Starch-based materials in food packaging processing, characterization and applications 9780128094396, 0128094397, 9780128122570, 0128122579

Table of contents :
Content: 1. Starch 2. Starch thermal-processing: technologies at laboratory and semi-industrial scale 3. Bio-based materials from traditional and non-conventional native and modified starches 4. Composites and nanocomposites based on starches. Effect of mineral and organic fillers on processing, structure and final properties of starch 5. Thermoplastic starch-based blends: processing, structure and final properties 6. Food packaging: properties and characteristics. 7. Active and intelligent food packages 8. Potential use of starch in food packaging 9. Future tendencies

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Starch-Based Materials in Food Packaging

Starch-Based Materials in Food Packaging Processing, Characterization and Applications

Edited by

Marcelo A. Villar Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina; Departamento de Ingeniería Química, Universidad Nacional del Sur, Buenos Aires, Argentina

Silvia E. Barbosa Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina; Departamento de Ingeniería Química, Universidad Nacional del Sur, Buenos Aires, Argentina

M. Alejandra García Centro de Investigación en Criotecnología de Alimentos, CIDCA (UNLP-CONICET), Universidad Nacional de La Plata, La Plata, Argentina

Luciana A. Castillo Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina; Departamento de Ingeniería Química, Universidad Nacional del Sur, Buenos Aires, Argentina

Olivia V. López Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina

Academic Press is an imprint of Elsevier 125 London Wall, London EC2Y 5AS, United Kingdom 525 B Street, Suite 1800, San Diego, CA 92101-4495, United States 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom Copyright © 2017 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-12-809439-6 For Information on all Academic Press publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Nikki Levy Acquisitions Editor: Nina D. Bandeira Editorial project Manager: Mariana L. Kuhl Production Project Manager: Paul Prasad Chandramohan Cover Designer: Greg Harris Typeset by MPS Limited, Chennai, India

List of Contributors Norma D’ Accorso Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales (FCEyN), Ciudad Universitaria, Buenos Aires, Argentina Edith Agama-Acevedo Instituto Politécnico Nacional, Yautepec, México M. Alejandra García Centro de Investigación y Desarrollo en Criotecnología de Alimentos (UNLP-CONICET), La Plata, Argentina Vera A. Alvarez Thermoplastic Composite Materials Group (CoMP), Reasearch Institute of Materials Science and Technology (INTEMA), National Scientific and Technical Research Council (CONICET), National University of Mar del Plata (UNMdP), Mar del Plata, Argentina Silvia E. Barbosa Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina; Departamento de Ingeniería Química, Universidad Nacional del Sur, Buenos Aires, Argentina Luis A. Bello Perez Instituto Politécnico Nacional, Yautepec, México Jeannine Bonilla Universidade de São Paulo (USP), São Paulo, Brazil Luciana A. Castillo Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina; Departamento de Ingeniería Química, Universidad Nacional del Sur, Buenos Aires, Argentina Amparo Chiralt Universitat Politécnica de Valencia (UPV), Valencia, Spain Flávia Debiagi State University of Londrina, Londrina, PR, Brazil Nancy L. Garcia Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales (FCEyN), Ciudad Universitaria, Buenos Aires, Argentina Silvia Goyanes Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales (FCEyN), Ciudad Universitaria, Buenos Aires, Argentina María P. Guarás Thermoplastic Composite Materials Group (CoMP), Reasearch Institute of Materials Science and Technology (INTEMA), National Scientific and Technical Research Council (CONICET), National University of Mar del Plata (UNMdP), Mar del Plata, Argentina Norziah M. Hani Universiti Sains Malaysia, George Town, Malaysia Olivia V. López Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina Leandro N. Ludueña Thermoplastic Composite Materials Group (CoMP), Reasearch Institute of Materials Science and Technology (INTEMA), National Scientific and Technical Research Council (CONICET), National University of Mar del Plata (UNMdP), Mar del Plata, Argentina Suzana Mali State University of Londrina, Londrina, PR, Brazil

xi

xii  List of Contributors Léa Rita P.F. Mello State University of Londrina, Londrina, PR, Brazil Mario D. Ninago Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina Rodrigo Ortega-Toro Universitat Politécnica de Valencia (UPV), Valencia, Spain Laura Ribba Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales (FCEyN), Ciudad Universitaria, Buenos Aires, Argentina Hayati Samsudin Universiti Sains Malaysia, George Town, Malaysia Carmen C. Tadini University of São Paulo, São Paulo, Brazil Pau Talens Universitat Politécnica de Valencia (UPV), Valencia, Spain Florencia Versino Centro de Investigación y Desarrollo en Criotecnología de Alimentos (UNLP-CONICET), La Plata, Argentina Marcelo A. Villar Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Buenos Aires, Argentina; Departamento de Ingeniería Química, Universidad Nacional del Sur, Buenos Aires, Argentina David K. Wang The University of Queensland, Brisbane, QLD, Australia Fengwei Xie The University of Queensland, Brisbane, QLD, Australia Binjia Zhang Huazhong Agricultural University, Wuhan, China

Preface Development of materials based on biodegradable polymers from renewable sources has received considerable attention from academic and industrial sectors. Among other biopolymers, starch is a good candidate for this purpose mainly due to its biodegradable character, low cost, worldwide availability, and functionality. Thus the use of this polysaccharide in the packaging industry is an interesting and promissory option for the designing of biomaterials for specific applications. Accordingly main topics discussed in this book are related to the most recent advances in the development of biomaterials from different starches, applying several technologies at laboratory and semiindustrial scales. Besides the effect of formulations and processing conditions on structural and final properties of starch-based materials are included. Finally potential applications of starch materials in diverse fields, especially in food packaging, are also presented. The main purpose of this book is to provide the state of the art of the development of biomaterials based on different starches, including processing and characterization, as well as, evaluation of their possible applications. Even though, in the current literature several books related to this topic are available, this book offers complementary information mainly related to the possibility of obtaining materials at large scale by adapting the existing technology for synthetic polymers, which implies a low-cost investment by the industrial sector. Besides current commercial applications of starch materials are reported, as well as, new possibilities of uses are also evaluated as a function of their final properties. An experimental approach based on the processing and characterization of biopolymers derived from different starches, is mainly presented. It includes fundamental knowledge and practical applications, and it also covers valuable experimental case studies. This book offers a comprehensive overview concerning to biodegradable polymers, covering the new trends on their applications. Concerning to the style of the book, it is proposed for academics, researchers, and all those involved in the manufacture and use of biodegradable materials based on thermoplastic starch. Moreover, it intended to be a reliable reference source for those wanting to learn more about this important class of polymeric materials. World experts from Australia, Brazil, Mexico, Argentine, China, Malaysia, and Spain have written different book chapters. This book is focused

xiii

xiv  Preface

toward an ecological proposal to partially replace synthetic polymers arising from nonrenewable sources for specific applications. Thus the use of starch as feedstock to develop biodegradable materials is a good and promissory alternative. With the contributions and collaboration of experts in the development and study of starch-based materials, this book pretends to be an up-to-date showing the versatility of this polysaccharide and its potential use, especially for food packaging.

Chapter 1

Starch Luis A. Bello Perez and Edith Agama-Acevedo Instituto Politécnico Nacional, Yautepec, México

1.1  GENERAL ASPECTS Starch is considered the main storage carbohydrate of green plants and it is produced in two organelles. In the photosynthesis process, during light periods, starch is produced in the chloroplasts and is used as energy source by the plant to achieve the metabolic process. Starch that is not used in this via is accumulated in the chloroplasts for its later usage during the dark periods, named as transitory starch. Additionally, this polysaccharide is stored in other organelles called amyloplasts for long time. This stored starch can be used during the seeds sprouting process. On the other hand, it can be isolated and used as raw material in different applications, for example, foods and pharmaceutical products, plastics, fermentation, adhesives, paints, paperboard, etc. Commercial starches are obtained mainly from maize, potato, wheat, rice, and cassava (Fig. 1.1). The use of starch in those products is due to its physicochemical and functional properties such as water retention, viscosity, gel formation, etc. However, the properties native starches are limited and hence they are modified by chemical, physical, or enzymatic methods to improve their functionality. Many years ago, it was suggested that both the shape and size of starch granules are responsible for their physicochemical and functional characteristics. Also, granule size distribution is related to starch functionality. In addition, the amylose/amylopectin ratio and the chain-length distribution of amylopectin are suggested as important characteristics to explain starch physicochemical and functional features. More recently, starch structure, which is the arrangement of its components in the granules of both native and modified derivatives, is also reported as a factor of its functionality. Diverse microscopy techniques have been reported to analyze the shape and surface of starch granules. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) give information about the appearance of granules surfaces. Thus, small protrusions of 10–50 nm were observed on granules surface of native wheat starch by AFM (Baldwin, Adler, Davies, & Melia, 1995). Starch-Based Materials in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-0-12-809439-6.00001-7 © 2017 Elsevier Inc. All rights reserved.

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2  Starch-Based Materials in Food Packaging

FIGURE 1.1  Isolation of starch from diverse botanical sources.

Additionally, large spherical protrusions (200–500 nm) were detected for native potato granules. Besides, SEM is a useful technique to examine their internal structures. In this sense, the presence of pores and channels in cereal starches and in granules hydrolyzed by α-amylase was evidenced. On the other hand, the internal arrangement of starch components in concentric rings was evidenced by transmission electron microscopy (TEM) (Fig. 1.2). In addition, this technique has been employed to obtain information about the starch structure modifications during its hydrolysis. Thus, the structure of starch nanocrystals produced by acid hydrolysis has been revealed by TEM (Wang, Yu, & Yu, 2008). Starch is classified as a homo-polysaccharide and its basic unit is glucose. It is considered as a biopolymer mainly due to its natural origin, constituted by two main components: amylose and amylopectin. Amylose is an essential lineal polymer where glucose units are joined by α-(1–4) bonds, with few branching points, conforming the amorphous regions of the starch granules. On the other hand, amylopectin is the branched component where glucose units are also joined by α-(1–4) bonds in the lineal sections, and by α-(1–6) bonds in the branching points. Amylopectin is responsible of the starch crystalline lamella, although their branching points are part of the amorphous one. The presence of amorphous and crystalline regions in starch granules confers to this biopolymer a semicrystalline entity. In the “cluster” model, it is suggested that amylose is intermixed with amylopectin in the branching points (Pérez & Bertoft, 2010). Also, gelatinization studies suggest that amylose is concentrated toward the periphery of the granules (Jane, 2007). However, amylose location as well as the

FIGURE 1.2  Projection of starch granule, figure modified of O’neill C.O & Field R.A (2015).

4  Starch-Based Materials in Food Packaging

nature of the amorphous regions within starch granules is not well understood yet (Wang & Copeland, 2013). Generally, “normal” starches are constituted by 25–30% amylose and 70–75% amylopectin. However, there are some starches that show high amylopectin content (98–99%), named “waxy”; and others with high-amylose content (50–70%). All of the aforementioned characteristics as well as other starch granules aspects, for example, shape and size, amylose/amylopectin ratio, chain-length distribution, and components arrangement are involved in the functionality of this biopolymer. For example, “waxy” rice starch, which presents small granule size and a great amount of short amylopectin chains, is widely used to formulate coatings for mushrooms to maintain their turgor during storage. Isolated starch from some botanical sources can present minor constituents as proteins, lipids, and phosphates groups. Particularly, starch from potato presents phosphate monoesters and phospholipids that give special functional gel characteristics. Meanwhile, potato starch gels show high peak viscosity and transparency attributed to those phosphate groups joined to the amylopectin branching points, being the amylose/amylopectin ratio not responsible of these functional characteristics. The lipids present in some starches as maize and rice can complex with amylose and modify their functionality and digestibility.

1.2  STRUCTURAL CHARACTERISTICS OF STARCH GRANULES In general, isolated native starches present an ordering of the components, organized in concentric rings, which is observed by a Maltase cross under polarized light. The positive birefringence showed by the Maltase cross indicates a radial orientation of the principal axis of lineal amylopectin chains that form the crystalline zones of starch granules. The Maltase cross indicates that order of starch components is present in the granule without reference to any crystalline form. When starch disorganization is occurred, the level of birefringence lost depends on the starch granules damage. Crystalline zones that are formed due to the lineal section of amylopectin chains have a specific X-ray diffraction (XRD) pattern, indicating a periodicity of about 9–10 nm within the granular structure. Besides, this technique has been used to identify starches from different botanical sources. Thus, cereal starches present patterns arbitrary named A-type; meanwhile diffractograms of starches from tubers, rhizomes, and high-amylose maize are designed as B-type. On the other hand, some seeds and legumes show a C-type pattern that is a mix of A- and B-types. Besides, modified starches can present these C-type specific diffractograms. However, XRD pattern of native starches is modified or lost when structure disorganization occurred, for example, during gelatinization process. The crystallites of both A- and B-type are organized in left-handed, parallelstranded double helices, sixfold structures, with a crystallographic repeat distance of 1.05 nm. The double helix of glucose chains presents hydrogen bonds between the two strands; being this conformation very compact, without any

Starch  Chapter | 1  5

space for water or any other molecule. In the A-type, amylopectin chains are crystallized in a monoclinic lattice. In this unit cell, 12 glucopyranosyl units are located in the two double helices that are packed in a parallel arrangement. Meanwhile, four water molecules are located between the helices, producing a more densely packed crystal structure. In the B-type, chains are crystallized in a hexagonal lattice in double helices like to A-type unit cell, but 36 water molecules are present, producing a more opened crystal structure. It is important to mention that the arrangement of starch components, observed by the Maltase cross and the XRD pattern, is lost when starch dispersion is heated, a mandatory step during its processing or before its consumption. However, it is important to point out that the remnant starch granules (ghosts), observed after starch gelatinization, are conformed by disorganized amylopectin and reorganized starch chains in a “new” crystalline structure. The presence of “ghosts” conditions not only starch functionality but also its digestibility in cooked products. Another starch characteristic, which determines its functionality and digestibility, is the amylopectin chain-length distribution. This characteristic is determined after starch enzymatic hydrolysis using debranching enzymes. The first studies were carried out with size-exclusion chromatography columns at low pressure, using diverse gels. Those studies showed that the amylopectin chainlength distribution could determine the total carbohydrate content of each fraction and the reducing sugars corresponding to the fraction containing the highest carbohydrate amount. Moreover, it was possible to calculate the average degree of polymerization (DP) of amylopectin chains. Depending on the starch botanical source, a bimodal distribution of amylopectin chains was found, with variations in the proportion of each fractions and DP. For example, cereal starches presented a bimodal distribution with high amount of short chains; on the other hand, tuber starches showed similar bimodal distribution, but containing higher amount of long chains than cereal ones. Besides, amylopectin chain-length distribution was related to starch digestibility. In this sense, even though cereals native starches have short amylopectin chains, their great proportion makes these starches slowly digestible. Meanwhile, potato starch with long chains showed higher resistance to hydrolysis by digestive enzymes (Zhang, Ao, & Hamaker, 2008; Zhang, Venkatachalam, & Hamaker, 2006). Starch characteristics as molecular weight, gyration, and hydrodynamic radius give information about polysaccharide behavior in solution. Understanding molecular features of starch components is essential to produce derivatives by modifying its structure to develop new products or to widen its application. If the method used to study starch components characteristics requires its solubilization, it is important do not alter starch structure, avoiding its apparent degradation. Thus, moderate conditions of pH, temperature, and time are required to keep an intact structure. Concerning to starch molecular weight, it is more appropriated the term “molecular weight distribution” since this polysaccharide is constituted by a range of molecular weights. Devices employed to determine this physical property use separation by size (gel permeation chromatography),

6  Starch-Based Materials in Food Packaging

FIGURE 1.3  Models of amylopectin where concept has been adapted. denotes the reducing end; A, B, and C are external and internal chain segment. (A) Haworth et al. model (1937); (B) Borovsky, Smith, Whelan, French, and Kikumoto (1979) and (C) Staudinger & Husemann model (1937).

not by molecular weight. It is important to highlight that even two molecules can present similar size, they could have different molecular weights. In this sense, starch molecular weight will be depending on the method for its determination (Gidley et al., 2010; Gilbert et al., 2010). Flow field flow fractionation has been suggested to estimate the starch molecular weight due to the separation is based on the diffusion coefficient (Rolland-Sabaté, Colonna, Mendez-Montealvo, & Planchot, 2007). However, more investigation is required to determine the conditions to produce more reliable results. Starch molecular weight influences the functionality, for example, high molecular weight produces high viscosity, which can be desirable for some applications, or starch with low molecular weight has reduced viscosity, being suitable to prepare filmogenic solutions. The organization of starch components in semicrystalline rings consists of stacks of alternating crystalline and amorphous zones, where the amylopectin, as main component of starch granules, is the responsible of this ordering. For this reason, amylopectin has received more attention and several models were proposed (Fig. 1.3) to explain the starch functionality (Bertoft, 2013). Until some years ago, one of the most accepted model was the “cluster” one, which was published in 1969 by Nikuni, but it was widely known when it was published in English by Nikuni (1978). French (1972) proposed a similar model that was refined by Robin, Mercier, Charbonniere, and Guilbot (1974) and by Manners and Matheson (1981). The use of high-performance size-exclusion chromatography led to propose a model with a subclassification of B-chains (long amylopectin chains in the “cluster” model) in B1, B2, and B3. However, this polymodal model of Hizukuri (1986) was considered as a refined version of the original “cluster” one. Microscopic studies using AFM led to the

Starch  Chapter | 1  7

reemergence of the “blocklet” concept in 1997, where a crystalline structure level between the large “growth” rings and the amylopectin lamellae was suggested (Baldwin, Adler, Davies, & Melia, 1998; Gallant, Bouchet, & Baldwin, 1997). In 1999, Bertoft et al. introduced the building block concept, where the blocks are considered the basic units in the backbone model. From a conceptual point of view, the building blocks can be classified in two types (external and internal) and they are outspread along an amylopectin backbone that consists mainly of long chains. The backbone concept represents a challenge about the biosynthesis of starch granules (Bertoft, 2013).

1.3  PRODUCTION OF STARCH FROM DIFFERENT BOTANICAL SOURCES Starch application in diverse industries requires high availability of raw material. Starch is commercially available from diverse botanical sources as maize, potato, rice, wheat, and cassava. Many studies have been reported with the use of nonconventional starchy sources as taro, banana, plantain, mango, amaranth, quinoa, etc., for starch isolation. Uses of nonconventional starches include encapsulation, film or cover materials, stabilizing agent for emulsion, nanocrystals preparation, etc. These isolated starches from the diverse botanical sources are known as native starches. Generally, they do not meet the functional requirements for the diverse industries and then they must be modified by different methods as it is mentioned in the next section. Two general methods for starch isolation have been reported. Wet milling is a method where the starchy source (grains and pulp) is immersed in water or solution where a reagent to avoid the material oxidation is included (e.g., citric acid, sodium bisulfite, etc.). When grains are used, they are steeped in the solution for several hours (e.g., 8–10 h) to soft the tissue. Thereafter, the starchy material and the solution are milled to obtain a solution that is sieved with different mesh sizes as 50, 100, and 200 U.S. The residue is then washed in tap water until the water has not shown apparent residues of starch. Starch dispersion is maintained several hours in order to produce the sedimentation. The supernatant is decanted and the residue is centrifuged to recover the wet starch, which is dried in convection oven at 40–45°C for 24 h. A modification of the wet-milling process includes in a first step the production of flour from the grains, tuber, or pulp. Flour is obtained after milling of the grain, but when the starchy source has high water content (e.g., tuber or pulp) is dried in a convection oven at 40–45 °C for 24 h. After that, flour is mixed with water or solution and the process for starch isolation is achieved as mentioned earlier. Laboratory procedure for starch isolation from corn was reported using wet milling and tabling method (Eckhoff et al., 1996). This methodology separates the protein and starch by density differences. This separation method uses tables with an inclination where starch (white residue) is retained. After, starch is removed with a spatula. Other method employs hydroclycone to separate

8  Starch-Based Materials in Food Packaging

protein-starch in laboratory wet milling (Singh & Eckhoff, 1995). A review of the wet milling methods for starch isolation at laboratory and pilot-plant scale showed that although there are significant differences in the procedures, starch yield and other components (protein, fiber) can result comparable to those obtained for industrial level (Singh & Eckhoff, 1996). Dry milling method uses sieving and air classification for separation of the grain components (proteins, starch and fiber), but less efficiency is obtained. This technique separates germ and pericarp from endosperm. Good starch yield was produced when 8 h of steeping is achieved. Starch recovery using dry milling methods is not satisfactory even when fine grinding of grains and air classification are used. In this sense, wet milling can produce a commercially satisfactory yield and quality of starch. Attempts have been carried out to isolate starch combining wet and dry milling. In this sense, starch was recovered from corn flour using alkaline solutions (Mistry & Eckhoff, 1992a, 1992b) or it was separated from corn grits using sulfur dioxide (Eckhoff, Jayasena, & Spillman, 1993). Recently, it was reported the isolation of plantain starch on a large laboratory scale using a procedure that employs minor water amount in the washing step during the sieving of the pulp dispersion. Water recirculation that flow down during the sieving decreases the water amount required in the starch isolation, a critical point in the wet milling process that can be improved when the procedure will be scale up to pilot or industrial level of operation (Ramirez-Cortes, Bello-Pérez, Gonzalez-Soto, Gutierrez-Meraz, & Alvarez-Ramirez, 2015).

1.4  PHYSICOCHEMICAL AND FUNCTIONAL PROPERTIES OF STARCHES Understanding of the physicochemical and functional characteristics is required in order to find proper applications of starch in diverse products. A basic knowledge of some properties of native and modified starches as pasting profile, gelatinization, retrogradation, and rheological features is necessary to determine their best applications. The most important physicochemical properties of starch are evaluated during cooking or heating with water given that starch or starchy products are cooked before consumption obtaining the desirable food characteristics. Besides, the starch dispersion heating leads specific properties to the final product (e.g., viscosity). The pasting profile of starch during heating depends on the temperature and water content. During heating of starch dispersion, its polymeric chains, mainly amylose, is solubilized toward the continuous phase. This material influences the texture, viscosity, water retention and digestibility of starchy matrix due to a gel is developed. Also, heating of starch dispersion with plasticizers produce a filmogenic solution that is used to elaborate films or coatings. The characteristics of the gel and filmogenic solutions depend on the amylose/amylopectin ratio, starch type, and molecular structure.

Starch  Chapter | 1  9

In the pasting profile, it is possible to find a peak of the maximum viscosity, which is related to the maximum granules swelling. This phenomenon is due to the water diffusion within starch granules, where hydrogen bonds are produced among amylopectin chains with the lixiviated amylose ones, facilitated by the heating. High amylopectin starches (waxy starches) produce a high peak viscosity compared with their normal starches counterparts (around 70% amylopectin and 30% amylose). This pattern is due to the high molecular weight of the amylopectin. However, there are other starches that show a high peak viscosity, for example, potato starch, attributed to the phosphate groups present in the amylopectin. Modified starches, for example cross-linked ones, present a small peak viscosity due to the limited granules swelling. However, under acid conditions, it is possible to find a defined peak viscosity in the cross-linked starches. Restricted swelling during pasting profile is shown by native bean starches, suggesting a molecular arrangement of their components that can produce specific functionality. Under shear stress, during the pasting test, native and modified starches present a breakdown due to the rupture of swollen granules favored by the combination of shear stress and high temperature. Starch components are dispersed in the continuous phase, producing an important decrease of the viscosity. During the dispersed starch cooling, a setback step is produced due to reorganization of its components where a network of amylose chains includes the “ghosts” of the swollen granules. The setback depends on the granules amylose content in order to produce a strong gel. The pasting profile of native or modified starches can be modified by the presence of other components as lipids, proteins, sugars, and salts. Gelatinization is a starch physicochemical property, produced when it is heated with water excess is present in the system, which determines its thermal processing. Gelatinization is a mandatory step before consumption of starchy products, but also this property gives the functionality at diverse products where starch is used as ingredient. This phenomenon involves diverse changes in the granules as loss of birefringence, swelling, solubilization, and viscosity increase. Microscopy observation was used to evidence starch gelatinization when 50% of granule birefringence is lost. Nowadays, the use of differential scanning calorimetry allows determining the range of gelatinization temperature and the involved enthalpy. Table 1.1 shows the thermal properties of starches from different botanical sources. In general, native starches from tubers and roots show gelatinization temperature slightly lower than cereal ones (corn, wheat, and rice). Also, starch modification produces changes in the gelatinization property, decreasing the temperature and enthalpy values compared to its native counterpart. Gelatinization enthalpies of several hydrolyzed starches are included in Table 1.2. However, the modification named “annealing” produces an increase in the gelatinization temperature due to this method led to a more perfect crystallites within the granules. Gelatinization range can be narrow or wide, depending on the granules size distribution. These conditions of starch gelatinization

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TABLE 1.1 Thermal Properties of Acetylated Starches from Different Botanical Sources Starch

Gelatinization Temperature (°C)

Gelatinization Enthalpy (J/g)

Reference

Barley

56.27

1.28

El Halal et al. (2015)

Rice

54–42

8.7–7

Colussi et al. (2015)

High-amylose rice

50–54

0.01–1.17

Colussi et al. (2014)

Black bean

65.8

11.9

Pinto bean

58.3

11.7

Simsek, OvandoMartínez, Whitney, and Bello-Pérez (2012)

Waxy maize

64–72

5–10

High-amylose maize

65–77

5–9

Plantain

70–71

7–9

Guerra-Della Valle, Bello-Pérez, González-Soto, Solorza-Feria, and Arámbula-Villa (2008)

Potato

48–67

10.1–11.4

Maize

65–77

8.52

Singh, Chawla, and Singh (2004)

Luo and Shi (2012)

are important to determine the use of this polysaccharide and the thermal treatment during its processing. Other important phenomenon that is occurred in gelatinized starch is the retrogradation that is achieved upon cooling when chains are reassociated to produce an “ordered” structure. Some starches, mainly those with high-amylose content, produce a fast and high retrogradation; meanwhile, this phenomenon is slow and low for waxy starches. Amylose and amylopectin chains may form a simply juncture point and those junctions can increase with the time until produce a strong network. During retrogradation, different steps can be observed: first, an opaque and cuttable gel is developed and, at longest times, this system becomes rubbery with water loss, named as syneresis. Under this point of view, retrogradation is a negative phenomenon in starchy derivatives, but in other products is an advantage, giving to them the desired texture. Retrogradation

Starch  Chapter | 1  11

TABLE 1.2 Gelatinization Enthalpy of Native and Hydrolyzed Starches Starch Source

Gelatinization Temperature (ºC)

Wheat Native

11.8

Hydrolyzed (24 h)

11.5

Barley (normal) Native

8.4–10.4

Hydrolyzed (140 h)

20–25

Barley(waxy)

References Jacobs, Eerlingen, Rousen, Colonna, and Delcour (1998)

Morrison, Tester, Gidley, and Karkalas (1993) Morrison et al. (1993)

Native

12–13.5

Hydrolyzed (140 h)

17–19

Potato

Jacobs et al. (1998)

Native

18.7

Hydrolyzed (24 h)

23.0

Hydrolyzed (7 days)

18.6

Chickpea

Jacobs et al. (1998)

Native

12.6

Hydrolyzed (24 h)

13.0

Plantain Native

25.1

Hydrolyzed (6 h)

19.0

Aparicio-Saguilán et al. (2005)

is characterized by a crystalline structure due to the reorganization of starch components after the gelatinization process, being relevant to choose the proper starch for specific applications. Regarding to starch films, retrogradation phenomenon is produced during their storage, detected by an increase in the peaks of crystallinity due to the reorganization of starch components, regardless starch botanical sources. The presence of plasticizers and lipids delays the reorganization of starch chains in the film matrix, inhibiting the retrogradation. Reorganization of starch chains in the films produces changes in their functionality because when this phenomenon is present at high level, materials result harder with a brittle structure

12  Starch-Based Materials in Food Packaging

(Romero-Bastida et  al., 2005). Moreover, this reorganization can result in a reduced water and gas films permeability, as well as, in their elongation at break.

1.5  SYNTHESIS OF STARCH DERIVATIVES BY CHEMICAL AND PHYSICAL MODIFICATIONS Native starches from different botanical sources have unique properties; however, in many applications, they are not the most appropriate, and often they lack versatility for a wide range of products such as foods, drugs, plastics, cosmetics, etc. (Thomas & Atwell, 1999). These limitations are related to low shear resistance, thermal decomposition and high tendency to retrogradation, reducing its use in industrial applications (Sandhu & Singh, 2007). Obtaining modified starches by enzymatic, physical, and chemical methods (Fig. 1.4) is an alternative that has been used to improve the starch properties, extending its applications (Eliasson & Gudmundsson, 1996; Thomas & Atwell, 1999). Starch modification involves altering both physical and chemical characteristics of native one in order to improve its functional properties. Particularly, chemical modification involves the introduction of functional groups within the starch molecules, altering their physicochemical properties such as gelatinization, pasting, and retrogradation (Sandhu & Singh, 2007). Chemical modification consists of reacting native starch with small amounts of specific reagents (Rutenberg & Solarek, 1984; Thomas & Atwell, 1999), approved by the Regulatory Agency of United States (Title 21 Federal regulations code, section 172.892) (Thomas & Atwell, 1999). Reactions are usually performed in aqueous medium, typically 30–45% solids (by weight), commonly at pH 7–12, under stirring conditions and controlled temperature. It must be avoided that reaction temperature reaches to the starch gelatinization. In this sense, this polysaccharide can be recovered after water washes to eliminate unreacted reagents, salts and other soluble products, before final recovery in its dried form (Rutenberg & Solarek, 1984). The reaction is stopped by neutralizing the medium, obtaining a purified and dried starch with a higher efficiency than 70% (Thomas & Atwell, 1999). Chemical modification involves reactions associated with the hydroxyl groups (–OH) of starch polymer. The modification magnitude is determined by the degree of substitution (DS), a measure of the –OH groups average number in each anhydroglucosyl unit (GSU), which are replaced by functional groups. Each GSU has three -OH available for substitution, so the maximum DS is 3. If the substituent group (acetate, phosphate) reacts strongly with reagent, the reaction can form polymeric substituents. Another form to express the modification level is the molar substitution (MS), which refers to the moles of substituent groups per mole of GSU (Rutenberg & Solarek, 1984). In general, commercially produced derivatives have a DS less than 0.2. Chemically modified starches do not cause harm to health, due to they be toxicologically safe and can be used in food and drugs without limitation or quantitative restrictions. Derivatization and conversion are used to obtain chemically

FIGURE 1.4  Methods of modified starches.

14  Starch-Based Materials in Food Packaging

modified starches. Conversion method reduces the viscosity of native starch, which is important for some applications, such as salad dressings. In addition, modified starches by conversion can be used in some application at high concentrations (more than 6%) due to their greater solubility than its native counterpart. Conversion methods include acid hydrolysis, oxidation, dextrinization, and enzymatic treatment; providing starch products with different functionality (Tharanathan, 2005). Derivatization of starches modifies the gelatinization and cooking characteristics and decreases the tendency to retrogradation and gelling of amylose. As a consequence, water retention capacity at low temperatures is increased, minimizing syneresis due to an increment in the starch hydrophilic character. Moreover, substitution imparts hydrophobic properties and/or ionic substituents can be introduced. Derivatization can induce thickening, gelling, binding properties, and film formation (Rutenberg & Solarek, 1984). Techniques included in this modification method are crosslinking, oxidation, esterification or etherification, acid or enzymatic hydrolysis and dextrinization (Light, 1990; Rutenberg & Solarek, 1984; Thomas & Atwell, 1999). Oxidized starch has been used to elaborate films. It was found that oxidation produces an increase in the starch hydrophilic character, increasing the water vapor permeability and solubility. When the oxidation level is further increased, films tensile strength raised (Zamudio-Flores, Vargas-Torres, Pérez-González, BosquezMolina, & Bello-Pérez, 2006; Zamudio-Flores, Bautista-Baños, Salgado-Delgado, & Bello-Pérez, 2009). Meanwhile, acetylation increases the starch hydrophobic character, being the obtained derivatives suitable for films and coating materials (Fringant, Rinaudo, Gontard, Guilbert, & Derradji, 1998; Larotonda, Matsui, Paes, & Laurindo, 2003). Acetylation decreases the films solubility and water vapor permeability due to the reduced starch hydrophilic character. The solubility of acetylated starch films decreases at longest storage time due to the reorganization of starch components (amylose and amylopectin) in the film matrix (ZamudioFlores et al., 2009). Dual modification (oxidation and acetylation) of starch was tested to improve the films mechanical and barrier properties. The aim of this dual modification was to obtain films with an amphiphilic character, modifying their properties. Some properties of films based on dual modified starches are different from those corresponding to oxidized or acetylated ones (Zamudio-Flores et al., 2009, Zamudio-Flores, Gutierrez-Meraz, & Bello-Pérez, 2011). Particularly, films obtained from dual modified starches have higher elastic modulus and lower water vapor permeability compared to their oxidized counterparts. Additionally, starch can be physically modified to get the desirable properties in order to be incorporated to different products and materials. In this sense, physical treatments involve changes in the native starches structure. Processes used for physical modification include heat treatment, high pressure, microwaves (MW), ultraviolet light, radiation, ohmic heating, wet treatments, and mechanical stress (extrusion). The changes in the native starch structure alter its

Starch  Chapter | 1  15

functional properties and the obtained derivatives can be used in diverse applications such as paper industry, textile, plastics, chemicals, food industry, etc. Modified starches by these methods are considered safe and natural materials, which are preferred over the derivatives obtained by chemical modifications (Jacobs & Delcour, 1998). Particularly, oven-drying method has been used to modify rheological properties of waxy corn starch, final viscosity and shear strength. The addition of xanthan gum, carboxymethylcellulose and guar gum induces slight changes in the physicochemical and rheological characteristics of oven dried starch. These minor changes were attributed to variations in the amorphous regions, leaving the crystalline regions intact due to the drying effect (Lim, Han, BeMiller, & Lim, 2007). Few attempts to study the effect of physical processing methods on the functional properties of starch have been made. In this sense, a cooking index based on the starch degradation degree during its processing (Whalen, 1999). The process to elaborate films by extrusion includes a starch physical modifications. Processing parameters such as temperature and pressure, condition the modification degree of the granular structure. Temperature profile in the extruder produces a partial gelatinization where amylose lixiviation toward the continuous phase, developing a network. Also, the shear stress by the screw originates changes in the granules morphology, inducing their breakage under certain conditions and giving specific functionality to starch films. Besides, chemically modified starches can be used to obtain films by extrusion with improved mechanical and barrier properties (Vargas-Torres, Zamudio-Flores, Salgado-Delgado, & Bello-Pérez, 2007).

1.6 CONCLUSIONS Starch can be considered from two point of view: (1) it is a component of diverse foods such as bakery goods, pasta, beans and potato based products, etc.; (2) it is used as raw material in food products such as salad dressings, meat goods, filling pies, etc., as well as, in pharmaceutical drugs and packaging films. Starch structure and its components (amylose and amylopectin) are important to determine its functionality. Diverse models have been proposed to explain the starch structure-function relationship. Recently, Bertoft (2013) proposed a model that includes new analysis methods, involving the different chains present in the amylopectin structure. The search of nonconventional starch sources has increased in the last years, diversifying and exploiting their underuse. Besides, these nonconventional derivatives would allow the finding of new starch applications and the enhancement of the traditional ones. However, the modification of starch using chemical, physical, enzymatic, or combined methods improves or alters starch functionality. The wide starch use, for example, in plastic materials, is opening not only a promissory opportunity, but also new challenges in starch investigation.

16  Starch-Based Materials in Food Packaging

REFERENCES Aparicio-Saguilán, A., Flores-Huicochea, E., Tovar, J., García-Suárez, F., Gutiérrez-Meraz, F., & Bello-Pérez, L. A. (2005). Resistant starch-rich powders prepared by autoclaving of native and lintnerized banana starch: Partial characterization. Starch/Stärke, 57(9), 405–412. Baldwin, P. M., Adler, J., Davies, M. C., & Melia, C. D. (1995). Starch damage part 1: Characterisation of granule damage in ball-milled potato starch study by SEM. Starch/Staerke, 47(7), 247–251. Baldwin, P. M., Adler, J., Davies, M. C., & Melia, C. D. (1998). High resolution imaging of starch granule surfaces by atomic force microscopy. Journal of Cereal Science, 27(3), 255–265. Bertoft, E. (2013). On the building block and backbone concepts of amylopectin structure. Cereal Chemistry, 90(4), 294–311. Borovsky, D., Smith, E. C., Whelan, W. J., French, D., & Kikumoto, S. (1979). The mechanism of Q-enzime action and its influence on the structure of amylopectin. Archives of Biochemistry and Biophysics, 198, 627–631. Colussi, R., El Halal, S. L. M., Pinto, V. Z., Bartz, J., Gutkoski, L. C., Zavareze, E., et al. (2015). Acetylation of rice starch in an aqueous medium for use in food. Food Science & Technology, 62(2), 1076–1082. Colussi, R., Pinto, V. Z., El Halal, S. L. M. E., Vanier, N. L., Villanova, F. A., Silva, R. M., et al. (2014). Structural, morphological, and physicochemical properties of acetylated high, medium, and low-amylose rice starches. Carbohydrates Polymers, 103, 405–413. Eckhoff, S. R., Jayasena, W. V., & Spillman, C. K. (1993). Wet milling of maize grits. Cereal Chemistry, 70, 257–259. Eckhoff, S. R., Singh, S. K., Zehr, B. E., Raush, K. D., Fox, E. J., Mistry, A. K., et al. (1996). A 100-g laboratory corn wet milling procedure. Cereal Chemistry, 73, 54–57. El Halal, S. L. M. E., Colussi, R., Pinto, V. Z., Bartz, J., Radunz, M., Carreño, N. L. V., et al. (2015). Structure, morphology and functionality of acetylated and oxidised barley starches. Food Chemistry, 168, 247–256. Eliasson, A. C., & Gudmundsson, M. (1996). Starch: Physicochemical and functional aspects. In A. C. Eliasson (Ed.), Carbohydrates in foods (pp. 431–503). New York: Marcel Dekker Inc. French, D. (1972). Fine structure of starch and its relationship to the organization of starch granules. Journal of Japanese Society of Starch Science, 19, 8–25. Fringant, C., Rinaudo, M., Gontard, N., Guilbert, S., & Derradji, H. (1998). A biodegradable starch based coating to waterproof hydrophilic materials. Starch-Starke, 50(7), 292–296. Gallant, D. J., Bouchet, B., & Baldwin, P. M. (1997). Microscopy of starch: Evidence of a new level of granule organization. Carbohydrate Polymers, 32, 177–191. Gidley, M. L., Hanashiro, I., Hani, N. M., Hill, S. E., Huber, A., Jane, J. L., et al. (2010). Reliable measurements of the size distributions of starch molecules in solution: Current dilemmas and recommendations. Carbohydrate Polymers, 79, 255–261. Gilbert, R. G., Gidley, M. J., Hill, S., Kilz, P., Rolland-Sabaté, A., Stevenson, D. G., et al. (2010). Characterization the size and molecular weight distribution of starch: Why it is important and why it is hard. Cereal Foods World, 55(3), 139–143. Guerra-Della Valle, D., Bello-Pérez, L. A., González-Soto, R. A., Solorza-Feria, J., & ArámbulaVilla, G. (2008). Effect of reaction time on the acetylation of plantain starch. Revista Mexicana de Ingeniería Química, 7(3), 283–291. Hizukuri, S. (1986). Polymodal distribution of the chain lengths of amylopectins, and its significance. Carbohydrate Research, 147, 342–347. Jacobs, H., & Delcour, J. A. (1998). Hydrothermal modifications of granular starch, with retention of granular structure. A review. Journal Agricultural Food Chemistry, 46, 2895–2905.

Starch  Chapter | 1  17 Jacobs, H., Eerlingen, R. C., Rousen, N., Colonna, P., & Delcour, J. A. (1998). Acid hydrolysis of native and annealed wheat, potato and pea starches-DSC melting features, and chain length distributions of lintnerised starches. Carbohydrate Research, 308, 359–371. Jane, J. L. (2007). Structure of starch granules. Journal of Applied Glycoscience, 54, 31–36. Larotonda, F. D. S., Matsui, K. S., Paes, S. S., & Laurindo, J. B. (2003). Impregnation of Kraft paper with cassava-starch acetate—Analysis of the tensile strength, water absorption and water vapor permeability. Starch/Stärke, 55(11), 504–510. Light, J. M. (1990). Modified food starches: Why, What, Where, and How. Cereal Food World, 35(no.11), 1081–1092. Lim, H., Han, J. A., BeMiller, J., & Lim, S. T. (2007). Physical modification of waxy maize starch by dry heating with ionic gums. Journal of Applied Glycoscience, 53(4), 281–286. Luo, Z. G., & Shi, Y. C. (2012). Preparation of acetylated waxy, normal, and high-amylose maize starches with intermediate degrees of substitution in aqueous solution and their properties. Journal of Agricultural and Food Chemistry, 60(37), 9468–9475. Manners, D. J., & Matheson, N. K. (1981). The fine structure of amylopectin. Carbohydrate Research, 90, 99–110. Mistry, A. H., & Eckhoff, S. R. (1992a). Alkali debranning of corn to obtain corn bran. Cereal Chemistry, 69, 202–205. Mistry, A. H., & Eckhoff, S. R. (1992b). Characteristics of alkali-extracted starch obtained from corn flour. Cereal Chemistry, 69, 296–303. Morrison, W. R., Tester, R. F., Gidley, M. J., & Karkalas, J. (1993). Resistance to acid hydrolysis of lipid-complexed amylose and lipid-free amylose in lintnerised waxy and non-waxy barley starches. Carbohydrate Research, 245(2), 289–302. Nikuni, Z. (1978). Studies on starch granules. Starch/Stärke, 30, 105–111. Pérez, S., & Bertoft, E. (2010). The molecular structures of starch components and their contribution to the architecture of starch granules: A comprehensive review. Starch/Stärke, 62, 389–420. Ramirez-Cortes, R., Bello-Pérez, L. A., Gonzalez-Soto, R. A., Gutierrez-Meraz, F., & AlvarezRamirez, J. (2015). Isolation of plantain starch on a large laboratory scale. Starch/Stärke, 67, 1–8. Robin, J. P., Mercier, C., Charbonniere, R., & Guilbot, A. (1974). Lintnerized starches. Gel filtration and enzymatic studies of insoluble residues from prolonged acid treatment of potato starch. Cereal Chemistry, 51, 389–406. Rolland-Sabaté, A., Colonna, P., Mendez-Montealvo, M. G., & Planchot, V. (2007). Branching features of amylopectins and glycogen determined by asymmetrical flow field flow fractionation coupled with multiangle laser light scattering. Biomacromolecules, 8, 2520–2532. Romero-Bastida, C. A., Bello-Pérez, L. A., García, M. A., Martino, M. N., Solorza-Feria, J., & Zaritzky, N. E. (2005). Physicochemical and microstructural characterization of films prepared by thermal and cold gelatinization from non-conventional sources of starches. Carbohydrate Polymers, 60(2), 235–244. Rutenberg, M. W., & Solarek, D. (1984). Starch derivatives: Production and uses. In R. Whistler, J. BeMiller, & E. Paschall (Eds.), Starch chemistry and technology (pp. 311–366). New York: Academic Press. Sandhu, K. S., & Singh, N. (2007). Some properties of corn starches II: Physicochemical, gelatinization, retrogradation, pasting and gel textural properties. Food Chemistry, 101(4), 1499–1507. Simsek, S., Ovando-Martínez, M., Whitney, K., & Bello-Pérez, L. A. (2012). Effect of acetylation, oxidation and annealing on physicochemical properties of bean starch. Food Chemistry, 134(no.4), 1796–1803.

18  Starch-Based Materials in Food Packaging Singh, N., Chawla, D., & Singh, J. (2004). Influence of acetic anhydride on physicochemical morphological and thermal properties of corn and potato starch. Food Chemistry, 86, 601–608. Singh, S. K., & Eckhoff, S. R. (1995). Hydrocyclone operation for starch-protein separation. Cereal Chemistry, 72, 344–348. Singh, H., & Eckhoff, S. R. (1996). Wet milling of corn—A review of laboratory-scale and pilot plant-scale procedures. Cereal Chemistry, 73(6), 659–667. Tharanathan, R. N. (2005). Starch—Value addition by modification. Critical Reviews in Food Science and Nutrition, 45(5), 371–384. Thomas, D. J., & Atwell, W. A. (1999). Starch modifications. In D. J. Thomas & W. A. Atwell (Eds.), Starches (pp. 43–48). MN: American Association of Cereal Chemists, St. Paul. Vargas-Torres, A., Zamudio-Flores, P. B., Salgado-Delgado, R., & Bello-Pérez, L. A. (2007). Morphological, thermal and mechanical studies of film elaborated with the blend low-density polyethylene and chemical modified banana starch. Journal of Applied Polymer Science, 106(6), 3994–3999. Wang, S., & Copeland, L. (2013). Molecular disassembly of starch granules during gelatinization and its effect on starch digestibility: a review. Food & Function, 4, 1564–1580. Wang, S., Yu, J., & Yu, J. (2008). The semi-crystalline growth rings of C-type pea starch granule revealed by SEM and HR-TEM during acid hydrolysis. Carbohydrate Polymers, 74(3), 731–739. Whalen, P. J. (1999). Measuring process effects in ready-to-eat breakfast cereals. Cereal Foods World, 44, 407–412. Zamudio-Flores, P. B., Bautista-Baños, S., Salgado-Delgado, R., & Bello-Pérez, L. A. (2009). Effect of oxidation level on the dual modification of banana starch: The mechanical and barrier properties of its films. Journal of Applied Polymer Science, 112(2), 822–829. Zamudio-Flores, P. B., Gutierrez-Meraz, F., & Bello-Pérez, L. A. (2011). Effect of low and high acetylation degree in the morphological, physicochemical and structural characteristics of barley starch. Starch/Stärke, 63(9), 550–557. Zamudio-Flores, P. B., Vargas-Torres, A., Pérez-González, J., Bosquez-Molina, E., & Bello-Pérez, L. A. (2006). Films prepared with oxidized banana starch: Mechanical and barrier properties. Starch/Stärke, 58(6), 274–282. Zhang, G., Ao, Z., & Hamaker, B. R. (2008). Nutritional property of endosperm starches from maize mutant: A parabolic relationship between slowly digestible starch and amylopectin fine structure. Journal of Agricultural and Food Chemistry, 56, 4686–4694. Zhang, G., Venkatachalam, M., & Hamaker, B. R. (2006). Structural basis for the slow digestion property of native cereal starches. Biomacromolecules, 7, 3259–3266.

FURTHER READING Bertoft, E., Zhu, Q., Andtfolk, H., & Jungner, M. (1999). Structural heterogeneity in waxy-rice starch. Carbohydrate Polymers, 38, 349–359. Haworth, W. N., Hirst, E. L., & Isherwood, F. A. (1937). Polysaccharides. Part XXIV. Yeast mannan. Journal of Chemical Society, 784–791. Nikuni, Z. (1969). Starch and cooking. Science Cooking, 2, 6–14. Staudinger, H., & Husemann, E. (1937). Über hochpolymere verbindungen. Mitt. Über die konstitution der stärke. Liebigs Annalen der Chemie, 527, 195–236.

Chapter 2

Bio-Based Materials from Traditional and Nonconventional Native and Modified Starches Carmen C. Tadini University of São Paulo, São Paulo, Brazil

2.1  BIOMATERIALS DEVELOPMENT FROM TRADITIONAL NATIVE STARCHES Polysaccharides, otherwise known as carbohydrates, are the most widespread polymers in nature and play essential roles to sustain living organisms. They are natural-based materials possessing a unique combination of functional properties and environment-friendly features (nontoxic, biodegradable, and renewable materials) (Gurunathan, Mohanty, & Nayak, 2015). Nowadays, many investigations are conducted regarding the development and characterization of biopolymers since conventional synthetic plastic materials are resistant to microbial attack and biodegradation (Sanyang, Sapuan, Jawaid, Ishak, & Sahari, 2016). Among the natural polymers, starch has been considered as one of the most promising materials because of its attractive combination of availability, low price, and thermoplastic behavior, besides the fact that it is biodegradable, recyclable, and renewable (Souza, Ditchfield, & Tadini, 2010). Unfortunately, these materials still have poor mechanical properties, remarkable sensitivity to moisture, difficulty of processing, and brittleness, which make it unsatisfactory in some industrial purposes. Starch is a natural polysaccharide that can be found in several plant resources, such as roots (sweet potatoes, tapioca), tubers (potatoes), stems (sago palm), cereal grains (corn, rice, wheat, barley, oats, and sorghum), and legume seeds (peas and beans) (Gurunathan et  al., 2015). Nowadays, the uses of starch are divided around 60% for food and 40% for industrial applications (Le Corre & Angellier-Coussy, 2014).

Starch-Based Materials in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-0-12-809439-6.00002-9 © 2017 Elsevier Inc. All rights reserved.

19

20  Starch-Based Materials in Food Packaging

As it is well-known starch is composed of a mixture of two polymers, an essentially linear polymer amylose and a highly branched one amylopectin and it mainly consists of about 70%–80% amylopectin and 20%–30% amylose. The different molecular weights and degrees of branching of both molecules are responsible for the quite different properties of starch isolated from sources with diverse amylose/amylopectin relative ratios. The amount of these macromolecules depends upon its source, as amylomaize (rich-amylose starch) or waxy maize (rich-amylopectin starch) meanwhile bio-based materials properties depend upon the amount of amylose and amylopectin present within the starch granule (Tharanathan, 2003). The main starch sources that are produced worldwide are corn, potato, and cassava. Many other sources are available like wheat, rice, sweet potato, yam, green banana, peas, beans, sorghum, arrowroot, and lentils, among others. Physically, most native starches are semicrystalline, and their crystallinity has been reported to be between 20% and 45%. Amylose and amylopectin are arranged in granules in complex structures consisting of crystalline and amorphous regions in alternate layers within the starch granules. The crystalline regions are formed as a consequence of the particular arrangement of the branches in the amylopectin chain. The short branches are supposed to form double helices, which largely are organized into crystallites (Gurunathan et al., 2015). Averous (2004) in his review presented the starch composition, the granule diameter and degree of crystallinity of starches from different sources (Table 2.1). As can be seen, the amylomaize contains low amylopectin content, therefore shows lower percentages of crystallinity. Among the other starches, all those with high amylopectin content: wheat, maize and waxy starch, showed the percentage of crystalline between 36% and 39%, whereas potato is 25%. Currently, the predominant raw material for the production of starch polymers is corn. Others sources of starch are also being utilized where price and availability permits it. Examples include the use of potato starch in Germany and Netherlands, and cassava (tapioca) in some parts of the world, like Brazil. Nowadays, the market of starch-based polymers accounts for about 70 % of the global market for bioplastics, representing about 25,000 ton in 2003. The global consumption of starch-based biodegradable polymers increased up to 114,000 ton in 2007. However, the production capacity according to the latest data reported by the University of Utrecht shows as projected increase to 810,000 ton for 2020 (Gurunathan et al., 2015; Shen, Worrel, & Patel, 2009; Souza et al., 2010). Some starch-based blends are nowadays marketed at commercial scale, with trademarks as Mater-Bi® (Novamont, Italy), Bioplast® (Biotech, Germany), Novon™ (produced by Chisso in Japan and Warner-Lambert in USA), Biopar® (BIOP Biopolymer Technologies AG, Germany), Gaialene® (Roquette, France), and Solanyl (Rodenburg Biopolymers, Netherlands). Moreover, 75% of starch polymers are used for packaging applications including soluble films, films for bags

TABLE 2.1 Composition (Determined as Dry Basis), Granule Diameter, and Crystallinity of Different Starches Starch

Amylose Content (g/100 g)

Amylopectin Content (g/100 g)

Lipid Content (g/100 g)

Protein Content (g/100 g)

Moisture Contenta (g/100 g)

Granule Diameter (μm)

Crystallinity (%)

Wheat

26–27

72–73

0.63

0.30

13

25

36

Maize

26–28

71–73

0.63

0.30

12–13

15

39

Waxy starch

1000

73.1 ± 1.0

7.0 ± 0.4

>1000

15 ± 2

2.2 ± 0.7

455 ± 90

3.0 ± 0.3

1.5 ± 0.2

1.0 ± 0.2

N.R.

1.5 ± 0.2

0.3 ± 0.2

TPS/LDPE (50/50) + PE-g-MA (2.5%) + CF (5%) TPS/LDPE (50/50) + PE-g-MA (2.5%) + CG (10%) TPS/LDPE (50/50) + PE-g-MA (2.5%) + CF (5%) + CG (10%) Native starch

TPS/PCL (20/80) TPS/PCL (50/50)

Blends with synthetic biodegradable polymer.

Gly: 38% Eq. RH: 50%

3000

Plasticizer. New sources of starch.

Gly and MalA Eq. RH: N.R.

N.R.

TPS/PCL (80/20)

Compression moulding

Aesculus hippocastanum starch (A.H)

TPS (30% Gly)

Araucaria Araucana starch (A.A.)

TPS (30% Gly)

4.0 ± 0.5

2.4 ± 0.2

1.1 ± 0.2

TPS (15% Gly) + 15% MalA

N.R.

2.0 ± 0.3

0.8 ± 0.2

Corn starch

TPS

110 ± 2

1049 ± 38

10.7 ± 0.2

2.4 ± 0.3

TPS/CH (86/14)

139 ± 2

1188 ± 68

12.5 ± 0.8

1.6 ± 0.2

TPS/CHT (86/14)

121 ± 3

1081 ± 58

12.6 ± 0.6

1.9 ± 0.4

TPS (15% Gly) + 15% MalA

Blends with natural biopolymer.

Gly: 30% Eq. RH: 60%

Li & Favis 2010

Castaño et al., 2014

Lopez et al., 2014

(Continued)

TABLE A.9.1 Mechanical Properties of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Final Properties (Continued) Method

Starch

Formulation

Strategy to Improve

Plasticizer and Eq. RH

Thickness (µm)

EM (MPa)

TS (MPa)

ε (%)

Reference

TPS

Blends with nonbiodegradable plastic. Compatibilizer.

Gly: 35% Eq. RH: N.R.

2000

250

12

300

231

9

140

Sabetzadeh et al., 2012

140

6.5

80

337

10.5

425

342

11

385

380

10

343

150

2.5

83

235

4

59

268 ± 28

278 ± 75

10 ± 2

28 ± 10

204 ± 28

262 ± 70

10.0 ± 1.1

21 ± 7

158 ± 13

380 ± 90

9.1 ± 0.5

12 ± 7

N.R.

23 ± 2

1.19 ± 0.04

62 ± 4

TPS/TN (97/3)

25 ± 2

1.80 ± 0.13

59.1 ± 1.5

TPS/TN (95/5)

38 ± 3

2.34 ± 0.04

59.0 ± 1.1

TPS/LDPE (20/80) + PE-g-MA (3%) TPS/LDPE (40/60) + PE-g-MA (3%) TPS/PCL (20/80) TPS/PCL (20/80) + PCL-g-DEM

Blends with synthetic biodegradable polymer. Compatibilizer.

Without plasticizer Eq. RH: N.R.

2000

TPS/PCL (20/80) + PCL-g-GMA TPS/ESO (99/1) + Et3N (0.2%): MTPS

Starch modification: Et3N and ESO.

Gly: 28% Eq. RH: 40%

2000

TPS/ESO (97/3) ++ Et3N (0.2%): MTPS TPS TPS/HPMC (83.3/16.7) TPS/HPMC (83.3/16.7) + CA (1%) TPS

Blends with natural biopolymer. Compatibilizer. Plasticiser.

Gly: 30% Eq. RH: 53%

Inorganic filler.

Gly: 30% Eq. RH: 60%

Sugih et al., 2009

Belhassen et al., 2014

Ortega-Toro et al., 2014

López et al. (2015)

TABLE A.9.1 Mechanical Properties of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Final Properties Method

Starch

Formulation

Strategy to Improve

Plasticizer and Eq. RH

Thickness (µm)

EM (MPa)

TS (MPa)

ε (%)

Reference

TPS-GlyPh/PLA (20/80)

Organic filler. Other additives: flame retardant, surface treating agent

Gly and GlyPh: 25% Eq. RH: N.R.

4000

1600

33

2.6 ± 0.2

Bocz et al. (2014)

1500

26

1.9 ± 0.2

1700

21

1.3 ± 0.2

850

32

30

980

42

250

740

30

230

200 ± 7

39 ± 4

1.7 ± 0.4

11 ± 3

192 ± 12

83 ± 5

4.3 ± 0.5

15.7 ±1.4

193 ± 9

64 ± 6

3.0 ± 0.4

12 ± 3

500

188 ± 20

17.3 ± 0.6

556 ± 12

141 ± 18

13.0 ± 0.7

79 ± 20

151 ± 8

15.5 ± 0.9

56 ± 4

60 ± 9

1.7 ± 0.2

19 ± 2

422 ± 23

3.7 ± 0.5

2.6 ±0.5

214 ± 56

2.8 ± 0.4

5.5 ±1.4

TPS-GlyPh/PLA (20/80) + Flax-Psil (35%) TPS-GlyPh/PLA (20/80) + Flax-Psil (40%) + APP (16%) Wheat starch

TPS + PA12 (30/70) TPS + PA12 (30/70) + DGEBA (1%)

Blends with synthetic biodegradable polymer. compatibilizer.

Gly: 20% Eq. RH: 50%

1000

TPS + PA12 (30/70) + Lotader 3410 (5%) Cassava starch

TPS

Organic filler.

TPS + cassava bagasse (98.5/1.5)

Gly: 30% Eq. RH: 60%

TPS + cassava root peel (98.5/1.5) MTPS/PLA (20/80) MTPS/PLA (30/70)

Starch modification: MA

Gly: 25% Eq. RH: N.R.

MTPS/PLA (40/60) TPS/PLA (70/30) TPS/PLA (70/30) + CH (spray) TPS/PLA (70/30) + CH (immersion)

Blends with synthetic biodegradable polymer. Coating with natural biopolymer.

Gly: 30% Eq. RH: N.R.

900–1200

Teyssandier et al., 2011

Versino et al., 2015

Wootthikanokkhan et al., 2012

Soares et al., 2013

(Continued)

TABLE A.9.1 Mechanical Properties of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Final Properties (Continued) Method

Starch

Formulation

Strategy to Improve

Plasticizer and Eq. RH

Thickness (µm)

EM (MPa)

TS (MPa)

ε (%)

Reference

TPS/PLA (70/30)

Blends with synthetic biodegradable polymer. Coating with natural biopolymer.

Gly: 30% Eq. RH: N.R.

N.R.

60 ± 9

1.7 ± 0.2

19 ± 2

Soares et al., 2014

382 ± 126

6±2

1.9 ± 0.4

422 ± 23

3.7 ± 0.5

2.6 ± 0.5

Organic Filler. Compatibilizer. Plasticisers.

Gly: 30% Eq. RH: 53%

1182 ± 165

16.5 ± 1.3

14.5 ± 0.7

1664 ± 126

19.9 ± 0.9

2.0 ± 0.3

Blends with synthetic biodegradable polymer. Inorganic filler.

Gly: 30% Eq. RH: N.R.

146 ± 6

1.8 ± 0.2

3.6 ± 0.9

305 ± 14

5.6 ± 0.3

4.3 ± 0.9

329 ± 14

7.9 ± 0.3

6.0 ± 1.2

TPS/PLA (70/30) + CH (C.S.) TPS/PLA (70/30) + CH (C.F.) Cassava starch

TPS/PLA (80/20) + CA (2%) + SA (2%)

Cassava bagasse (b)

TPSb/PLA (80/20) + CA (2%) + SA (2%)

Potato starch

TPS TPS/PLA (60/40) TPS/PLA (60/40) + Na-MMT (1%)

N.R.

N.R.

Teixeira et al., 2007

Ayana et al., 2014

TABLE A.9.2 Water Vapor Permeability of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Method

Starch

Formulation

Strategy to Improve

Plasticizer

Δ Relative Humidity

Extrusion and Extrusioncoated

Corn starch

TPS + LDPE (95/5)

Blends with nonbiodegradable plastic.

TPS + LDPE (90/10)

100%–50%

GP + 1 layer SBC (1.2 g/m ) 2

GP + 2 layers SBC (3 g/m ) 2

LPB + 1 layer SBC (3.8 g/m ) 2

LPB + 2 layers SBC (7.1 g/m2) LPB + 2 layers SBC (9.1 g/m2) Corn starch

MTPS/TPS (12.5/87.5) MTPS/TPS (94/6)

Inorganic filler. Starch modification: Hydroxypropylated and oxidized. SBC: starch + PEG + 33% Na-MMT based on dry starch: total solid content 20.3%).

PEG 400: 30%

Starch modification: acetylated starch.

Gly: 20%

MTPS/TPS (17.5/82.5) MTPS/TPS (54.5/45.5) Cassava starch

TPS TPS/PBAT (80/20) TPS/PBAT (50/50)

100%–50%

Reference

2.2 (×10−4)

400–500

Pushpadass et al., 2010

1.7 (×10 )

400–500

1.9 (×10−4)

400−500

−10

5.1 (×10

)

N.R.

Olsson et al., 2014

80 ± 8

López et al., 2013

−10

4.2 (×10

)

−10

47.4 (×10

)

13.7 (×10−10) 6.2 (×10−10) 75%–0%

1.4 ± 0.3 (×10−10) −10

Gly: 15%

0.88 ± 0.05 (×10

Gly: 20%

1.3 ± 0.2 (×10−10)

Gly: 30%

)

−10

1.2 ± 0.2 (×10

Gly: 15% Plasticizer. Method of production.

Thickness (µm)

−4

TPS + LDPE (85/15) Potato starch

Blow extrusion

Gly: 30%

WVP (g day−1 Pa−1 m−1)

90%–64%

)

−7

20 ± 4 (×10 )

76 ± 14 123 ± 12 129 ± 14 N.R.

−7

3.94 ± 0.03 (×10 )

Brandelero et al., 2011

2.4 ± 0.2 (×10−7)

(Continued)

TABLE A.9.2 Water Vapor Permeability of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement (Continued) Method

Starch

Formulation

Strategy to Improve

Plasticizer

Δ Relative Humidity

TPS/PBAT(55/45) TPS/PBAT (55/45) + CA (1.5%)

Blends with synthetic biodegradable polymer. Compatibilizer. Plasticizer.

Gly: 18%

75%–33%

TPS/PBAT (55/45) + MA (1.5%)

TPS/PBAT (55/45) + MaA (0.375%)

Blends with synthetic biodegradable polymer. Compatibilizer. Plasticizer.

Gly: 18%

75%–33%

TPS/PBAT (60/40) + CA (0.8%)

Blends with synthetic biodegradable polymer. Compatibilizer. Plasticizer.

TPS/PBAT (60/40) + CA (0.8%) + SHP (0.38%) TPS/PBAT (33/67)

TPS/PBAT (33/67) + Tween 80 (2%)

Reference

3.11 ± 0.02 (×10−5)

100-150

1.69 ± 0.02 (×10−5)

100-150

Olivato et al., 2012b

3.3 ± 0.7 (×10−5)

100-150

Blends with synthetic biodegradable polymer. Additives.

4.0 ± 0.3 (×10 )

100-150

1.5 ± 0.2 (×10−5)

100-150

−5

TPS/PBAT (55/45) + TA (0.375%) TPS/PBAT (60/40)

Thickness (µm)

−5

TPS/PBAT (55/45) + CA (0.75%) + MA (0.75%) TPS/PBAT (55/45) + CA (0.375%)

WVP (g day−1 Pa−1 m−1)

Gly: 11%

75%–33%

1.6 ± 0.2 (×10 )

100-150

1.6 ± 0.2 (×10−5)

100-150

5.8 ± 0.6 (×10−6)

100-150

−5

Gly: 10.2%

3.50 ± 0.13 (×10 )

100-150

Gly: 10.2%

3.8 ± 0.4 (×10−5)

100-150

0.57 ± 0.02 (×10−7)

147 ± 58

Gly: 30%

33%–0%

−7

90%–64%

2.4 ± 0.2 (×10 )

147 ± 58

33%–0%

5.3 ± 0.3 (×10−7)

1206 ± 200

90%–64%

22 ± 6 (×10−7)

1206 ± 200

Olivato et al., 2012a

García et al., 2014

Brandelero et al., 2010

TABLE A.9.2 Water Vapor Permeability of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Method

Starch

Formulation

Strategy to Improve

Plasticizer

Δ Relative Humidity

TPS/PBAT (60/40) + CA (0.01%) + Ms (0.5%) TPS/PBAT/PLA (50/40/10) + CA (0.01%) + Ms (0.5%)

Blends with synthetic biodegradable polymer. Compatibilizer. Plasticizer.

Gly: 32%

64%–33%

TPS/PBAT/PLA (40/40/20) + CA (0.01%) + Ms (0.5%) Injection moulding

Wheat flour

TPS/PLA (75/25) TPS/PLA (75/25) + CA (2%)

Blends with synthetic biodegradable polymer. Compatibilizer. Plasticizer.

Gly: 15%

60%–0%

TPS/PLA (75/25) + CA (10%) TPS/PLA (75/25) + CA (20%) Compression molding

Cornstarch

TPS TPS/HPMC (83.3/16.7)

TPS/CH (86/14)

Blends with natural biopolymer. Compatibilizer. Plasticizer.

Gly: 30%

100%–53%

Blends with natural biopolymer.

Gly: 30%

100%–50%

TPS/CHT (86/14) TPS

Thickness (µm)

Reference

7.2 ± 0.2 (×10−6)

103 ± 9

Shirai et al., 2013

6.3 ± 0.3 (×10−6)

131 ± 10

5.0 ± 0.7 (×10−6)

405 ± 59

1.4 ± 0.2 (×10−5)

1000 ± 100

0.24 ± 0.02 (×10−5)

1100 ± 20

0.29 ± 0.06 (×10−5)

1000 ± 100

−5

1000 ± 100

−4

1.16 ± 0.06 (×10 )

268 ± 28

0.58 ± 0.05 (×10−4)

204 ± 28

0.34 ± 0.04 (×10−4)

158 ± 13

1.26 ± 0.14 (×10 )

TPS/HPMC (83.3/16.7) + CA (1%) TPS

WVP (g day−1 Pa−1 m−1)

Inorganic filler.

Gly: 30%

50%–0%

−4

110 ± 2

−4

0.75 ± 0.03 (×10 )

138 ± 2

0.51 ± 0.02 (×10−4)

121 ± 3

1.11 ± 0.09 (×10−4)

N.R.

1.15 ± 0.08 (×10 )

−4

TPS/TN (97/3)

0.80 ± 0.05 (×10 )

TPS/TN (95/5)

0.830 ± 0.009 (×10−4)

Abdillahi et al., 2013

OrtegaToro et al., 2014

Lopez et al., 2014

López et al., 2015

(Continued)

TABLE A.9.2 Water Vapor Permeability of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement (Continued) Method

Starch

Formulation

Strategy to Improve

Plasticizer

Δ Relative Humidity

Cassava starch

TPS/PLA (70/30) TPS/PLA (70/30) + CH (spray) TPS/PLA (70/30) + CH (immersion) TPS/PLA (70/30) TPS/PLA (70/30) + CH (C.S.) TPS/PLA (70/30) + CH (C.F.) TPS

Blends with synthetic biodegradable polymer. Coating with natural biopolymer.

Gly: 30%

Blends with synthetic biodegradable polymer. Coating with natural biopolymer.

Gly: 30%

Inorganic filler.

Gly: 25%

75%–0%

WVP (g day−1 Pa−1 m−1)

Thickness (µm)

Reference

4.3 ± 0.5 (×10−7)

900-1200

Soares et al., 2013

N.R.

Soares et al., 2014

394 ± 28

Müller et al., 2012

3.1 ± 0.2 (×10−7) 3.3 ± 0.2 (×10−7) 75%–0%

4.3 ± 0.5 (×10−7) −7

1.75 ± 0.05 (×10 ) 3.1 ± 0.2 (×10−7) 75%–0%

1.9 ± 0.2 (×10−5) −5

485 ± 37

−5

0.7 ± 0.2 (×10 )

TPS/MMT (96/4) TPS/MMT(94/6)

0.7 ± 0.2 (×10 )

515 ± 37

TPS

1.30 (×10−5)

200 ± 7

TPS + cassava bagasse (98.5/1.5)

1.30 (×10−5)

192 ± 12

TPS + cassava root peel (98.5/1.5)

1.34 (×10−5)

193 ± 9

Organic filler.

Gly: 30%

50%–0%

Versino et al., 2015

TABLE A.9.3 Oxygen Permeability (O2P) of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Method

Starch

Formulations

Strategy to Improve

Plasticizer and Eq. RH

O2P (cm3 m−1 s Pa)

Thickness (µm)

Reference

Blown extrusion

Cornstarch

MTPS/TPS (12.5/87.5)

Starch modification: acetylated starch.

Gly: 20%; Eq. RH: 65%

4.13 ± 0.11 (×10−10)

80 ± 8

Gly: 15%; Eq. RH: 65%

2.08 ± 0.08 (×10−10)

76 ± 14

López et al., 2013

MTPS/TPS (94/6) MTPS/TPS (17.5/82.5)

Gly: 20%; Eq. RH: 65%

MTPS/TPS (54.5/45.5) Injection moulding

Corn starch

TPS/Lotader 3210 (80/20) TPS/Lotader 3210 (80/20) + LS (2%)

Filler. Compatibilizer.

TPS/PLA (75/25) TPS/PLA (75/25) + CA (2%) TPS/PLA (75/25) + CA (10%) TPS/PLA (75/25) + CA (20%)

Compression moulding

Corn starch

TPS/HPMC (83.3/16.7) TPS/HPMC (83.3/16.7) + CA (1%) TPS/HPMC (83.3/16.7) TPS TPS/TN (97/3) TPS/TN (95/5)

129 ± 14

)

2.98 ± 0.08 (×10

Gly: 35% Eq. RH: N.R.

7.8 (×10−12)

400

6.0 (×10−12)

400

6.1 (×10 Blends with synthetic biodegradable polymer. Compatibilizer. Plasticizer.

123 ± 12

−10

3.31 ± 0.08 (×10

Gly: 15%; Eq. RH: 65%

TPS/Lotader 3210 (80/20) + LS (4%) Wheat flour

−10

Gly: 15% Eq. RH: 50%

−12

)

Gly: 30% Eq. RH: 53%

Inorganic filler

Gly: 30% Eq. RH: 75%

Privas et al., 2013

400 −13

5.44 ± 0.02 (×10

)

1000 ± 100

0.35 ± 0.02 (×10−13)

1100 ± 20

1.60 ± 0.03 (×10−13)

1000 ± 100

1.40 ± 0.2 (×10

Blends with natural biopolymer. Compatibilizer. Plasticizer.

)

−13

)

−13

1.3 ± 0.5 (×10

1000 ± 100

)

268 ± 28

4.0 ± 1.0 (×10−13)

204 ± 28

5.0 ± 1.0 (×10−13)

158 ± 13

6.0 ± 0.5 (×10−11)

N.R.

4.6 ± 0.3 (×10−11) 4.4 ± 0.2 (×10−11)

Abdillahi et al., 2013

OrtegaToro et al., 2014

López et al., 2015

TABLE A.9.4 Gas Permeability of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Method

Starch Formulation

Extrusioncoated

Potato starch

GP + 1 layer SBC (1.2 g/m2) GP + 2 layers SBC (3 g/m ) 2

LPB + 1 layer SBC (3.8 g/m ) 2

LPB + 2 layers SBC (7.1 g/m ) 2

LPB + 2 layers SBC (9.1 g/m ) 2

Blown extrusion

Corn starch

MTPS/TPS (12.5/87.5)

Strategy to Improve

Plasticizer and Eq. RH

Gas

Permeability

Thickness Reference (µm)

Inorganic filler. Starch modification: hydroxypropylated and oxidized. SBC: starch + PEG + 33% Na-MMT based on dry starch: total solid content 20.3%).

PEG 400 (30%) Eq. RH: 50%

Air (nm Pa.s)

0

N.R.

Olsson et al., 2014

Starch modification: acetylated starch.

Gly: 20% Eq. RH: 65%

5.0 ± 0.3 (×10−9)

80 ± 8

López et al., 2013

0 >65 1.9 0.3

CO2 (cm3/m s Pa)

MTPS/TPS (94/6)

Gly: 15% Eq. RH: 65%

2.7 ± 0.2 (×10−9)

76 ± 14

MTPS/TPS (17.5/82.5)

Gly: 20% Eq. RH: 65%

4.13 ± 0.14 (×10−9)

123 ± 12

MTPS/TPS (54.5/45.5)

Gly: 15% Eq. RH: 65%

3.85 ± 0.04 (×10−9)

129 ± 14

TABLE A.9.5 Thermal Properties of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Method

Starch

Formulation

Strategy to Improve

Plasticizer and Eq. RH

Thermal Properties (ºC)

Reference

Extrusion

Corn starch

TPS

Starch modification: MA

Gly: 25% Eq. RH: N.R.

TGA Onset: 302

Hablot et al., 2013

TPS/PBAT (40/60) TPS/PBAT (40/60) + MA (2%) Injection molding

Compression moulding

Corn starch

TGA Onset: 321 TGA Onset: 295 Tgβ: −48, Tgα: 67

TGA Onset: 252

Tgβ: −47, Tgα: 75

TGA Onset: 230

TPS/CHNC (80/20)

Tgβ: −47, Tgα: 76

TGA Onset: 222

TPS/CHNF (90/10)

Tgβ: −46, Tgα: 74

TGA Onset: 259

TPS

Organic filler

TPS/CHNC (90/10)

Aesculus Hippocastanum starch (A.H) and

TPS (30% Gly)

Araucaria Araucana starch (A.A.)

TPS (30% Gly)

TGA Tmax: 307

TPS (15% Gly) + 15% MalA

TGA Tmax: 307

Corn starch

TPS

TPS (15% Gly) + 15% MalA

TPS/HPMC (83.3/16.7) TPS/HPMC (83.3/16.7) + CA (1%)

Plasticizer. New sources of starch

Gly: 30% Eq. RH: 50%

Blends with natural biopolymers. Compatibilizer. Plasticizer.

Gly and MalA Eq. RH: N.R.

Gly: 30% Eq. RH: 0%

TGA Tmax: 302 TGA Tmax: 302

Tg: 125 ± 4 Tg: 112 ± 3

Salaberria et al., 2014

Castaño et al., 2014

Ortega-Toro et al., 2014

Tg: 105 ± 9 (Continued)

TABLE A.9.5 Thermal Properties of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement (Continued) Method

Starch

Formulation

Strategy to Improve

Plasticizer and Eq. RH

Thermal Properties (ºC)

Reference

TPS

Blends with natural biopolymer.

Gly: 30% Eq. RH: 60%

Tm: 155 ± 12

Lopez et al., 2014

TPS/CH (86/14)

Tm: 147 ± 12

TPS/CHT (86/14) TPS TPS/PLA (20/80) TPS/PLA (20/80) + GPOE (15%) TPS TPS/PCL (40/60) TPS/PCL (60/40) TPS/PU2(80/20) TPS/PU3 (80/20) TPS/PU4 (80/20 TPS TPS/PP-ATBC (70/30) TPS/PP-ATBC (70/30) + MMT (1%)

Tm: 152 ± 14

Blends with synthetic biodegradable polymer. Compatibilizer

Gly: 20% Eq. RH: N.R.

Blends with synthetic biodegradable polymer.

Gly: 30% Eq. RH: N.R.

Blends with synthetic biodegradable polymer.

Without Eq. RH: 60%

Blends with nonbiodegradable plastics. Compatibilizer. Plasticizer. Inorganic filler.

Glycerol (25% based on starch) and ATBC 15% based on PP) Eq. RH: 80%

TGA Onset: 270

Shi et al., 2011

TGA Onset: 280 TGA Onset: 290 TGA Onset: 290

Cai et al., 2014

TGA Onset: 288 TGA Onset: 278 TGA Tmax: 337

Zhang et al., 2012

TGA Tmax: 340 TGA Tmax: 343 TGA Tmax: 305 TGA Tmax: 309 TGA Tmax: 308

Ferreira et al., 2014

TABLE A.9.5 Thermal Properties of Starch-Based Films Taking Into Account the Preparation Technique and the Strategies for Improvement Method

Starch

Formulation

Strategy to Improve

Plasticizer and Eq. RH

Thermal Properties (ºC)

Reference

Cassava starch

TPS

Organic filler.

Gly: 30% Eq. HR: 60%

Tgβ: −45 ± 4, Tgα: 27 ± 8

Tm: 155 ± 10

Versino et al., 2015

TPS + cassava bagasse (98.5/1.5)

Tgβ: −45 ± 5, Tgα: 46 ± 8

Tm: 219.1 ± 0.9

TPS + cassava root peel (98.5/1.5)

Tgβ: −48 ± 5, Tgα: 77 ± 8

Tm: 187 ± 3

TGA Onset: 296

TGA Tmax: 319

TGA Onset: 311

TGA Tmax: 311

TGA Onset: 306

TGA Tmax: 306

TGA Onset: 290

TGA Tmax: 300

TGA Onset: 310

TGA Tmax: 340

TGA Onset: 310

TGA Tmax: 341

TPS

Organic filler.

TPS/Coconut fiber (80/20)

Gly: 30% Eq. RH: N.R.

TPS/Coconut fiber (70/30) Potato starch

TPS TPS/PLA (60/40) TPS/PLA (60/40) + Na-MMT (1%)

Rice starch

TPS TPS/CF (90/10) TPS/LDPE (70/30)

Blends with synthetic biodegradable polymers. Inorganic filler.

Gly: 30% Eq. RH: N.R.

Blends with nonbiodegradable plastics Organic filler. Compatibilizer.

Gly: 50% Eq. RH: 50%

TGA Onset: 301 TGA Onset: 303 TGA Onset: 301

Lomelí-Ramírez et al., 2014

Ayana et al., 2014

Prachayawarakorn et al., 2010

TABLE A.9.6 Mechanical, Thermal, and Barrier Properties and Degradation in Soil of Conventional Polymers and Typical Biodegradable Polymers (Continued) Polymer

Properties Mechanical

Thermal (ºC)

WVP

O2P

CO2P

(g/(day·Pa·m)

(cm3 m−1·s·Pa)

(cm3 m−1·s·Pa)

Soil Degradation

HDPE

TM: 862 MPa TS: 21-52 MPa %ε: 10%–500% Harper (ed. 2004)

Tm: 205–280 Harper (ed. 2004)

(1.16–2.52) × 10−9 (90% RH, 25 µm) Harper (ed. 2004)

(0.13–1.12) × 10−11 (0% RH, 25 µm) Harper (ed. 2004)

(1.12–2.90) × 10−11 (0% RH, 25 µm) Harper (ed. 2004)

0% mass loss in 2 years Bastioli (ed. 2005)

LDPE

TM: 138–278 MPa TS: 8.3–17.2 MPa %ε: 225%–600% Harper (ed. 2004)

Tm: 180–280 (Harper, 2004) Tg: −30 Bastioli (ed. 2005)

4.66 × 10−9 (90% RH, 25 µm) Harper (ed. 2004)

(1.12–3.78) × 10−11 (0% RH, 25 µm) Harper (ed. 2004)

(2.25–22.5) × 10−11 (0% RH, 25 µm) Harper (ed. 2004)

Molecular weight decrease after 32–37 years Ohtake, Kobayashi, Asabe, Murakami, & Ono, 1998

LLDPE

TM: 172 MPa TS: 24–55 MPa %ε: 400%–800% Harper (ed. 2004)

Tm: 160–280 (Harper, 2004) Tg: −122 to − 20.5 Yam (ed. 2009)

4.66 x 10−9 (90% RH, 25 µm) Harper (ed. 2004)

(1.12–3.78) × 10−11 (0% RH, 25 µm) Harper (ed. 2004)

(2.25–22.5) × 10−11 (0% RH, 25 µm) Harper (ed. 2004)

PP

TS: 81.4 MPa TM: 2760 MPa (Harper, 2004) %ε: 35%–475% Yam (ed. 2009)

Tm: 220–225 Harper (ed. 2004) Tg: −14 to 5 Yam (ed. 2009)

Oriented: 1.50 × 10−9 (25 µm, 90% RH) Nonoriented: 3.76 × 10−9 (25 µm, 90% RH) Harper (ed. 2004)

Oriented: 0.72 × 10−11 (25 µm, 90% RH) Nonoriented: 1.07 × 10−11 (25 µm, 90% RH) Harper (ed. 2004)

Oriented: (1.35–2.43 × 10−11 Nonoriented: (2.25–3.6) × 10−11 (25ºC) Yam (ed. 2009)

3% CO2 in 12 weeks Bastioli (ed. 2005)

PS

EM: 2.800 MPa TS: 45 MPa TM: 3100 MPa Harper (ed. 2004)

Tg: 83–94 Yam (ed. 2009)

3.34 × 10−6 (25 µm) Harper (ed. 2004)

(1.12–18) × 10−8 Yam (ed. 2009)

(3.14–6.7) × 10−8 Yam (ed. 2009)

No degradation after 32 years Albertsson & Karlsson 1988

TABLE A.9.6 Mechanical, Thermal, and Barrier Properties and Degradation in Soil of Conventional Polymers and Typical Biodegradable

Polymers Polymer

Properties Mechanical

Thermal (ºC)

WVP

O2P

(g/(day·Pa·m) −9

3

CO2P −1

3

(cm m ·s·Pa)

Soil Degradation −1

(cm m ·s·Pa) −9

8.67 × 10−13 (oriented polymer) Yam (ed. 2009)

PET

TS: 159 MPaTM: 9960 MPaUE: 30%–300% Harper (ed. 2004)

Tm: 212–265°C Harper (ed. 2004)

6.9 × 10 Yam (ed. 2009)

(1.32–1.77) × 10 Yam (ed. 2009)

Nylon 6

TS: 52 MPa TM: 2300 MPa %ε: 50%–200% Harper (ed. 2004)

Tm: 230–280 Harper (ed. 2004)

4.14 × 10−8 Yam (ed. 2009)

(8.96–13.4) × 10−11 Yam (ed. 2009)

(44.8–53.7) × 10−11 Yam (ed. 2009)

EVOH

TS: 71.6 MPa EM: 2647 MPa %ε: 230% (Ethylene content: 32 mol% Yam (ed. 2009)

Tm: 156–196 (24–48 mol % ethylene content) Yam (ed. 2009)

5.5 × 10−9 (40ºC, 90% RH, 44 mol% ethylene) 14.7 × 10−9 (40ºC, 90% RH, 32 mol% ethylene) Yam (ed. 2009)

4.48 x 10−15 (23ºC, aw: 0) 134 x 10−15 (23ºC, aw: 0.95) Bastioli (ed. 2005)

Oriented: 4.5 x 10−15 (25 µm, 70 % RH, 32 mol% ethylene) Oriented: 4.5 x 10−14 (25 µm, 90 % RH, 44 mol% ethylene) Harper (ed. 2004)

PVOH

TS: 36 MPa (Extruded, 25ºC) %ε: 225% (Extruded, 25ºC) Mark (ed. 1999)

Tm: 200ºC Mark (ed. 1999)

4.5 x 10−13 (38ºC, 90% RH) Yam (ed. 2009)

2.65 × 10−11 (24ºC) Yam (ed. 2009)

2.7 × 10−15 (Dry conditions) Yam (ed. 2009)

8% mass loss in 2 years Bastioli (ed. 2005)

PLA

TM: 3834 MPa FM: 3689 %ε: 4% Bastioli (ed. 2005) EM: 8.6 MPa Yam (ed. 2009)

Tm: 184 Tg: 60 Bastioli (ed. 2005)

1.51 ± 0.04 × 10−6 (25ºC) Yam (ed. 2009)

1.7 ± 0.09 × 10−12 (25ºC) Yam (ed. 2009)

3.88 ± 0.07 × 10−12 (25ºC) Yam (ed. 2009)

14% CO2 in 45 days McCarthy, Ranganthan & Ma 1999

~15% CO2 in 2 years ISO 2007

(Continued)

TABLE A.9.6 Mechanical, Thermal, and Barrier Properties and Degradation in Soil of Conventional Polymers and Typical Biodegradable Polymers (Continued) Polymer

Properties Mechanical

Thermal (ºC)

WVP

O2P

CO2P

(g/(day·Pa·m)

(cm3 m−1·s·Pa)

(cm3 m−1·s·Pa)

PCL

EM: 304 ± 11 TSy: 18 ± 1 MPa % ε: > 1000% % εy: 13 ± 4% Ortega-Toro, CollazoBigliardi, Talens, & Chiralt, 2015a

Tm: 63.5 ± 0.6 Tc: 12.6 ± 0.6 Ortega-Toro et al., 2015a

2.88 ± 0.9 × 10−6 (25ºC, 53% RH) Ortega-Toro et al., 2015a

PHB

TS: 40 MPa FM: 3500 MPa % ε: 8% Bastioli (ed. 2005)

Tm: 180 Tg: 4 Bastioli (ed. 2005)

1.9 × 10−13 (23ºC, 50% RH) Petersen, Nielsen & Olsen 2001

5.12 × 10−12 (23ºC, 50% RH) Petersen et al., 2001

MaterBi: corn starch A

TS: 9 ± 1 MPa TeS: 480 ± 123 MPa % ε: 23 ± 7% (thickness: 20 µm) Petersen et al., 2001

3.7 × 10−9 (23°C and 50% RH) Petersen et al., 2001

9.9 × 10−12 (23ºC, 0% RH oxygen and 75% RH nitrogen) Petersen et al., 2001

1.35 × 10−10 (23ºC, 0% RH oxygen and 75% RH nitrogen) Petersen et al., 2001

MaterBi: corn starch B

TS: 18 ± 2 MPa TeS: 145 ± 42 MPa % ε: 6 ± 0% (thickness: 20 µm) Petersen et al., 2001

6.9 × 10−12 (23ºC, 0% RH oxygen and 75% RH nitrogen) Petersen et al., 2001

0.84 × 10−10 (23ºC, 0% RH oxygen and 75% RH nitrogen) Petersen et al., 2001

Soil Degradation

95% mass loss in 1 year PCL/starch blend: 48% mass loss in 40 days Bastioli (ed. 2005)

~97% mass loss in 2 years Calmon, Guillaume, Bellon, Feuilloley, & Silvestre, 1999

EM, elastic modulus; ε, elongation at break point; εy, elongation at yield point; FM, flexural modulus; Tc, crystallization temperature; TeS, tear strenght; Tg, glass transition temperature; TM, tensile modulus; Tm, melting temperature; TS, tensile strength; TSy, tensile strength at yield point; UE, ultimate elongation.

Future of Starch-Based Materials in Food Packaging  Chapter | 9  305

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Index

Note: Page numbers followed by “f” and “t” refer to figures and tables, respectively.

A

Acetic anhydride, 101–103 Acetone, 81–82 Acetylation/acetylated starch, 83, 84f, 101–104 acetic anhydride, 101–103 Black bean starch, 101 Musa AAB (poovan banana), 101 Pinto bean starch, 101 Acetyl tributyl citrate (ATBC), 278–279 Acid conversion, 87–88 Acid hydrolysis, 108–109 Acrylonitrile, and polysaccharides, 81. See also Cyanoethyl starches Active packaging, 231, 236t–237t bio-based materials, 238 cassava, 238–239 petroleum-based materials, 238 starches, 238–239 WVP, 238–239 Additives, 204–205 Aesculus hippocastanum seed starch (AH), 269 Ageless Eye, 239–241 Agriculture, starch-based materials in, 260 Alcohols butyl, 81–82 isopropyl, 81–82 methyl, 81–82 Alkyl groups, 82 Amylomaize, 20 Amylopectin, 20 chain-length distribution of, 1 chemical structures of, 191f crystalline, 20 lamella, 2–4 starch-based materials, 260–261, 261f Amylose, 20 chemical structures of, 191f “cluster” model, 2–4 crystalline, 20

glucose units, 2–4 starch-based materials, 260–261, 261f Amylose/amylopectin ratios, 198–199 Annealing, 92–93, 109 gelatinization, 9–10 glass transition temperature, 92–93 Araucaria araucana seed starch (AA), 269 Ascorbic acid, 104 Atomic force microscopy (AFM), 1–2

B

Bacterial cellulose nanowhiskers (BCNW), 242–244 Ball milling, 93 Basmati (BC) rice starch, 103–104 BCNW. See Bacterial cellulose nanowhiskers (BCNW) Bentonite, 125–126 Bio-based materials, 19–29 active packaging, 238 packaging and, 33–34. See also Packaging processing routes, 24f, 24t Biodegradable materials, feedstock for, 29–31 Biodegradable polymers, blends, 159–169, 160t poly-3-hydroxybutyrate (PHB), 165–167 poly(butylene adipate-co-terephthalate) (PBAT), 167–168 poly(lactic acid) (PLA), 163–165 poly(vinyl) alcohol (PVA), 159–162 Biodegradation of modified starches, 113–114 Biologically modified starch, 94–95, 94t genetic modification, 95 Biomedical uses, starch-based materials, 283 Bioplastics, 258 described, 259 European Bioplastics Association on, 259 Biopolymers, 22 Bisphenol A diglycidyl ether (DGEBA), 279

313

314  Index Black bean starch, 101 Blending, 206–207, 207f Blends biodegradable polymers, 159–169, 160t poly-3-hydroxybutyrate (PHB), 165–167 poly(butylene adipate-co-terephthalate) (PBAT), 167–168 poly(lactic acid) (PLA), 163–165 poly(vinyl) alcohol (PVA), 159–162 compatibilizers/compatibilization, 169–178 cassava, 172 chemical, 169 cocontinuous microstructures, 170 grafting, 170–171 graft modification of polyolefins with maleic anhydride, 170 interfacial tension, 172 LDPE-LLDPE-TPS, 174 maleated polymers, 171 morphological properties, 169–170 nonbiodegradable synthetic polymer, 171–172 PE-g-MA, 172–173 reactive, 171 immiscible, 169 miscible, 169 overview, 153–155 starch-based materials, 273–279 natural biopolymers, 274–275, 274f nonbiodegradable plastics, 277–279 synthetic biodegradable polymers, 275–277, 276f synthetic polymers, 155–159, 160t Botanical sources, starch, 1, 2f, 4 dry milling, 8 water recirculation, 8 wet milling, 7–8 Butyl alcohol, 81–82

C

Carbonic starches, 82 quaternary ammonium starch ether, 82 tertiary aminoalkyl starch ether, 82 Carboxymethylation, 81–82 Carboxymethyl cellulose (CMC), 33, 279 Cassava active packaging, 238–239 acylation, 103 compatibilizers/compatibilization, 172 crosslinking, 33 genetic transformation of, 95 organic fillers, 144–145 Cassava starch films, intelligent packaging, 241

Cationizing reagents, 82 Chemically treated starches, 101–109 acetylation/esterification, 101–104 acid hydrolysis, 108–109 cross-linking, 106 enzymatic hydrolysis, 109 graft copolymerization, 106–107 hydroxypropylated starches, 105–106 oxidation, 107–108 surface modification, 104–105 Chemical modification combination, 90–91 cross-linked with oxidized starches, 91 hydroxypropylated with cross-linked starches, 91 conversion, 87–90 acid, 87–88 defined, 87 dextrinization, 89 enzymatic, 89–90, 90f oxidized hypochlorite, 88 pyroconversion, 89, 89f derivatization. See Derivatization extrinsic factors affecting, 78–79 extrusion, 205–206 overview, 77, 79f principal methods, 79 reagents, 78–79 starch, 6f, 12–15 Chitosan montmorillonite (MMT), 131–132 packaging, 244–246 3-Chloro-2-hydroxypropyltrimethylammoni um, 82 Chloroplasts, 1 Clay surface modification, 131 Clostridium perfringens, 242–244 CMC. See Carboxymethyl cellulose (CMC) Cocontinuous microstructures, 170 Coextrusion, 265 Combination, chemical modification, 90–91 cross-linked with oxidized starches, 91 hydroxypropylated with cross-linked starches, 91 Compatibilizers/compatibilization agents, 131 blends and, 169–178 cassava, 172 chemical, 169 cocontinuous microstructures, 170 grafting, 170–171 graft modification of polyolefins with maleic anhydride, 170

Index  315 interfacial tension, 172 LDPE-LLDPE-TPS, 174 maleated polymers, 171 morphological properties, 169–170 nonbiodegradable synthetic polymer, 171–172 PE-g-MA, 172–173 reactive, 171 packaging, 244–246 starch-based materials, 279–282 Composites characterization methods, 128 formulations of, 128 mechanical performance, 125–126 mineral particles, 129–141 overview, 125–128 properties, 125–126, 128–129 starch-based materials, 51–53 blends, 52–53 fillers, 51–52 Compression molding, 214–216, 215f starch-based materials, 263 advantage of, 263 flashing, 263 thermosetting resins, 263 Conversion, 12–14, 87–90. See also Chemical modification acid, 87–88 defined, 87 dextrinization, 89 enzymatic, 89–90, 90f oxidized hypochlorite, 88 pyroconversion, 89, 89f Cornstarches, 105–106 Cross-linking, 33, 78, 247–248 CMC, 33 derivatization, 86–87, 87f hydroxypropylated starches with, 91 modification, 102 oxidized starches with, 91 sodium trimetaphosphate, 33 Crystallinity, 20, 21t Cush-cush yam, 33 Cyanoethyl starches, 81

D

Depolymerization of starch. See Conversion Derivatization carbonic starches, 82 quaternary ammonium starch ether, 82 tertiary aminoalkyl starch ether, 82 carboxymethylation, 81–82

cross-linking, 86–87, 87f defined, 79 esterification, 83–86 acetylate starch, 83, 84f octenyl succinate starch, 84, 85f phosphate monoesters, 85–86, 86f succinate starch, 84, 85f etherification, 80–81 cyanoethyl starches, 81 hydroxyethylated starch, 80, 80f hydroxypropylated starches, 81, 81f reactions, 79 Dextrinization, 89 DGEBA. See Bisphenol A diglycidyl ether (DGEBA) Diethylaminoethyl chloride, 82 Differential scanning calorimetry analysis, 244–246 Disodium hydrogen phosphate, 85–86 Distarch phosphate, 85–86 Dodecenyl succinic anhydride (DDSA), 105 Drug delivery applications, 283 Dry milling, 8 Dual-modified starches, 110–111

E

Elastic properties, plasticized starch melts, 199–200 extensional viscosity, 199–200 normal stress difference, 199–200 Trouton ratio, 199–200 Electrospraying, 201 El Mercado Común del Sur, 231 Enzymatic conversion, 89–90, 90f Enzymatic hydrolysis, 109 Escherichia coli, 242–244 Esterification, 83–86, 101–104. See also Derivatization acetylate starch, 83, 84f octenyl succinate starch, 84, 85f phosphate monoesters, 85–86, 86f succinate starch, 84, 85f Esterification modification, 33 Etherification, 80–81. See also Derivatization cyanoethyl starches, 81 hydroxyethylated starch, 80, 80f hydroxypropylated starches, 81, 81f Etherification reaction, 80, 80f Ethylene oxide, 80, 80f European Bioplastics Association, 259 European Food Safety Authority, 231 Extensional viscosity, 199–200

316  Index Extruders. See also Extrusion single-screw extruder (SSE), 202 films/sheets or foams, 203 twin-screw extruder (TSE), 202 plasticized starch resins, 203 schematic representation, 203, 204f Extrusion, 202–214 extruders, 202–203 schematic representation, 202, 203f starch-based materials process, 263–264 reactive, 264–265 strategies and issues, 204–208 additives, 204–205 blending, 206–207, 207f chemical modification, 205–206 molecular degradation, 208 plasticizer, 204–205 techniques, 208–214 film blowing, 210–212, 212f film casting, 208–210, 209t, 211f foaming, 213 reactive extrusion (REX), 213–214

F

Fillers, 51–52, 125–126. See also Composites mineral, 125–127 organic, 141–147 renewable, 127 starch matrix and, 131 Film blowing, 210–212, 212f starch-based materials, 267 Film casting, 208–210, 209t, 211f Flashing, 263 Flory–Huggins equation, 244–246 Foaming, 213 Foaming technology, 248 Food additives, 279–282 Food Agricultural Organization, 249 Food packaging active, 231, 236t–237t bio-based materials, 238 cassava, 238–239 petroleum-based materials, 238 starches, 238–239 WVP, 238–239 intelligent, 239–241 cassava starch films, 241 described, 239 as electronic label, 239 modified atmosphere packaging (MAP), 239–241 needs driving, 239

RFID tags, 239–241 TTI, 239–241 materials and food packages, commercialized, 232t–235t modified starches used for, 111–114 advantages, 112 biodegradation, 113–114 toxic concerns, 113 oxygen permeability, 32 starch-based materials, 241–248, 260 advantages and disadvantages, 248–249 chitosan, 244–246 compatibilization approach, 244–246 differential scanning calorimetry analysis, 244–246 foaming technology, 248 hydroxyl groups, 241–242, 247–248 microwave radiation, 246–247 plasticizers, 242–244 polymer blending, 244–246 ultrasonic waves, 246–247 yerba mate, 242–244 vegetables, 249–250 water vapor, 32 Food Sentinel System, 239–241, 240f

G

Gelatinization, 11t, 22 annealing, 9–10 microscopy observation, 9 in phase transition to plasticized starch, 189–191, 192f retrogradation, 10–12 Genetic engineering, 95 Genetic modification, 95 Glass, for food packaging, 229 Graft copolymerization, 106–107 Grafting, 170–171 Graft modification, 170 Granules, starch, 1 atomic force microscopy (AFM), 1–2 Maltase cross, 4 molecular features, 5–6 projection of, 3f scanning electron microscopy (SEM), 1–2 semicrystalline rings, 6–7 size distribution, 1 structural characteristics, 4–7 X-ray diffraction (XRD), 4–5

H

Hansen solubility parameters, 244–246 High-density polyethylene (HDPE), 238

Index  317 Hydrogen monosodium phosphate, 85–86 Hydrogen peroxide, 107 Hydrophilic nature, starch-based materials, 39–42 Hydrophilic polymers, 22 Hydroxyethylated starch, 80, 80f Hydroxyl groups, 22, 241–242 packaging, 241–242, 247–248 Hydroxypropylated rice starch (HPRS), 105 Hydroxypropylated starches, 81, 81f advantages of, 81 with cross-linked starches, 91 modification, 105–106 Hydroxypropylated waxy corn, 105–106 Hydroxypropylation of high amylose starch, 229–230 Hylon VII, 105–106

I

Immiscible polymer blends, 244–246 Indirect food additive, 279 Injection molding starch-based materials, 266, 283 starch processing, 216 “In-line” measurements, 195–197 Intelligent packaging, 239–241 cassava starch films, 241 described, 239 as electronic label, 239 modified atmosphere packaging (MAP), 239–241 needs driving, 239 RFID tags, 239–241 TTI, 239–241 Irri (IC) rice starch, 103–104 Isopropyl alcohol, 81–82

K

Kaolinite, 126–127

L

Laboratory scale, starch processing, 201–202 electrospraying, 201 plasticizers, 201 LDPE (low-density PE), 156 cornstarch, 157–158 film packaging applications, 156 hydrophobic, 156 TPS, 157–158 LDPE-LLDPE-TPS, 174 Listeria monocytogenes, 242–244 LLDPE (linear low-density PE), 156 TPS films blends, 158

Low-density polyethylene (LDPE), 238 Luffa fibers, 142

M

Maleated polymers, 171 Maleated thermoplastic starch (MTPS), 99–100 Maleic anhydride (MA), 100, 244–246 Maleic anhydride esterified cornstarch, 33 Maltase cross, 4 Mars Chocolate, 229–230 Mechanical properties, starch-based materials, 42–46 enhancement of, 53–59 Metal, for food packaging, 229 Methyl alcohols, 81–82 Micrographs, 131 Microscopy observation, 9 Microstructural changes, 199f Microwave radiation, 246–247 Mineral fillers, 125–127 Modification methods, starch-based materials, 47–50 Modified atmosphere packaging (MAP), 239–241 Modified starch applications of, 112t chemically treated, 101–109, 102t acetylation/esterification, 101–104 acid hydrolysis, 108–109 cross-linking, 106 enzymatic hydrolysis, 109 graft copolymerization, 106–107 hydroxypropylated starches, 105–106 oxidation, 107–108 surface modification, 104–105 dual-modified starches, 110–111 enhancing properties of, 31–34 packaging material, 111–114 advantages, 112 biodegradation, 113–114 toxic concerns, 113 physically treated, 109–110, 112t Molecular degradation, 208 Molecular features, 5–6 Montmorillonite (MMT), 125–126, 129 chitosan, 131–132 cornstarch composites, 132 hydrophilic character, 129–130 loadings of, 129–130 thermogravimetric analysis (TGA), 129–130 Morpholinoethyl, 82 Musa AAB (poovan banana), 101

318  Index

N

Nanocomposite films, 129 FETPS-EMMT, 132–133 MMT. See Montmorillonite (MMT) Nanoparticles, 31–32 Native starch. See Starch Natural cellulosic fibers, 127 Natural fibers, 127–128 NatureWorks LLC, 229–230 Nisin, 242–244 Nonbiodegradable synthetic polymer, 171–172 Nonconventional native starches, 29–31 Normal stress difference, 199–200

O

Oat starch, 29–30 Octenyl succinate starch, 84, 85f 1-Octenyl succinic anhydride (OSA), 84 Optical properties of organic fillers, 146, 146t Optimum Flour Plast, 229–230 Organic fillers, 141–147 cassava roots peel and bagasse, 144–145 FTIR spectra, 145, 145f glycerol plasticized-corn starch, 143–144 luffa fibers, 142 mechanical properties, 147t native cornstarch and lignocellulosic fiber strands, 143 optical properties of, 146, 146t SEM, 144–145, 144f thermal degradation, 145–146, 146f winceyette fibers, 142 WVP, 147, 147f Orthopedic implant devices, starch-based materials, 283 Oxidized banana starch (OBS), 108 Oxidized hypochlorite, 88 Oxidized starches/oxidation, 14, 107–108 cross-linking with, 91 hydrogen peroxide, 107 molecular structures, 107 oxidizing agents, 107–108 ozone, 108 Oxidizing agents, 107–108 Oxygen gas indicators, 239–241 Oxygen permeability, 32 Ozone, 108

P

Packaging active, 231, 236t–237t bio-based materials, 238 cassava, 238–239

petroleum-based materials, 238 starches, 238–239 WVP, 238–239 intelligent, 239–241 cassava starch films, 241 described, 239 as electronic label, 239 modified atmosphere packaging (MAP), 239–241 needs driving, 239 RFID tags, 239–241 TTI, 239–241 materials and food packages, commercialized, 232t–235t modified starches used for, 111–114 advantages, 112 biodegradation, 113–114 toxic concerns, 113 starch-based materials, 241–248, 260 advantages and disadvantages, 248–249 chitosan, 244–246 compatibilization approach, 244–246 differential scanning calorimetry analysis, 244–246 foaming technology, 248 hydroxyl groups, 241–242, 247–248 microwave radiation, 246–247 plasticizers, 242–244 polymer blending, 244–246 ultrasonic waves, 246–247 yerba mate, 242–244 vegetables, 249–250 Palmae family, 30 Pasting profile of starch, 8–9 PE-g-MA, 172–173 Pehuen starch, 30 Petroleum-based materials, active packaging, 238 Phase transition to plasticized starch, 189–191 gelatinization of, 189–191, 192f shear condition, 195, 196f shearless condition, 191–195, 193f Phosphate monoesters, 85–86, 86f Phosphorylated starch, 85–86, 86f Photosynthesis process, 1 Physically treated starches, 109–110 Physical modification, 6f, 12–15, 91–94 annealing, 92–93 glass transition temperature, 92–93 blends with other polymers, 93–94 granular cold-water soluble starch, 92 heat moisture treatment of starches (HMT), 93 mechanical milling starch, 93 pregelatinized starch, 92

Index  319 Physicochemical properties, 8–12 Pinto bean starch, 101 pKa (acid dissociation constant), 82 Plantic, 229–230 Plasticized starch melts elastic properties, 199–200 extensional viscosity, 199–200 normal stress difference, 199–200 Trouton ratio, 199–200 viscous properties, 195–199 amylose/amylopectin ratios, 198–199 “in-line” measurements, 195–197 microstructural changes, 199f rheometers, 195–197, 198f temperature or plasticizer content, 197–198 viscometer, 195–197 Plasticizers, 50–51, 204–205. See also Packaging; Starch-based materials for hydrophilic polymers, 22 laboratory scale starch processing, 201 packaging, 242–244 Plastics. See also Packaging; Thermoplastic starch (TPS) for food packaging. See Packaging global production of, 258, 259f massive use, 258 Poly-3-hydroxybutyrate (PHB), 165–167, 242–244 Poly(butylene adipate-co-terephthalate) (PBAT), 167–168 Poly(ε-caprolactone) blends, 244–246 Poly(ethylene-co-butyl acrylate-co-maleic anhydride) terpolymer, 279 Polyethylene terephthalate (PET), 238 Poly(lactic acid) (PLA), 163–165, 259 production of, 230–231 Polymer blending, 244–246 Polymers, 19 Polypropylene (PP), 238 Polysaccharides, 1, 19 acrylonitrile and, 81 Polyurethane (PU), 31 aqueous dispersion, 31–32 hydrogen bonding, 31–32 Poly(vinyl) alcohol (PVA), 159–162 Potassium hydroxide, 82 Potato starch, nanocomposite films, 129 Projection of, 3f Propylene oxide, 81, 81f Pyroconversion, 89, 89f. See also Conversion

Q

Quaternary ammonium starch ether, 82

R

Radio frequency identification (RFID) tags, 239 Reactive compatibilizers, 171 Reactive extrusion (REX), 213–214 Resistant starch (RS), 101 Retrogradation, 10–12, 283–284 Rheometers, 195–197, 198f Rice starch, succinylation, 103–104 Rodenburg Biopolymers, 229–230

S

Sam’s Club, 229–230 Scaling up process drying, 96–97 extrusion primary aim of, 98–99 problems encountered, 95 reactive extrusion (REX), 99–101 similarities, 96 singles-screw extruder (SSE), 97 twin-screw extruder (TSE), 97, 98f solution casting, 96–97 Scanning electron microscopy (SEM), 1–2 Semicrystalline rings, 6–7 Shear condition, phase transition to plasticized starch, 195, 196f Shearless condition, phase transition to plasticized starch, 191–195, 193f Simple, Inexpensive, Rapid, Accurate (SIRA) Technologies Inc., 239–241 Single-screw extruder (SSE), 202 films/sheets or foams, 203 scaling up process, 97 Size distribution, 1 Sodium monochloroacetate, 81–82 Sodium trimetaphosphate, 33 Sodium trimetaphosphate (STMP), 81 Soil burial degradation time, 33 Solanyl, 229–230 Sorbitol, 29–30 Sorghum, succinylation, 104 Staphylococcus aureus, 242–244 Starch active packaging, 238–239 botanical sources, 1, 2f, 4 dry milling, 8 water recirculation, 8 wet milling, 7–8 chemical modification, 6f, 12–15 chloroplasts, 1 commercial, 1 conversion, 12–14

320  Index Starch (Continued) degree of polymerization (DP), 189 derivatization of, 12–14 functional properties, 8–12 gelatinization, 11t, 22 annealing, 9–10 microscopy observation, 9 retrogradation, 10–12 granules, 1, 188–189, 190f atomic force microscopy (AFM), 1–2 Maltase cross, 4 molecular features, 5–6 projection of, 3f scanning electron microscopy (SEM), 1–2 semicrystalline rings, 6–7 size distribution, 1 structural characteristics, 4–7 X-ray diffraction (XRD), 4–5 as homo-polysaccharide, 2–4 overview, 1–4 oxidized, 14 pasting profile of, 8–9 phase transition. See Phase transition to plasticized starch photosynthesis process, 1 physical modification, 6f, 12–15 physicochemical properties, 8–12 polysaccharide, 1, 189 structures of, 188–189 transitory, 1 Starch-based films, 267–269 Starch-based materials amylopectin, 260–261, 261f amylose, 260–261, 261f biomedical uses, 283 blends, 273–279 natural biopolymers, 274–275, 274f nonbiodegradable plastics, 277–279 synthetic biodegradable polymers, 275– 277, 276f challenges for, 283–284 coextrusion, 265 commercial applications, 282–284 compatibilizers, 279–282 composites, 51–53 blends, 52–53 fillers, 51–52 compression molding, 263 advantage of, 263 flashing, 263 thermosetting resins, 263 extrusion process, 263–264 reactive, 264–265

film blowing, 267 food additives, 279–282 general properties, 37–47 global production of, 259–260 hydrophilic nature, 39–42 injection molding, 266 market leaders, 260 mechanical properties, 42–46 enhancement of, 53–59 modification methods, 47–50 modified starches enhancing properties of, 31–34 packaging, 241–248, 260 advantages and disadvantages, 248–249 chitosan, 244–246 compatibilization approach, 244–246 differential scanning calorimetry analysis, 244–246 foaming technology, 248 hydroxyl groups, 241–242, 247–248 microwave radiation, 246–247 plasticizers, 242–244 polymer blending, 244–246 ultrasonic waves, 246–247 yerba mate, 242–244 plasticizers, 50–51, 279–282 processability, 46–47 enhancement of, 62–64 processing of, 262 properties factors affecting, 262 organic and inorganic fillers, 271–273 starch modification, 269–271 strategies improving, 259–260 water stability enhancement of, 59–61 Starch foaming technology, 248 Starch processing compression molding, 214–216, 215f extrusion, 202–214 extruders, 202–203 schematic representation, 202, 203f strategies and issues, 204–208 techniques, 208–214 injection molding, 216 laboratory scale, 201–202 electrospraying, 201 plasticizers, 201 overview, 187–188 STMP. See Sodium trimetaphosphate (STMP) Strategies and issues, extrusion for starch processing, 204–208 additives, 204–205 blending, 206–207, 207f

Index  321 chemical modification, 205–206 molecular degradation, 208 plasticizer, 204–205 Stress-strain curves, 131–132 Structural characteristics, 4–7 Succinate starch, 84, 85f, 103–104 Sugar palm starch (SPS), 30–31 Sugar palm tree, 30 Synthetic polymers blends, 155–159, 160t nonbiodegradable, 171–172

T

Talc, 126–127 Temperature or plasticizer content, 197–198 Tertiary aminoalkyl starch ether, 82 TGA. See Thermal gravimetric analysis (TGA) Thermal degradation, organic fillers, 145–146, 146f Thermal gravimetric analysis (TGA), 129–130, 268–269 Thermoplastic corn starch, 107 Thermoplastic cornstarch (TPCS), 242–244 oxidized starch, 247–248 Thermoplastic quinoa starch (TPQS), 242–244 antimicrobial efficacy, 242–244 Thermoplastic starch (TPS), 230–231, 259–262 blends, 159–169, 160t. See also Blends poly-3-hydroxybutyrate (PHB), 165–167 poly(butylene adipate-co-terephthalate) (PBAT), 167–168 poly(lactic acid) (PLA), 163–165 poly(vinyl) alcohol (PVA), 159–162 chemical modifications, 246–247 compatibilization, 244–246 drawbacks of, 77, 244 maleic anhydride (MA), 244–246 modification, 104 physical modifications, 246–247 plasticizers, 23, 242–244 polymer blending, 244 residual lignocellulosic fibers, 30 surface modification, 104 Thermoplastic sugar palm starch (TPSPS), 242–244 Thermosetting resins, 263

Timestrip, 239–241 Time-temperature indicators (TTI), 239–241 Toxic concerns, 113 TPCS. See Thermoplastic cornstarch (TPCS) TPCS-poly(ε-caprolactone) blends, 244–246 plasticizers, 244–246 WVP of, 244–246 Transitory starch, 1 Trellis Bioplastics, 229–230 Trouton ratio, 199–200 Twin-screw extruder (TSE), 202 plasticized starch resins, 203 scaling up process, 97, 98f schematic representation, 203, 204f

U

Ultrasonic waves, 246–247

V

Viscometer, 195–197 Viscous properties, of plasticized starch melts, 195–199 amylose/amylopectin ratios, 198–199 “in-line” measurements, 195–197 microstructural changes, 199f rheometers, 195–197, 198f temperature or plasticizer content, 197–198 viscometer, 195–197

W

Wal-Mart, 229–230 Water recirculation, 8 Water stability, 59–61 Water vapor, 32 Water vapor permeability (WVP), 238–239 active packaging, 238–239 organic fillers, 147, 147f Waxy maize, 20 nanocrystals, 32 Wet milling, 7–8 Winceyette fibers, 142

X

X-ray diffraction (XRD), 4–5, 99

Y

Yerba mate, 242–244