Tai Lieu Chat Luong BIOPOLYMER NANOCOMPOSITES WILEY SERIES ON POLYMER ENGINEERING AND TECHNOLOGY Richard F Grossman and Domasius Nwabunma, Series Editors Polyolefin Blends / Edited by Domasius Nwabunma and Thein Kyu Polyolefin Composites / Edited by Domasius Nwabunma and Thein Kyu Handbook of Vinyl Formulating, Second Edition / Edited by Richard F Grossman Total Quality Process Control for Injection Molding, Second Edition / M Joseph Gordon, Jr Microcellular Injection Molding / Jingyi Xu Poly(lactic acid): Synthesis, Structures, Properties, Processing, and Applications / Edited by Rafael Auras, Loong-Tak Lim, Susan E M Selke, and Hideto Tsuji Hyperbranched Polymers: Synthesis, Properties, and Applications / Edited by Deyue Yan, Chao Gao, and Holger Frey Advanced Thermoforming: Methods, Machines and Materials, Applications and Automation / Sven Engelmann Biopolymer Nanocomposites: Processing, Properties, and Applications / Edited by Alan Dufresne, Sabu Thomas, and Laly A Pothan BIOPOLYMER NANOCOMPOSITES PROCESSING, PROPERTIES, AND APPLICATIONS Edited By Alain Dufresne Grenoble Institute of Technology (Grenoble INP) The International School of Paper Print Media, and Biomaterials (Pagora) Saint Martin d’Hères Cedex, France Sabu Thomas School of Chemical Sciences Mahatma Gandhi University Kottayam, Kerala, India Laly A Pothan Department of Chemistry Bishop Moore College Mavelikara, Kerala, India Copyright © 2013 by John Wiley & Sons, Inc All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permissions Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by sales representatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You should consult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002 Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Library of Congress Cataloging-In-Publication Data: Biopolymer nanocomposites : processing, properties, and applications / edited by Alain Dufresne, Sabu Thomas, Laly A Pothan pages cm Includes index ISBN 978-1-118-21835-8 (hardback) Biopolymers Nanocomposites (Materials) I Dufresne, Alain, 1962– editor of compilation II Thomas, Sabu, editor of compilation III Pothan, Laly A, editor of compilation TP248.65.P62B5457 2013 572–dc23 2013002843 Printed in the United States of America 10 CONTENTS Foreword vii Contributors ix Bionanocomposites: State of the Art, Challenges, and Opportunities Alain Dufresne, Sabu Thomas, and Laly A Pothan Preparation of Chitin Nanofibers and Their Composites 11 Shinsuke Ifuku, Zameer Shervani, and Hiroyuki Saimoto Chemical Modification of Chitosan and Its Biomedical Application 33 Deepa Thomas and Sabu Thomas Biomimetic Lessons for Processing Chitin-Based Composites 53 Otto C Wilson, Jr and Tiffany Omokanwaye Morphological and Thermal Investigations of Chitin-Based Nanocomposites 83 Ming Zeng, Liyuan Lu, and Qingyu Xu Mechanical Properties of Chitin-Based Nanocomposites 111 Merin Sara Thomas, Laly A Pothan, and Sabu Thomas Preparation and Applications of Chitin Nanofibers/Nanowhiskers 131 Jun-Ichi Kadokawa Preparation of Starch Nanoparticles 153 Déborah Le Corre and Alain Dufresne Chemical Modification of Starch Nanoparticles 181 Jin Huang, Qing Huang, Peter R Chang, and Jiahui Yu 10 Starch-Based Bionanocomposite: Processing Techniques 203 Rekha Rose Koshy, Laly A Pothan, and Sabu Thomas 11 Morphological and Thermal Investigations of Starch-Based Nanocomposites 227 Peter R Chang, Jin Huang, Qing Huang, and Debbie P Anderson 12 Mechanical Properties of Starch-Based Nanocomposites 261 Hélène Angellier-Coussy and Alain Dufresne v vi CONTENTS 13 Applications of Starch Nanoparticles and Starch-Based Bionanocomposites 293 Siji K Mary, Laly A Pothan, and Sabu Thomas 14 Preparation of Nanofibrillated Cellulose and Cellulose Whiskers 309 David Plackett and Marco Iotti 15 Bacterial Cellulose 339 Eliane Trovatti 16 Chemical Modification of Nanocelluloses 367 Youssef Habibi 17 Cellulose-Based Nanocomposites: Processing Techniques 391 Robert A Shanks 18 Morphological and Thermal Investigations of Cellulosic Bionanocomposites 411 Anayancy Osorio-Madrazo and Marie-Pierre Laborie 19 Mechanical Properties of Cellulose-Based Bionanocomposites 437 B Deepa, Saumya S Pillai, Laly A Pothan, and Sabu Thomas 20 Review of Nanocellulosic Products and Their Applications 461 Joe Aspler, Jean Bouchard, Wadood Hamad, Richard Berry, Stephanie Beck, Franỗois Drolet, and Xuejun Zou 21 Spectroscopic Characterization of Renewable Nanoparticles and Their Composites 509 Mirta I Aranguren, Mirna A Mosiewicki, and Norma E Marcovich 22 Barrier Properties of Renewable Nanomaterials 541 Vikas Mittal 23 Biocomposites and Nanocomposites Containing Lignin 565 Cornelia Vasile and Georgeta Cazacu 24 Preparation, Processing and Applications of Protein Nanofibers 599 Megan Garvey, Madhusudan Vasudevamurthy, Shiva P Rao, Heath Ecroyd, Juliet A Gerrard, and John A Carver 25 Protein-Based Nanocomposites for Food Packaging 613 Hélène Angellier-Coussy, Pascale Chalier, Emmanuelle Gastaldi, Valérie Guillard, Carole Guillaume, Nathalie Gontard, and Stéphane Peyron Index 655 FOREWORD It is important to minimize the environmental impact of materials production by decreasing the environmental footprint at every stage of their life cycle Therefore, composites where the matrix and reinforcing phase are based on renewable resources have been the subject of extensive research These efforts have generated environmental friendly applications for many uses such as for automotive, packaging, and household products to name some Cellulose is the most abundant biomass on the earth and its use in the preparation of biobased nanomaterials has gained a growing interest during the last ten years This interest can be illustrated by how the number of scientific publications on the cellulose nanomaterial research has grown very rapidly and reached more the 600 scientific publications during 2011 The research topics have been extraction of cellulose nanofibers and nanocrystals from different raw material sources, their chemical modification, characterization of their properties, their use as additive or reinforcement in different polymers, composite preparation, as well as their ability to self-assemble Nanocelluloses, both fibers and crystals, have been shown to have promising and interesting properties, and the abundance of cellulosic waste residues has encouraged their utilization as a main raw material source Cellulose nanofibers have high mechanical properties, which combined with their enormous surface area, low density, biocompatibility, biodegradability, and renewability make them interesting starting materials for many different uses, especially when combined with biobased polymers Since bionanocomposites are a relatively new research area, it is necessary to further develop processing methods to make these nanomaterials available on a large scale, so that new applications based on them can be developed Information about this emerging research field could also prove to be a catalyst and motivator not only for industries but also to a large number of students and young scientists A matrix of tools that could aid such work could be developed through research enterprise The book Biopolymer Nanocomposites: Processing, Properties, and Applications by Alain Dufresne, Sabu Thomas, and Laly A Pothan, as the authors themselves have pointed out elsewhere, “is an attempt to introduce various biopolymers and bionanocomposites to a student of materials science Going beyond mere introduction, the book delves deep into the characteristics of various biopolymers and bionanocomposites and discusses the nuances of their preparation with a view to vii viii FOREWORD helping researchers find out newer and novel applications.” Students, researchers, and industrialists in the field of biocomposites will be greatly benefitted by this book since its chapters are authored by an impressive array of prominent current researchers in this field Sincere attempts like this at promoting the use of green materials for sustainable growth of humanity should be lauded indeed Kristiina Oksman Luleå University of Technology CONTRIBUTORS Debbie P Anderson, Bioproducts and Bioprocesses National Science Program, Agriculture and Agri-Food Canada, Saskatoon, SK, Canada Hélène Angellier-Coussy, UnitéMixte de RechercheIngénierie des Agropolymères et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Université Montpellier II, Montpellier Cedex, France Mirta I Aranguren, INTEMA-CONICET, Facultad de Ingeniería-Universidad Nacional de Mar del Plata, Mar del Plata, Argentina Joe Aspler, FPInnovations, Pointe Claire, QC, Canada Stephanie Beck, FPInnovations, Pointe Claire, QC, Canada Richard Berry, FPInnovations, Pointe Claire, QC, Canada Jean Bouchard, FPInnovations, Pointe Claire, QC, Canada John A Carver, School of Chemistry and Physics, The University of Adelaide, Adelaide, SA, Australia; Research School of Chemistry, Australian National University, ACT, Australia Georgeta Cazacu, PetruPoni” Institute of Macromolecular Chemistry, Physical Chemistry of Polymers Department, Ghica Voda Alley, Iasi, Romania Pascale Chalier, Unité Mixte de Recherche Ingénierie des Agropolymères et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Université Montpellier II, Montpellier Cedex, France Peter R Chang, Bioproducts and Bioprocesses National Science Program, Agriculture and Agri-Food Canada, Saskatoon, SK, Canada; Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon, SK, Canada B Deepa, Department of Chemistry, Bishop Moore College, Mavelikara, Kerala, India; Department of Chemistry, C.M.S College, Kottayam, Kerala, India Franỗois Drolet, FPInnovations, Pointe Claire, QC, Canada Alain Dufresne, Grenoble Institute of Technology (Grenoble INP), The International School of Paper, Print Media, and Biomaterials (Pagora), Saint Martin d’Hères Cedex, France ix 678 INDEX Semicontinuous processing, bacterial cellulose production, 343–344 Shaking cultivation, bacterial cellulose production, 343 Shrimp shells See Crustacean hard tissue Silicates See also Layered silicates chitin nanocomposites, SEM/TEM analysis, 86–93 chitosan-clay nanocomposites, 115–118 inorganic fillers, 265–267 polymer layered silicate nanocomposites: barrier properties, 548–550, 556–560 melt intercalation technique, 214–219 protein nanocomposites: isodimensional particles, 620 mechanical properties, 628–632 starch-based nanocomposites, 206–207, 228 inorganic reinforcements, 268–274 layered silicate nanofillers, 229–232 Silicon dioxide nanofiller, fracture morphology, 239–242 Silk fibroin, thermal analysis, differential scanning calorimetry, 98–99 Silylation, cellulose nanocomposites, 376–378 Simulated body fluid (SBF), chitin nanocomposites, 68 Single-walled carbon nanotubes (SWCNTs): elongated particles, 621 inorganic fillers, 265–267 mechanical properties, 118–122 starch nanocomposites, carbon nanoparticles, 232–234 Small angle neutron scattering (SANS), nanocellulose noncovalent surface modification, 369–371 Small molecule conjugation, starch nanocrystals, 184–189 Smectite clays: inorganic fillers, 265–267 starch-based nanocomposites, 206 Sodium hydroxide, cellulose nanocomposite solubility, 397–398 Sodium lignosulfonate (LSS), protein/ lignin bionanocomposites, 577–579 Sodium montmorillonite: chitosan-clay nanocomposites, 117–118 food industry applications, 300–302 starch/poly(vinyl alcohol)/ sodium montmorillonite nanocomposite, 210–211 Sodium trimetaphosphate (STMP): cross-linked starch nanoparticles, 191 starch nanoparticle preparation, 160 Sol-gel synthesis, starch-based nanocomposites, 228 Solubility, cellulose nanocomposites, 394–398 Solution-based regeneration, chitin nanofibers, 142–145 Solution casting (intercalation): chitin nanowhisker acid hydrolysis, 137–138 protein-based nanocomposites, 622–623 starch-based nanocomposites, 209–214 flax cellulose nanocomposites, 211–212 glycerol plasticized pea starch/ nano-ZnO composites, 210 green hemp nanocrystal reinforced composites, 212–213 starch/poly(vinyl alcohol)/sodium montmorillonite, 210–211 technology, 228 wheat cellulose nanofibers, 213–214 Soy protein isolates (SPIs): barrier properties, 557–560 chitin nanowhisker acid hydrolysis, 139–140 filler-matrix interface compatibilization, starch nanoparticles, 192–194 protein-based nanocomposites, 618–619 barrier property modulation, 637–641 dry processing, 624 mechanical properties, 628–632 INDEX protein/lignin bionanocomposites, 577–579 Specific migration limit (SML), protein nanocomposites, safety issues, 644–646 Spectroscopic analysis: bacterial cellulose, 513–515 cellulose nanocomposites, 510, 515–518 chitin nanoparticles, 518–521 chitosan nanoparticles, 521–523 modified starch nanocomposites, 526–533 esterification, 526–531 urethane linkages, 532–533 nanocomposites, 509–536, 523–524 plant cellulose, 510–513 starch nanocomposites, 524–526 starch nanoparticles, 533–535 Squid pen β-chitin: mechanical processing, 148–149 TEMPO-mediated nanofibers, 141–142 Stannous octoate (Sn(Oct)2), cellulose nanocomposites, 381–382 Starch/cellulose acetate (SCA), biomedical applications, 302–304 Starch/ethylene vinyl alcohol (SEVA-C), biomedical applications, 302–304 Starch nanocolloids, chemical modification, 191–192 Starch nanocomposites: applications, 299–304 agricultural applications, 304 biomedical applications, 302–304 food industry, 300–302 bacterial cellulose, 354 basic properties, 206–208 cellulose nanocomposites, 207–208 as filler, 278–285 future research issues, 248–249 lignin-based composites, 579–580 manufacturing techniques, 208–209 mechanical properties, 261–286 filler properties, 278–286 nanocrystal reinforcement effects, 278–283 679 nanocrystal surface, chemical modification, 283–284 reinforcing mechanisms, 285 matrix properties, 262–278 aging, 264 amylose/amylopectin ratio, 262–263 fillers, 264–268 inorganic reinforcements, 268–274 organic reinforcements, 274–278 plasticization, 263 melt intercalation technique, 214–219 thermoplastic corn starch-reinforced cotton cellulose nanofibers, 218–219 thermoplastic starch/clay hybrids, 215–218 morphological analysis, 229–245 fracture morphologies, 238–242 matrix crystallinity, 242–243 nanofiller distribution, 229–238 carbon nanoparticles, 232–234 layered silicates, 229–232 miscellaneous nanofillers, 237–238 polysaccharide nanocrystals, 234–237 retrogradation effects, 243–245 research background, 203–205 in situ intercalative polymerization, 219–221 nanosilicate layer/polycaprolactone composites, 220–221 solution casting, 209–214 flax cellulose nanocomposites, 211–212 glycerol plasticized pea starch/ nano-ZnO composites, 210 green hemp nanocrystal reinforced composites, 212–213 starch/poly(vinyl alcohol)/sodium montmorillonite, 210–211 wheat cellulose nanofibers, 213–214 spectroscopic analysis, 524–526 structural properties, 227–228 synthetic polymer-based nanocomposites, 208 thermal behavior, 245–248 680 INDEX Starch nanocomposites (cont’d) decomposition, 246–248 glass transition temperature, 245–246 Starch nanocrystals, 161–171 acid hydrolysis kinetics, 162–164 chemical modification, 183–189 mechanical effects, 283–284 polymer grafting, 185–189 as filler, 278–285 morphology, 168–169 organic fillers, 267–268 preparation protocol, 164–168 protein-based nanocomposites, 622 protein nanocomposites, mechanical properties, 628–632 regenerated starch nanoparticles and, 171–173 small molecule conjugation, 184–189 spectroscopic analysis, 524–526 starch sources, 170–171 Starch nanoparticles (SNP): applications, 293–299 natural polymer matrices, 295–297 research background, 293–295 synthetic polymer matrices, 297–299 chemical modification, 181–196 applications, 192–195 cross-linked SNP, 191 future research issues, 195–196 nanomicelle assembly, 190–191 starch derivatives, 189–190 composition, 154 crystalline type, 156–157 current research issues, 5–9 multiscale structure, 154–156 patented nanoparticles, 160–161 preparation techniques, 153, 157–161, 157–174, 181–183 regeneration, starch nanocrystals vs., 171–173 spectroscopic analysis, 533–535 structure and properties, 153–157 Starch/poly(vinyl alcohol)/ sodium montmorillonite nanocomposite, 210–211 Static cultures, bacterial cellulose production, 342–344 Stearate-modified starch nanocrystals, esterification, 529–531 Storage modulus: cellulose nanocomposites, dynamic mechanical thermal analysis, 450–454 chitin/chitosan nanofillers, 124–127 chitosan-carbon nanotube composites, 121–122 Strain to failure, cellulose nanofibers, 438–439 Strength testing, nanofibrillated cellulose, 321 Styrene butadiene rubber (SBR), lignin-rubber composites, 581 Substrates, nanocellulose, 368–369 Succinic acid hydride, chitin nanowhisker acid hydrolysis, 138–139 Sulfuric acid, cellulose whiskers acid hydrolysis, 323–324 Supercritical solvent impregnation (SSI), chitosan drug delivery systems, 46–47 Supermicrofibrillated cellulose (SMFC), development of, 472–475 Surface chemistry: barrier performance, 560–562 nanofibrillated cellulose, 322 nanofiller fracture morphology, 241–242 starch content, 154 starch nanocomposites, layered silicate nanofillers, 230–232 Synthetic polymer matrices, starch nanofillers, 297–299 Targeted modification, starch nanoparticles, 194–195 “Technical lignins,” 567 Tensile strength (TS): cellulose nanocomposites, 440–447 cellulose whiskers, 325–326 chitin nanocomposites, 99–102 chitosan-carbon nanotube composites, 120–122 chitosan-clay nanocomposites, 116–118 chitosan-graphene oxide nanocomposites, 123–124 INDEX nanofibrillated cellulose, 321 protein-based nanocomposites, 625–632 starch-based nanocomposites: cellulose nanocomposites, 207–208 filler materials, 279–285 reinforcements, 268–274 Terminal complexes (TCs), nanocellulose substrates, 368–369 Tetraethoxysillane (TEOS), bacterial cellulose processing, 400–401 Tetra(ethylene) glycol dimethyl ether (TEGDME), nanocellulose nanocomposites, 425–426 Tetrafluoroethanol (TFE), lens crystallin nanofiber preparation and processing, 604–605 Tetrahydrofuran (THF) solution, nanomicelle formation, 190–191 Tetra-methoxy silane, nanocrystalline cellulose fillers, 494 2,2,6,6-Tetramethylpiperidine-1-oxy radical (TEMPO) oxidation: cellulose nanocomposites: dynamic mechanical thermal analysis, 450–454 tensile strength, 444–447 chitin nanofibers, 13, 140–142 spectroscopic analysis, 518–519 micro and nanocellulosic product comparisons, 467–469 nanocellulose modification, 371–374 nanocrystalline cellulose, 481 nanofibrillated cellulose treatment, 317–319 Textile industry, bacterial cellulose applications, 355–357 Thermal analysis: bacterial cellulose, 351 cellulose nanofibers, 415–426 future research issues, 426–428 mechanical properties, 449–454 polycaprolactone/cellulose nanocomposites, 422–424 poly(ethylene oxide)/cellulose nanocomposites, 424–426 polyhydroxyalkanoate/cellulose nanocomposites, 415–417 681 poly(lactic acid)/cellulose nanocomposites, 417–422 chitin nanocomposites, 97–105 differential scanning calorimetry, 97–99 dynamic thermal mechanical analysis, 99–102 thermogravimetric analysis, 102–104 thermomechanical analysis, 104 starch nanocomposites, 245–248 decomposition, 246–248 glass transition temperature, 245–246 starch nanocrystals, 170 Thermogravimetric analysis (TGA): bacterial cellulose, 351 cellulose nanofibers, mechanical properties, 450–454 chitin nanocomposites, 102–104 lignin-based bionanocomposites, 571–572 Thermomechanical analysis (TMA), chitin nanocomposites, 104 Thermoplastic composites: cellulose nanocomposites, 402–403 lignin compounds, 572–581 furfuryl alcohol/lignin, 576 lignin/rubber composites, 580–581 lignin/starch composites, 579–580 polycaprolactone/lignin, 575–576 poly(ethylene oxide)/organosolv lignin, 574–575 protein/lignin bionanocomposites, 576–579 protein-based nanocomposites, dry processing, 624 thermoplastic starch (TPS) nanocomposites: dynamic mechanical thermal analysis, 452–454 filler materials, 279–285 food industry applications, 301–302 glass transition temperature shift, 245–247 matrix structure, 242–245 nanoclay fillers, 231–232 poly(butylene adipate-coterephthalate) (PBAT) nanocomposites, 217–218 682 INDEX Thermoplastic composites (cont’d) retrogradation, 244–245 starch/clay hybrids, 215–216 starch/zein blends, 216–217 tensile strength, 441–447 wheat straw cellulose-reinforced nanofibers, 213–214 Thermoset composites: cellulose composites, 403 lignin compounds, 581–584 Thickness properties, chitin nanofiber acetylation, 27–28 Thio-containing chitosan, structure and properties, 39–40 Thioflavin T (ThT), protein nanofiber characterization, 606–607 Three-dimensional networks, chitosan hydrogels, 43–44 Three-points bending test, lignin-based bionanocomposites, 571–572 Time-lag value, permeation theory, 545–546 Tire biopolymers: patented starch nanoparticles, 160–161 starch nanofillers, natural polymer matrices, 295–297 Tissue engineering: bacterial cellulose, 352–354 chitin nanocomposites, 67–68 chitosan compounds, 44–45 Titanium dioxide nanoparticles, protein nanocomposites, 620 active packaging, controlled delivery systems, 643 mechanical properties, 628–632 Titanium-poly(vinyl alcohol) (PVA), cellulose nanocomposite solubility, 397–398 2,4-Toluene diisocyanate (2,4-TDI), starch nanocrystal polymer conjugation, 186–188 Tough nanostructure film, nanocrystalline cellulose, 483 Transmission electron microscopy (TEM): cellulose whiskers, 312–313, 322–324 chitin nanocomposites, 84–93 chitin nanofiber processing, 148–149 chitin nanowhisker acid hydrolysis, 133–134 insulin protein nanofiber, 600–602 nanofibrillated cellulose, 319–321 protein nanofiber characterization, 606–607 starch nanocomposites: MWCNT reinforcement fillers, 272–274 nanofillers, 230–232 starch nanocrystal morphology, 168–169 Transport process, barrier permeation, 544–546 Tricyclodecanedimethanoldimethacrylate (DCP), 24–25 N,N,N-Trimethyl chitosan chloride, 42–43 Tri-polyphosphate (TPP), chitosan nanoparticles, 521–522 Tubeworm β-chitin, TEMPO-mediated nanofibers, 141–142 Tumor-targeted delivery systems: starch nanoparticle chemical modification, 195 starch nanoparticles, 303–304 Tunicin whiskers: acid hydrolysis, 322–324 reinforcement properties, 275–278 Ultimate tensile strength (UTS): chitosan-clay nanocomposites, 116–118 chitosan-hydroxyapatite nanocomposites, 114–115 Ultrasonic techniques, chitin nanofiber processing, 148–149 Ultra Turrax centrifugation, nanofibrillated cellulose treatment, 319 Ultraviolet-shielding materials: bacterial cellulose, 339–340 starch nanocomposites, 228 titanium dioxide nanoparticles, 620 Unzipped multiwalled carbon nanotube oxides (UMCNOs), chitosan nanocomposites, 120–122 INDEX Urethanization: cellulose nanocomposites, 378 modified starch nanocomposites, spectroscopic analysis, 532–533 Uridinediphosphate glucose (UDPglucose), bacterial cellulose, 346–350 Vacuum-assisted resin transfer molding (VARTM), starch-based nanocomposites, 208–209 van der Waals interactions, chitosangraphene oxide nanocomposites, 123–124 Vicat softening temperature, lignin-based thermoplastic composites, 573–581 Waring blender, nanofibrillated cellulose treatment, 315–316 Water absorption kinetics: barrier performance, 560–562 protein-based materials, barrier property modulation, 636–641 Waterborne polyurethane (WPU): ATR-FT-IR characterization, 515–518 chitin whiskers, thermogravimetric analysis, 102–104 starch nanocomposite filler, 278–285 spectroscopic analysis, 533–535 starch nanofillers, 297–299 Water vapor permeability (WVP): bionanocomposite barrier properties, 552–560 protein-based materials, barrier property modulation, 636–641 Water vapor transmission rate (WVTR), nanocellulose barrier layers, 486–488 Waxy maize starch/MMT nanocomposites (WMNC), 231–232 Wet lay-up processing: protein-based nanocomposites, 622–623 starch-based nanocomposites, 208–209 Wheat gluten, protein-based nanocomposites, 619–620 dry processing, 624 683 Wheat straw nanofibers: cellulose nanocomposites, dynamic mechanical thermal analysis, 452–454 cellulose-reinforced nanofibers, thermoplastic starch nanocomposites, 213–214 cellulose whiskers acid hydrolysis, 324 lignin sources, 568 starch-based nanocomposites, cellulose nanocomposites, 207–208 tensile strength, 441–447 Whey proteins, nanocomposites: basic properties, 618 mechanical properties, 628–632 Wide-angle X-ray diffraction (WAXD): chitin nanoparticles, 520–521 chitin nanowhiskers, 523–524 plant cellulose, 511–513 starch nanocomposite retrogradation, 244–245 w/o emulsion crosslinking, starch nanoparticle preparation, 159–161 Wood cellulose nanofibers: dynamic mechanical thermal analysis, 450–454 lignin characteristics, 565–567 micro and nanocellulosic product comparisons, 467–469 structure and properties, 11–12 Wound healing, chitosan compounds, 45–46 X-ray diffraction (XRD): bacterial cellulose, 346–350, 514–515 chitin nanofiber processing, 148–149 chitin nanowhisker acid hydrolysis, 136–137 chitosan nanoparticles, 522–523 protein/lignin bionanocomposites, 577–579 starch crystallinity, 156–157 matrix structure, 242–245 starch nanocrystals, 169–170 starch nanoparticles, 525–526, 533–535 estrificatoin, 526–531 684 INDEX Young’s modulus: bacterial cellulose, 350–351 cellulose nanocomposites, 441–447 cellulose whiskers, 325–326 chitin nanofiber nanocomposites, 24–25 chitosan-carbon nanotube nanocomposites, 118–122 chitosan-graphene oxide nanocomposites, 123–124 chitosan-hydroxyapatite nanocomposites, 114–115 protein-based nanocomposites, 625–632 starch-based nanocomposites: filler materials, 279–285 reinforcements, 268–274 Zein blends: protein-based nanocomposites, 619 protein/lignin bionanocomposites, 576–579 thermoplastic starch/zein blends, 216–217 Zinc oxide particles: nanofiller surface structure, 241–242 starch nanoparticle formation, 210 Figure 2.11 Transparent thin (60 μm) DCP film reinforced with CNFs Figure 5.1 Representative photographic (top panel) and corresponding optical microscopic (bottom panel; magnification 200×) images of (a) neat alginate yarns, (b) alginate nanocomposite yarns containing 0.6% w/w of chitosan whiskers, and (c) neat chitosan yarns, after they had been stained with 0.01% w/v Amido Black 10B aqueous solution for 12 hours [4] Biopolymer Nanocomposites: Processing, Properties, and Applications, First Edition Edited by Alain Dufresne, Sabu Thomas, and Laly A Pothan © 2013 John Wiley & Sons, Inc Published 2013 by John Wiley & Sons, Inc Figure 5.12 Atomic force microscope images in tapping mode illustrating multilevel structure in ChiHAP50, PgAHAP50, and ChiPgAHAP50 nanocomposites Images are illustrative of the multilevel structure and are not to scale [77] Crystalline chitin nanofibril ⎧ ⎨ ⎩ Figure 7.2 50 ~ 300 nm ~ nm Protein layer Chitin-protein fiber Presence of native chitin in crustacean shells Figure 10.1 Starch multiscale structure: (a) starch granules from normal maize (30 μm), (b) amorphous and semicrystalline growth rings (120–500 nm), (c) amorphous and crystalline lamellae (9 nm), magnified details of the semicrystalline growth ring, (d) blocklets (20–50 nm) constituting a unit of the growth rings, (e) amylopectin double helices forming the crystalline lamellae of the blocklets, (f) nanocrystals: other representation of the crystalline lamellae called starch nanocrystals when separated by acid hydrolysis, (g) amylopectin’s molecular structure, and (h) amylose’s molecular structure (0.1–1 nm) Reprinted with permission from Reference [29] Copyright 2010 American Chemical Society (a) (b) 100 nm X 1.000 um/div Z 90.000 nm/div Rms (Rg) 10.500 nm 8.068 nm Ra 81.306 nm Rmax (c) (d) X 1.000 um/div Z 45.000 nm/div Rms (Rg) 10.082 nm 7.330 nm Ra 104.61 nm Rmax X 1.000 um/div Z 100.000 nm/div Rms (Rg) 17.926 nm 14.009 nm Ra Rmax 138.60 nm Figure 11.2 TEM image of graphene oxide (GO) powder (a); AFM images of glycerol plasticized pea starch (GPS) (b), and the GPS/GO nanocomposite films containing 3.0 wt% (c), and 5.0 wt% (d) GO Reprinted with permission from Reference [27] Figure 13.4 Toast packaged with a biodegradable film based on cassava starch formulated with glycerol, sucrose, and inverted sugar as plasticizers Reprinted with permission from Reference [27] Figure 14.4 NFC film and 0.4% consistency NFC gel produced at the Paper and Fiber Research Institute (PFI), Trondheim, Norway, being handled by Kristin Syverud (left) and Ingebjorg Leirset (right), respectively The photograph was taken by Oddbjørn Svarlien and kindly supplied by Kristin Syverud Figure 16.4 Aqueous 0.53% (w/v) suspensions of cellulose nanocrystals observed between crossed polarizers after production by HCl-catalyzed hydrolysis (left), and after their oxidation via TEMPO-mediated reactions (right) (taken from Reference [26]) = Thiol = Alkene = Functional group (a) Route hv Click“ ” Ene-functionalized cellulose film OR RO Si OR + MFC-OH in EtOH/H2O or OR Functionalized cellulose surfaces through thiol-ene click “ chemistry ” 1) Hydrolysis & condensation 2) Filtration 3) Drying RO Si OR Route hv Click“ ” Thiol-functionalized cellulose film (b) OH OHOH hv + + Click“ ” RO Si OR OH OH OH RO Si OR Cellulose film Route Sol-Gel EtOH/H2O OR OR Figure 16.7 Schematic illustration of NFC-based films surface functionalization using click chemistry (a) Synthesis of ene- and thiol-functionalized films with alkoxysilane molecules, and their subsequent “click” coupling reactions with thiol- (Route 1) and ene- (Route 2) molecules, respectively (b) Synthesis of a functional alkoxysilane molecule using thiol-ene “click” chemistry, and its subsequent coupling reaction with a cellulose film through a sol–gel process (Route 3) (reproduced from Reference [56] with permission of The Royal Society of Chemistry) Figure 18.6 Polarized optical microscopy images of PLLA, wt% CNW/PLLA (PLLA-CNC-1 in this figure), and wt% SCNW/PLLA (PLLA-SCNC-1 in this figure) acquired on the 0, 5th, and 10th minute at 125°C after quenched from melt at 210°C Scale bar: 200 µm (reprinted with permission from Pei et al [72] Copyright 2010 Elsevier Ltd.) Figure 18.10 POM micrographs obtained after isothermal crystallization for 100 seconds at 53.6°C for a POE-based film with (a) and (b) 10 wt% cellulose nanowhiskers (reprinted with permission from Azizi Samir et al [47] Copyright 2004 Elsevier Ltd.) Iso-PP melt Iso-PP spherulites Transcrystalline layer Cellulose nanocrystal film Figure 18.11 Crystallization of polypropylene against cellulose nanocrystal film i-PP initially melt at 220°C PLM images after minutes (left) and after 20 minutes (right) at 136°C The right image at higher magnification shows in detail the edge of the CNWs film in contact with i-PP melt Scale bars: 200 µm (reprinted with permission from Gray [92] Copyright 2007 Springer Science+Business Media B.V.) Figure 19.4 Transparent TOCN-93/PS and TOCN-310/PS nanocomposite films Reprinted with permission from Reference [60] (a) Figure 23.1 ence [16]) (b) Possibilities of obtaining lignin-based nanofibers (adapted from Refer-