from TEM. The bright and contrast regions shown in Fig. 2.7A indicate the polymer and nanoparticles, respectively. In Fig. 2.7B, the individual elements present in the nanocomposite such as Cds, Ag, and ZnO could be identified as bright, contrast, and dark regions.

Figure 2.6  FESEM images of MnO2/PPy nanocomposites (A) synthesized at pH value of 4.0 and (B) elemental mapping [43]. Source: Reproduced with the permission, License number 4685810206953.

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Figure 2.7  TEM images of nanocomposite (A) CdS-Ag with ZnO prepared by combustion synthesis (B) CdS-Ag with ZnO nanorods [44]. Source: Reproduced with the permission, License number 4685810008125.

Figure 2.8  Two-dimensional AFM image of Gelatin nanocomposite film (A) without laponite and (B) without laponite [45]. Source: Reproduced with the permission, License number 4685800956670.

2D AFM images obtained for gelatin nanocomposite film without laponite and with 6 g of laponite particles are shown in Fig. 2.8A and B. It can be noticed that nanocomposite with laponite particles have rougher surface (Fig. 2.8B) as compared to the smooth surface in the gelatin composite without laponite (Fig. 2.8A). The roughness characteristic of the nanocomposite can be measured as root mean square value. The information on thickness variation in the z-axis can be obtained from 3D AFM image of the nanocomposite as shown in Fig. 2.9A–C.

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29

Figure 2.9  Three-dimensional AFM image (A) PVP/gold nanocomposites at pH 1.2, (B) PVP/gold nanocomposites at pH 5.0, and (C) natural rubber/nanoclay composite [46,47]. Source: Reproduced with the permission, License number 4685801138632, 4685801353296.

4  Thermal properties It is well known that the nanofillers exhibit tendency to modify the thermal behavior of the composites when they are used as reinforcements. Over conventional composites, nanocomposites display enhanced thermal properties. The enhanced thermal properties of the nanocomposites are due to the high matrix—nanofiller interfacial area resulting in uniform and homogenous dispersion of the nanofillers [48]. Incorporation of nanofibers can also significantly improve the thermal properties of the composites. In this context, many researchers have used nano-sized fillers to improve the functional properties of the composites especially the mechanical and thermal properties. Jinhong et al. [49] studied the effects of functionalization of boron nitride nanoplatelets on thermal properties of epoxy composites. Their study revealed that the functionalization of boron nitride nanoplatelets through hyperbranched aromatic polyamide (HBP) resulted in a strong interface produced enhanced thermal properties such as glass transition, thermal degradation, thermal conductivity, and dynamic thermal mechanical modulus when compared to the functionalization of boron nitride nanoplatelets through octadecylamine (ODA). Sun et al. [50] investigated the effect of reinforcement of different nanofillers on the crystallization and thermal behavior of polyamide 6 (PA6) composites. Nanofillers such as MMT, silicon dioxide (SiO2), and CNTs were used as reinforcements to form PA6 nanocomposites. They reported that the nanofillers possessed significant role in the heterogeneous nucleation which resulted in increased crystalline temperature. On the other hand, the melting temperature was found to be the same for all nanocomposites at 225°C which was associated with the α-crystals of PA6 regardless to type of nanofiller. For obtaining high-performance nanocomposites, homogenous dispersion of the filler and the matrix–filler interactions are very important factors. The reinforcing effect of multi-walled carbon nanotubes (MWCNTs)/graphene hybrid nanofillers with silicone rubber was investigated by Pradhan et al. [51]. It was found that thermal stability of the nanocomposites was higher than that of the pure silicone rubber. This

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could be ascribed to the hindering effect of the confined geometry of MWCNTs/graphene hybrid structure on the diffusion of nitrogen and volatile products throughout the composite materials by reducing the initiation of silicone rubber chain scission. In earlier research works, it was established that the traditional epoxy resin has poor thermal conductivity and no longer meets the requirements of the electrical and electronics industry. Hence, high thermally conductive ceramic fillers can serve in enhancing the thermal conductivity of epoxy resins. In this regard, Peng et al. [52] fabricated epoxy/aluminum nitride nanocomposites and investigated and experimented the influence of surface modification of aluminum nitride nanoparticles in the nanocomposites. The hydroxyl groups and the impure ions present on the surface of the nanoparticles were removed during the silane treatment process. This improved the interactions between the nanofiller and the epoxy resin and subsequently enhances the thermal conductivity and glass transition temperatures. Significant improvements in the functional properties of the polymers can be achieved with even very small amounts of inorganic fillers at nanoscale. The effects of varying concentrations of nanofillers in nanocomposites have been reported by some researchers. Mishra et al. [53] investigated the effect of varying loadings of zirconia nanoparticles in polyether ether ketone (PEEK). Their report revealed that the infusion of nano-zirconia reduced the chain mobility of the polymer by imposing vast number of restriction zones which reduced the thermal vibration of C-C bonds. In this case, the nanocomposites require higher thermal energy for thermal decomposition of the polymer which in turn increases the thermal stability of the nanocomposites. Similarly, cellulose-based hybrid nanocomposite composed of banana peel powder and silver nanoparticles (AgNPs) exhibited enhanced thermal stability with increased filler content when compared to the pure cellulose. The enhanced thermal stability of the nanocomposites was attributed to the thermally stable banana peel powder and the infusion of AgNPs [54]. Polypropylene-based hybrid nanocomposites with fibrous micro-fillers and AgNPs were fabricated by Indira Devi et al. [55]. Their studies revealed that both the fibrous micro-fillers and AgNPs influenced the thermal stability of the hybrid nanocomposites. The presence of rigid polyphenols in the fibrous micro-fillers and thermally stable metal nanoparticles were the main reason behind the increased thermal stability. Similar kind of observation was also made in case of the polypropylene hybrid nanocomposites with fibrous micro-fillers and copper nanoparticles (CuNPs) [56]. It has been established that nano-sized fillers can provide improved thermal properties when compared to their micro-sized counter parts. Micro- and nano-sized silicafilled polypropylene composites were prepared by Leng et al. [57]. It was found in their research that the nanocomposites exhibited higher degree of crystallinity and thermal stability properties over the microcomposites. However, there was no change in the melting point of micro and nanocomposites. The most important challenge in the fabrication of polymer nanocomposite is obtaining a homogeneous and cluster-free dispersion of nanofillers in polymer matrix, which provides a unique set of enhanced properties at low filler loading [58]. With the enhanced properties, nanofiber/nanofiller-based composites can be utilized in different applications such as building and construction materials, automotive, aerospace,

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31

packaging, consumer products, etc. Furthermore, it could be possible to produce acoustic insulator and extremely thermally stable materials for variety of applications [59].

5  Antimicrobial properties Completely biodegradable polymers incorporated with nanoparticles have been proposed as a viable alternate for the conventional plastics in the packaging applications. This is because of the enhanced physiochemical, thermal, and mechanical properties of the biopolymers after addition of the nanoparticles [44]. Antimicrobial characterization using agar diffusion assay and colony count methods are the commonly used technique to assess the microbial resistance of such materials to the pathogens. In this method, the biopolymer film to be tested for antimicrobial resistance is placed in a petri dish container filled with Gram-positive or Gram-negative bacteria cultured in the potato dextrose agar-based medium [60]. The setup is then placed in the incubator maintained at 25–40°C for a period of 24–72 h. After conditioning in the incubator, the container is checked for the presence of inhibition zone. The diameter of inhibition zone can be measured with a sliding caliper in triplicate while the difference in area between the petri dish and the sample area with stain is denoted as the inhibition zone (Fig. 2.10). The specimen with no inhibition zones is identified as negative or zero while the specimen with inhibition zone is represented with a + sign and the area

Figure 2.10  Antimicrobial properties using Agar diffusion method (A) pure chitosan composite film against Klebsiella planticola, (B) pure chitosan composite film against Bacillus subtilis, (C) Chitosan/ZnO composite film against K. planticola, and (D) Chitosan/ ZnO composite film against B. subtilis [62]. Source: Reproduced with the permission, License number 4685790811268.

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of inhibition zone is represented as values. Inhibition zone can also be classified in detail based on the extent of area stained within the petri dish. In a recent study, the inhibition zone was classified into the following criteria: (1) totally inhibited “+++,” (2) partially inhibited “++,” (3) slightly inhibited “+,” and (4) inhibition “−” [61]. The widely employed microorganisms or pathogens for determining antimicrobial resistance of nanocomposite are given in Table 2.3. The Gram-positive organisms include such as Bacillus subtilis, Staphylococcus aureus, Micrococcus luteus, Listeria monocytogenes, etc. [63,64]. In case of the Gram-negative organisms, Klebsiella planticola, Escherichia coli, Salmonella enteritidis, Salmonella enterica serovar Typhimurium, etc., were employed in the studies [61,62,65].

Table 2.3  Different pathogens used for studying antimicrobial properties of nanoparticle incorporated nanocomposite materials. Material

Nanoparticle filler

Gelatin/AgNPs and Gelatin/AgNPs/clay

Silver nanoparticles (AgNP) Nanoclay (cloisite 30B) GnP/CFX/PLA Graphene nanoplatelets (GnP) and ciprofloxacin (CFX) Chitosan–nanocellulose Nanocellulose

ZnO-Hal/PLA

Chitosan/ZnO Potato starch–nanoclay

References

Listeria monocytogenes Escherichia coli

[64]

Micrococcus luteus

[63]

Staphylococcus aureus, E. coli, and Salmonella enteritidis E. coli and S. aureus

[66]

Zinc Oxide deposited halloysite nanotubes (ZnO-Hal) Zinc Oxide (ZnO) Klebsiella planticola and Bacillus subtilis Montmorillonite Aspergillus niger Persian (MMT) Type fungal culture Montmorillonite E. coli, S. aureus, and L. (MMT) monocytogenes

Alginate/clay nanocomposite films with clove, coriander, caraway, marjoram, cinnamon, and cumin essential oils PVA/GO/Starch/AgNP Graphene oxide (GO) Silver nanoparticles (AgNP) PVOH/MMT Montmorillonite (MMT) TiO2/sodium alginate

Test pathogens

Titanium dioxide (TiO2)

E. coli and S. aureus

[67]

[62] [60] [61]

[65]

L. monocytogenes, S. aureus [68] Salmonella enterica serovar Typhimurium and E. coli [69] C. albicans and Salmonella enterica serovar Typhimurium

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33

The following are general observations from the earlier studies on antimicrobial properties of nanocomposite in the literature: Incorporation of nanoparticle into the biopolymers helped them to achieve antimicrobial resistance as indicated by the presence of inhibition zones compared to the pure biopolymers where such zones were not observed. • Diameter and area of the inhibition zone got better with the increase in concentration of nanoparticle in the biopolymer. • The extent of inhibition zone, antimicrobial resistance, and time required to achieve the inhibitory properties in a biopolymer was influenced by the type of nanoparticle incorporated into the biopolymer. • The response of a biopolymer to Gram-negative and Gram-positive pathogens is unique and could vary from one nanocomposite to the other. A nanocomposite material could have strong resistance against a Gram-positive bacteria but least resistance to the Gram-negative bacteria. •

The assessment of antimicrobial properties through the colony count method is a two-step process: (1) composite specimens are immersed in the solution cultured with bacteria followed by incubation and (2) 100 µL diluted specimen from the previous step is then spread over an agar solution (15 g/L agar) and incubated for a period of 24 h. At the end of two-step process, the bacterial colony forming units per milliliter (CFU/mL) can be counted [67]. Fig. 2.11A and B shows the bacterial colonies formed on the pure PLA composite films at the end of two-step process. However, ZnO-Hal nanoparticle-incorporated

Figure 2.11  Antimicrobial properties (A) bacterial colonies in pure PLA against E. coli, (B) bacterial colonies in pure PLA against S. aureus, (C) bacterial colonies in ZnO-Hal/PLA against E. coli, and (D) bacterial colonies in ZnO-Hal/PLA against S. aureus [67]. Source: Reproduced with the permission, License number 4685780840196.

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Figure 2.12  Antifouling effect (A) Chitosan film without ZnO and (B) Chitosan film incorporated with ZnO [62]. Source: Reproduced with the permission, License number 4685790811268.

PLA composite films were resistant to the bacterial activities due to the absence of bacterial colonies as shown in Fig. 2.11C and D. Assessment of antifouling is related to the antimicrobial resistance of a material as well. The main objective of the antifouling test was to determine the resistance of the material (1) in preventing the adhesion of microorganism on the material surface and (2) to inhibit the multiplication of microorganism within their membrane. In a recent study, Malini et al. [62] studied the antifouling effect by immersing the chitosan/ZnO nanocomposite in wastewater for 24 h (Fig. 2.12A and B). Their results indicate that chitosan membrane without the ZnO had more bacterial colonies (Fig. 2.12A) than the chitosan with ZnO (Fig. 2.12B). This highlights the ability of ZnO nanoparticle to inhibit the growth of bacterial colonies in chitosan membrane.

6 Conclusion The nanoparticle-incorporated polymer materials have emerged as a new class of material. Addition of nanoparticles into the polymer matrix was found to be beneficial in terms of material properties. Studies from the literature indicate that significant improvements in thermal, crystallographic, chemical, morphological, and mechanical properties could be obtained in polymers and the fiber-reinforced composites due to their addition. The use of nanoparticle in many practical applications was made possible due to the advancements and inventions in characterization techniques. •

Imaging techniques: Micrographs obtained from such as SEM, TEM, and FESEM were helpful in the following ways: (1) to visualize the dispersion of nanoparticles into the matrix and (2) factors contributing to the improvement in mechanical properties of

Role of characterization techniques

35

polymer-based composites such as rougher surface texture, reduced fiber pullout, and improved fiber-matrix adhesion. Apart from visual images, these techniques were also found to provide the elemental disposition of the materials. 2D and 3D images obtained from atomic force microscope enable us to quantify the surface roughness that occurs as a result of nanoparticle addition. • Thermal characterization: Dynamic mechanical analysis, thermogravimetric analysis, and digital scanning calorimetry were the widely used techniques to assess the changes in thermal properties of the polymer matrix due to the addition of nanoparticles. Factors such as glass transition temperature, residual char, and onset and endset degradation temperature measured from these techniques provided information on the thermal stability. • Crystallographic properties: X-ray diffraction spectrometry and SAXS techniques were utilized to study the crystallographic changes in the lattice plane of polymer due to the addition of nanoparticle. Addition of nanoparticles was found to enhance the crystalline nature of the polymers as indicated by the presence of peak positions in the spectra corresponding to the respective lattice planes in the crystal structure. • Antimicrobial properties: Agar diffusion assay and colony count method were used to measure the microbial resistance of nanoparticle-reinforced polymer films. Pathogens such as Gram-positive bacteria and Gram-negative bacteria were introduced into the medium and added into container the nanocomposite film. The presence of inhibitory zones around the nanocomposite film was taken as antimicrobial resistance in the agar diffusion method while the number of bacterial colonies in the container was calculated.

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Self-healing based on composites and nanocomposites materials: from synthesis to application and modeling

3

Marya Rajia, Mounir El Achabyb, Rachid Bouhfida, Abou el kacem Qaissa a Moroccan Foundation for Advanced Science, Innovation and Research (MAScIR), Composites and Nanocomposites Center, Rabat, Morocco; bMaterials Science and Nanoengineering Department (MSN), Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco

1  Introduction Polymers and polymer nanocomposites have been commonly used in tremendous engineering fields due to their advantages such as good mechanical and thermal performances, simplicity in handling, light-weight, economic benefits and eco-friendliness, as well as good processability, and chemical stability at all atmospheric conditions in addition to other interesting specific properties which is indicated in the literature [1–3]. The structural application of this kind of polymeric materials which include sporting goods, transport vehicles (cars, aircrafts, ships, and spacecrafts), civil engineering, and electronics pieces nictitate long-term reliability and durability data but their environmental aging effortlessly leads to degradations of polymeric components, which is induced by mechanical, chemical, thermal, ultraviolet radiation, or a combination of these factors. In general, damage deep inside the polymeric materials at the nanoscale level and then it is amplified to the microscale level up to the macroscale until to total polymer composites cracking [4,5]. As known, it is difficult to perceived and repair the failed materials so had better have the ability to self-repair capabilities by blocking damage as it occurs at the nano/microscale and keep the original material properties. The ideal solution is the use of self-healing polymer composites [6]. Major advances have been made in the past decade within the topics in the area of self-healing polymers. The healing process in polymeric materials includes the ability to repair themselves and to recover functionality using the autonomic or externally resources inherently available to them [7,8]. This phenomenal material behavior is inspired by biological systems that are embodying the guiding principles behind the design of synthetic versions [9]. This kind of materials increase the reliability, safety and lifetime of airframe, launcher, and space structures by eliminating the propagation of fatigue crucks and mitigating the progression of nano-smaller damage in the structural materials [9,10]. According to the many parameters, healing composites and nanocomposites can be classified into four categories: (1) healing by crack-filling adhesion; (2) healing by diffusion; (3) healing by bond reformation; and (4) virgin Polymer Nanocomposite-Based Smart Materials. http://dx.doi.org/10.1016/B978-0-08-103013-4.00003-0 Copyright © 2020 Elsevier Ltd. All rights reserved.

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property strengthening in response to stress [11]. Such parameters include type of material being healed (e.g., thermoplastic polymers, thermoset polymers, composites, metals, etc.), the physical phase of the healing additive (solid vs. liquid) the external stimuli required to initiate healing event, and the intrinsic or extrinsic nature of the healing. Therefore the use of self-healing concept in polymers field provides a solution to the long-standing problem of materials systems with greatly extended lifetimes [12,13].

1.1  Types of healing process in polymers The requirement to enhance greatly the safety and durability of polymeric components offers another opportunity for broadening their structural and environmental applications. These needs that have been a issue of research for over 15 years are realized via a continuously sensing and responding to damage sites under harsh conditions over the life-time and as well as restoring the material performances such as fracture toughness, barrier properties, tensile strength, surface smoothness, etc. [11,14]. The researches in this field are still in the infancy; the knowledge of the concept of each of healing methods is essential to understanding the self-healing polymer composites as smart materials [15,16]. Accordingly, the intrinsic healing composites and nanocomposites are those that can heal cracks by themselves, however, in the case of extrinsic healing polymers in which healing agent has to be embedded into the materials in advance. Hence, each healing method differs based on the resource of self-recovery [17–19].

1.1.1  Intrinsic self-healing polymers As mentioned earlier, the drastic damage in the composites and nanocomposites commonly caused by the structural changes of atoms or molecules like as chain scission leading to rupture of the main matrix backbone [14,20]. Therefore the inverse reaction that is recombination and the cross-linking between the broken molecules of the polymer’s chains provoke, an intrinsic healing of the damage [21,22]. The intrinsic self-healing materials refer to the polymers and polymeric matrices that allow the cracks to repairing usually without the aid of any healing agent through the application of certain external stimulation such as heat or light, as shown in Fig. 3.1 [7,23]. The molecular mechanisms operated the autonomic healing processes between the dangling chains of polymer comprise two modes: (1) physical interactions and (2) chemical interactions [14,24]. The reversible physical or so-called also covalent interactions include hydrogen bonding, ionic interactions, hydrophobic interactions, π–π stacking, and host–guest interactions that are generally utilized in the stimulus-responsive healing process of self-healable rubber, film, and hydrogels [6,25]. On the other hand, noncovalent interactions or relatively strong dynamic covalent bonds comprise both structural stability and higher mechanical strength into intrinsic self-healing materials. In this case, acylhydrazone bonds, disulfide bonds, imine bonds, and urea bonds have been used into damaged polymers matrix for self-recovery [16,26]. There are many intrinsic self-healing strategies, such as employing thermoplastic/thermoset blends, thermally reversible covalent bonds and alkenes cyclization by light, sulfur-based

Self-healing based on composites and nanocomposites materials

43

Figure 3.1  Schematic representation of intrinsic healing system.

chemistry by light or initiators, resins containing reversible Diels–Alder cross links, hydrogen bonds polymers, molecular diffusion, ionomeric coupling, etc. [14,27,28]. All these procedures have been examined in an attempt to find a reliable, simple, and cost-effective solution to repair damage in composites [13]. The mechanisms of selfhealing polymeric materials for each category are detailed in Table 3.1.

1.1.2  Extrinsic self-healing polymers Unlike the intrinsic self-healing approach, in what is called extrinsic self-healing, the matrix resin itself is not a healable one and the healing agent should be incorporated into the matrix in advance [21,29]. In this approach, no external stimulant such as heating is necessary to activate the healing process. Broadly speaking, autonomic healing containers are classified into two primary conceptual approaches: In the first, incorporated vascular network (hollow tubes and fibers) serves as healing agent reservoir for sequestration of the polymer matrix. In the second, microcapsules containing reactive chemical species (particles and microcapsules) are embedded into the native polymer matrix (Fig. 3.2) [10,30]. Each approach utilizes a distinct mechanism with different recovery rate and also, they dictate the damage volume that have be sequestrated, in addition of the repeatability of healing agent, but which is essential, upon cracking damage, their healing contents released from the embedded fragile containers and undergo a healing reaction [31]. As a result of polymerization of the released healing-agent, the cracks are autonomously rebonded.

1.1.2.1  Vascular self-healing materials Inspired by natural healing processes that of human skin, vascular or fibers-based self-healing system, which enables multiple healing cycles with low load-bearing

Class

Healing mechanisms

Noncovalent interaction

Hydrogen bonds

Structure

44

Table 3.1  physical and chemical interaction in the intrinsic healing system. Example

Stimulus

Healing efficiency

Telechelic

120°C

87%–93%

PBA-UPy

100%

HBN-GO

98%±5%

SDS micelle

—

98%–100%

Ionic interactions

PIC (PMPTC/PNaSS)

Saline

66%

Metal bonding

Tyrosin-based amphiphiles and Ni2+

—

100%

Amino acid-based ligand and Zn

—

100%

Terpyridine ligand and Fe2+

100°C

—

2+

Polymer Nanocomposite-Based Smart Materials

Hydrophobic interactions

Class

Stimulus

Healing efficiency —

βCD-Ad-Fe

Wet

68%

Poly-β-CD and poly BrNp

—

—

NBD-Chol

—

—

Polyimde and pyrenyl end-capped polyamide Polyimde and pyrenyl end-capped polyurethane

140°C

100%

100°C

Meltable thermoplastics

Graphene and polyurethane

IR light

95% tensile modulus, 91% elongation, 77% toughness