Biopolymer Nanocomposites: Processing, Properties, and Applications

BIOPOLYMER

NANOCOMPOSITES

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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

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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)

1. Biopolymers. 2. 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 9 8 7 6 5 4 3 2 1

v

CONTENTS

Foreword vii

Contributors ix

1. Bionanocomposites: State of the Art, Challenges, and Opportunities 1

Alain Dufresne, Sabu Thomas, and Laly A. Pothan

2. Preparation of Chitin Nanofi bers and Their Composites 11

Shinsuke Ifuku, Zameer Shervani, and Hiroyuki Saimoto

3. Chemical Modifi cation of Chitosan and Its Biomedical Application 33

Deepa Thomas and Sabu Thomas

4. Biomimetic Lessons for Processing Chitin-Based Composites 53

Otto C. Wilson, Jr. and Tiffany Omokanwaye

5. Morphological and Thermal Investigations of Chitin-Based

Nanocomposites 83

Ming Zeng, Liyuan Lu, and Qingyu Xu

6. Mechanical Properties of Chitin-Based Nanocomposites 111

Merin Sara Thomas, Laly A. Pothan, and Sabu Thomas

7. Preparation and Applications of Chitin Nanofi bers/Nanowhiskers 131

Jun-Ichi Kadokawa

8. Preparation of Starch Nanoparticles 153

Déborah Le Corre and Alain Dufresne

9. Chemical Modifi cation 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

vi CONTENTS

13. Applications of Starch Nanoparticles and Starch-Based

Bionanocomposites 293

Siji K. Mary, Laly A. Pothan, and Sabu Thomas

14. Preparation of Nanofi brillated Cellulose and Cellulose Whiskers 309

David Plackett and Marco Iotti

15. Bacterial Cellulose 339

Eliane Trovatti

16. Chemical Modifi cation 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,

François 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 Nanofi bers 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

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 scien￾tifi c publications on the cellulose nanomaterial research has grown very rapidly

and reached more the 600 scientifi c publications during 2011. The research

topics have been extraction of cellulose nanofi bers and nanocrystals from dif￾ferent raw material sources, their chemical modifi cation, 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 fi bers 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 nanofi -

bers 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 rela￾tively new research area, it is necessary to further develop processing methods

to make these nanomaterials available on a large scale, so that new applica￾tions based on them can be developed.

Information about this emerging research fi eld 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 Nanocom￾posites: 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 bionanocom￾posites to a student of materials science. Going beyond mere introduction, the

book delves deep into the characteristics of various biopolymers and bionano￾composites and discusses the nuances of their preparation with a view to

FOREWORD

vii

viii FOREWORD

helping researchers fi nd out newer and novel applications.” Students, research￾ers, and industrialists in the fi eld of biocomposites will be greatly benefi tted

by this book since its chapters are authored by an impressive array of promi￾nent current researchers in this fi eld. Sincere attempts like this at promoting

the use of green materials for sustainable growth of humanity should be

lauded indeed.

K ristiina O ksman

Luleå University of Technology

Debbie P. Anderson , Bioproducts and Bioprocesses National Science

Program, Agriculture and Agri-Food Canada, Saskatoon, SK, Canada

Hélène Angellier-Coussy , UnitéMixte de RechercheIngénierie des Agropoly￾mères et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Uni￾versité Montpellier II, Montpellier Cedex, France

Mirta I. Aranguren , INTEMA-CONICET, Facultad de Ingeniería-Universi￾dad 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, Physi￾cal 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, Sas￾katoon, SK, Canada

B. Deepa , Department of Chemistry, Bishop Moore College, Mavelikara,

Kerala, India; Department of Chemistry, C.M.S. College, Kottayam, Kerala,

India

François Drolet , FPInnovations, Pointe Claire, QC, Canada

Alain Dufresne , Grenoble Institute of Technology (Grenoble INP), The Inter￾national School of Paper, Print Media, and Biomaterials (Pagora), Saint

Martin d’Hères Cedex, France

CONTRIBUTORS

ix

x CONTRIBUTORS

Heath Ecroyd , School of Biological Sciences, University of Wollongong, NSW,

Australia

Megan Garvey , Institute of Molecular Biotechnology, RWTH Aachen Uni￾versity, Aachen, Germany

Emmanuelle Gastaldi , Unité Mixte de Recherche Ingénierie des Agropoly￾mères et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Uni￾versité Montpellier II, Montpellier Cedex, France

Juliet A. Gerrard , Biomolecular Interaction Centre, University of Canterbury,

Christchurch, New Zealand; School of Biological Sciences, University of

Canterbury, Christchurch, New Zealand; MacDiarmid Institute, University

of Canterbury, Christchurch, New Zealand

Nathalie Gontard , Unité Mixte de Recherche Ingénierie des Agropolymères

et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Université

Montpellier II, Montpellier Cedex, France

Valérie Guillard , Unité Mixte de Recherche Ingénierie des Agropolymères et

Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Université

Montpellier II, Montpellier Cedex, France

Carole Guillaume , Unité Mixte de Recherche Ingénierie des Agropolymères

et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Université

Montpellier II, Montpellier Cedex, France

Youssef Habibi , Center of Innovation and Research in Materials and Poly￾mers, University of Mons, Belgium

Wadood Hamad , FPInnovations, Pointe Claire, QC, Canada

Jin Huang , College of Chemical Engineering, Wuhan University of Technol￾ogy, Wuhan, China; and State Key Laboratory of Pulp and Paper Engineer￾ing, South China University of Technology, Guangzhou, China

Qing Huang , College of Chemical Engineering, Wuhan University of Technol￾ogy, Wuhan, China

Shinsuke Ifuku , Department of Chemistry and Biotechnology, Graduate

School of Engineering, Tottori University, Koyama-cho Minami, Tottori,

Japan

Marco Iotti , Research Scientist, Paper and Fibre Research Institute, Trond￾heim, Norway

Jun-Ichi Kadokawa , Graduate School of Science and Engineering, Kagoshima

University, Korimoto, Kagoshima, Japan

Rekha Rose Koshy , Department of Chemistry, Bishop Moore College, Mave￾likara, Kerala, India

Marie-Pierre Laborie , Institute of Forest Utilization and Work Sciences,

Albert-Ludwigs University of Freiburg, Freiburg, Germany, and Freiburg

CONTRIBUTORS xi

Materials Research Centre—FMF, Albert-Ludwigs University of Freiburg,

Freiburg, Germany

Déborah Le Corre , University of Canterbury, New Zealand

Liyuan Lu , Engineering Research Center of Nano-Geomaterials of Ministry

of Education, China University of Geosciences, Wuhan, China

Norma E. Marcovich , INTEMA-CONICET, Facultad de Ingeniería-Univer￾sidad Nacional de Mar del Plata, Mar del Plata, Argentina

Siji K. Mary , Bishop Moore College, Mavelikara, Kerala, India

Vikas Mittal , Chemical Engineering Department, The Petroleum Institute,

Abu Dhabi, United Arab Emirates

Mirna A. Mosiewicki , INTEMA-CONICET, Facultad de Ingeniería-Univer￾sidad Nacional de Mar del Plata, Mar del Plata, Argentina

Tiffany Omokanwaye , Catholic University of America, BONE/CRAB Lab,

Department of Biomedical Engineering, Washington, DC

Anayancy Osorio-Madrazo , Institute of Forest Utilization and Work Sciences,

Albert-Ludwigs University of Freiburg, Freiburg, Germany, and Freiburg

Materials Research Centre—FMF, Albert-Ludwigs University of Freiburg,

Freiburg, Germany

Stéphane Peyron , Unité Mixte de Recherche Ingénierie des Agropolymères

et Technologies Emergentes, INRA/ENSA.M/UMII/CIRAD, Université

Montpellier II, Montpellier Cedex, France

Saumya S. Pillai , Department of Chemistry, Bishop Moore College, Mave￾likara, Kerala, India

David Plackett , Department of Chemical and Biochemical Engineering, Tech￾nical University of Denmark, Kgs. Lyngby, Denmark

Laly A. Pothan , Department of Chemistry, Bishop Moore College, Mave￾likara, Kerala, India

Shiva P. Rao , New Zealand Institute of Plant and Food Research, Christ￾church, New Zealand; Biomolecular Interaction Centre, University of Can￾terbury, Christchurch, New Zealand

Hiroyuki Saimoto , Department of Chemistry and Biotechnology, Graduate

School of Engineering, Tottori University, Koyama-cho Minami, Tottori,

Japan

Robert A. Shanks , School of Applied Sciences, RMIT University, Melbourne,

Vic., Australia

Zameer Shervani , Department of Chemistry and Biotechnology, Graduate

School of Engineering, Tottori University, Koyama-cho Minami, Tottori,

Japan

xii CONTRIBUTORS

Deepa Thomas , Department of Chemistry, Bishop Moore College, Mavelik￾kara, Kerala India

Merin Sara Thomas , Centre for Nanoscience and Nanotechnology, M.G. Uni￾versity, Kottayam, Kerala, India

Sabu Thomas , Centre for Nanoscience and Nanotechnology, M.G. University,

Kottayam, Kerala, India

Eliane Trovatti , CICECO and Department of Chemistry, University of Aveiro,

Aveiro, Portugal

Cornelia Vasile , PetruPoni” Institute of Macromolecular Chemistry, Physical

Chemistry of Polymers Department, Ghica Voda Alley, Iasi, Romania

Madhusudan Vasudevamurthy , New Zealand Institute of Plant and Food

Research, Christchurch, New Zealand; Biomolecular Interaction Centre,

University of Canterbury, Christchurch, New Zealand

Otto C. Wilson, Jr. , Catholic University of America, BONE/CRAB Lab,

Department of Biomedical Engineering, Washington, DC

Qingyu Xu , Hubei Research Institute of Chemistry, Wuhan, China, and Haiso

Technology Co., Ltd, Wuhan, China

Jiahui Yu , Institute of Biofunctional Materials and Devices, East China

Normal University, Shanghai, China

Ming Zeng , Engineering Research Center of Nano-Geomaterials of Ministry

of Education,China University of Geosciences, Wuhan, China, and State

Key Laboratory of Polymer Materials Engineering, Sichuan University,

Chengdu, China

Xuejun Zou , FPInnovations, Pointe Claire, QC, Canada

1

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.

CHAPTER 1

Bionanocomposites: State of the Art,

Challenges, and Opportunities

ALAIN DUFRESNE, SABU THOMAS, and LALY A. POTHAN

1.1 INTRODUCTION

Researchers are currently developing and modifying biobased materials that

have various applications in different fields. Ecological concerns are the main

reasons behind this renewed interest in natural and compostable materials.

Tailoring new products with the perspective of sustainable development is a

philosophy that is applied to more and more materials now. The importance

gained by natural polymers recently should be viewed from this perspective.

Compared with their synthetic counterparts, natural polymers are renewable,

biocompatible, and biodegradable. Production of nanocomposites from natural

polymers, such as starch, chitin, and cellulose, and specific research in this field

aimed at increasing the properties of the products and developing newer tech￾niques are the order of the day. Polysaccharide polymers that are abundant in

nature are increasingly being used for the preparation of nanocomposites.

Biopolymers are polymers that are biodegradable. They are designed to

degrade through the action of living organisms. They are the best alternatives

to traditional nonbiodegradable polymers whose recycling is unpractical or

not economical. The input materials for the production of such biodegradable

polymers may be either renewable (based on agricultural plant or animal

products) or synthetic. Biopolymers from renewable resources are more

important than others for obvious reasons [1]. Biopolymers are said to be

from renewable sources because they are made from materials that can be

grown each year, indefinitely. Plant-based biopolymers usually come from

agricultural nonfood crops. Therefore, the use of biopolymers would create a

2 Bionanocomposites: State of the Art, Challenges, and Opportunities

sustainable industry. In contrast, the feedstock of synthetic polymers derived

from petrochemicals will eventually run out. Biopolymers have also been

reported to be close to carbon-neutral. When a biodegradable material (neat

polymer, blended product, or composite) is obtained completely from renew￾able resources, we may call it a green polymeric material.

Nature provides an impressive array of polymers that are generally biode￾gradable and that have the potential to replace many current polymers, as

biodegradation is part of the natural biogeochemical cycle. Natural polymers,

such as proteins, starch, and cellulose, are examples of such polymers. Polymer

nanocomposites represent a new alternative to conventional polymers. Polymer

nanocomposites are materials in which nanoscopic inorganic or organic par￾ticles, typically 10–1000 Å in at least one dimension, are dispersed in an organic

polymer matrix in order to improve the properties of the polymer dramatically.

Owing to the nanometer length scale, which minimizes scattering of light,

nanocomposites are usually transparent and exhibit properties that are mark￾edly improved over those of pure polymers or their traditional composites.

They have increased modulus and strength, outstanding barrier properties,

improved solvency, heat resistance, and generally lower flammability, and they

do not have detrimental effects on ductility.

1.2 NANOCRYSTALLINE CELLULOSE

The hierarchical structure and semicrystalline nature of polysaccharides (cel￾lulose, starch, and chitin) allow nanoparticles to be extracted from naturally

occurring polymers. Native cellulose and chitin fibers are composed of smaller

and mechanically stronger long thin filaments, called microfibrils, consisting of

alternating crystalline and noncrystalline domains. Multiple mechanical shear￾ing actions can be used to release these microfibrils individually.

The extraction of crystalline cellulosic regions, in the form of nanowhiskers,

can be accomplished by a simple process based on acid hydrolysis. Samir et al.

have described cellulose whiskers as nanofibers that have been grown under

controlled conditions that lead to the formation of high purity single crystals

[2]. Many different terms have been used in the literature to designate these

rod-like nanoparticles. They are mainly referred to as whiskers or cellulose

nanocrystals. A recent review from Habibi et al. gives a clear overview of such

cellulosic nanomaterials [3].

Nanocrystalline cellulose (NCC) derived from acid hydrolysis of native

cellulose possesses different morphologies depending on the origin and hydro￾lysis conditions. NCCs are rigid rod-like crystals with a diameter in the range

of 10–20nm and lengths of a few hundred nanometers (Figure 1.1). Acid treat￾ment (acid hydrolysis) is the main process used to produce NCC, which are

smaller building blocks released from the original cellulose fibers. Native cel￾lulose consists of amorphous and crystalline regions. The amorphous regions

have lower density than the crystalline regions. Therefore, when cellulose