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Starch-Based Polymeric Materials and Nanocomposites: Chemistry, Processing, and Applications
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CRC Press is an imprint of the
Taylor & Francis Group, an informa business
Boca Raton London New York
Starch-Based Polymeric
Materials and
Nanocomposites
Chemistry, Processing, and Applications
Edited by
Jasim Ahmed
Brijesh K. Tiwari
Syed H. Imam
M.A. Rao
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2012 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20120224
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iii
Contents
Preface..............................................................................................................................................vii
Editors................................................................................................................................................ix
Contributors.......................................................................................................................................xi
Chapter 1
Introduction: Starch as Biopolymer and Nanocomposite...................................................................1
Jasim Ahmed, Brijesh K. Tiwari, Syed H. Imam, and M.A. Rao
Chapter 2
Starch: Chemistry, Microstructure, Processing, and Enzymatic Degradation...................................5
Syed H. Imam, Delilah F. Wood, Mohamed A. Abdelwahab, Bor-Sen Chiou,
Tina G. Williams, Gregory M. Glenn, and William J. Orts
Chapter 3
Starch as Gelling Agent.................................................................................................................... 33
Thava Vasanthan, Jihong Li, David Bressler, and Ratnajothi Hoover
Chapter 4
Plasticized Starch..............................................................................................................................69
Xiaofei Ma, Peter R. Chang, and Jiugao Yu
Chapter 5
Rheological and Thermal Properties of Starch and Starch-Based Biopolymers..............................85
M.A. Rao, JiraratTattiyakul, and Hung-Ju Liao
Chapter 6
Modification of Biodegradable Polymers through Reactive Extrusion-I........................................ 101
I. Moura and A.V. Machado
Chapter 7
Modification of Biodegradable Polymers through Reactive Extrusion-II...................................... 133
Sathya B. Kalambur
Chapter 8
Starch-Derived Cyclodextrins and Their Future in the Food Biopolymer Industry....................... 167
C. González-Barreiro, R. Rial-Otero, J. Simal-Gándara, G. Astray,
A. Cid, J.C. Mejuto, J.A. Manso, and J. Morales
iv Contents
Chapter 9
Functional and Physicochemical Properties of Cyclodextrins....................................................... 183
Jun Zhao and Shan-Jing Yao
Chapter 10
Introduction of Starch into Plastic Films: Advent of Starch in Plastics......................................... 231
R.E. Harry-O’kuru and Sherald H. Gordon
Chapter 11
Starch-Based Edible Films and Coatings....................................................................................... 239
Mahesh Gupta, Charles Brennan, and Brijesh K. Tiwari
Chapter 12
Starch as a Feedstock for Bioproducts and Packaging................................................................... 255
Gregory M. Glenn, Syed H. Imam, William J. Orts, and Kevin Holtman
Chapter 13
Chemometric Analysis of Multicomponent Biodegradable Plastics by
Fourier Transform Infrared Spectrometry: The R-Matrix Method................................................ 271
Sherald H. Gordon
Chapter 14
Starch Polymer as Advanced Material for Industrial and Consumer Products..............................287
Randal L. Shogren
Chapter 15
Recent Progress in Starch-Based Biodegradable Hybrids and Nanomaterials.............................. 301
Peter R. Chang, Xiaofei Ma, Debbie P. Anderson, and Jiugao Yu
Chapter 16
Mechanical, Rheological, and Thermal Properties of Starch-Based Nanocomposites.................. 325
Jasim Ahmed
Chapter 17
Starch Nanocomposites and Nanoparticles: Biomedical Applications........................................... 361
Anitha R. Dudhani
Contents v
Chapter 18
Application of Life Cycle Assessment for Starch and Starch Blends............................................. 373
Ali Abas Wani and Preeti Singh
vii
Preface
Biodegradable polymers from renewable resources have attracted much attention in recent years.
Starch has been considered as one of the most promising candidates among biopolymers mainly
because of its attractive combination of availability and price. Starch is unique in its application and versatility. In addition to its contribution to processing industries, research on starch is
currently more focused on the development of biodegradable packaging materials and the synthesis of starch derivatives, bionanoparticles, and bionanocomposites. In order to extend applications of starch as primary packaging materials, current research has focused on starch blends,
especially starch/polyester (e.g., polylactides [PLA], polycaprolactone [PCL], and polybutylene
succinate [PBS]) biodegradable blends. However, starch/polyester blends are not compatible for
blending and, therefore, a reactive compatibilization process known as reactive extrusion is used
to synthesize starch/polyester blends at high starch levels (>20 wt%). The process can also be
expanded to plasticized starch and nanocomposites by incorporating nanoparticles in the blend.
Such nanocomposites exhibit improved mechanical strength, solvent and UV resistance, gas barrier properties, thermal stability, and flame retardancy as compared to conventional composites.
Rheological and mechanical properties during plasticization and nanocomposite formation provide a better understanding of structural modification and degree of dispersions of nanoparticles
into biopolymers.
The starch industry is one the largest manufacturing industries, and the significant contribution
of food professionals to the industry is well recognized. A professional food/starch scientist should
be aware of the latest developments in starch chemistry, rheology, starch derivatives, starch-based
nanocomposites, and their applications. Starch-Based Polymeric Materials and Nanocomposites:
Chemistry, Processing and Applications has been written primarily to fulfill those expectations and
is intended for students undertaking graduate courses in food science, food technology, biotechnology, human nutrition, and related areas. The book has particular relevance to students’ understanding of starch from basics to applications as well as for their future professions. It should also be of
interest to graduates of other disciplines who are working in starch-related industries.
The chapters in this book have been contributed by leading experts who have both academic and
professional credentials. We are thankful to our contributors for their wonderful cooperation and,
finally, we are indebted to our families for their continued support throughout the project. It is worth
mentioning that there was an excellent coordination among editors that resulted in delivering the
book on time. Our special thanks to Steve Zollo, Senior Editor of Taylor & Francis, for his constant
encouragement and excellent communication.
ix
Editors
Dr. Jasim Ahmed has been associated with food processing teaching, research, and industry in
India, Canada, and the Middle East for about two decades. He is mostly involved in research areas
on food product development, food rheology and structure, novel food processing, and the thermal
behavior of foods. His current research focus is on bionanocomposites and application to food packaging. Dr. Ahmed recently moved to the Kuwait Institute for Scientific Research, Kuwait as research
scientist to develop the Food Processing Program. He has published 92 peer-reviewed research
papers and 21 book chapters. Dr. Ahmed is coeditor of four books including Novel Food Processing:
Effects on Rheological and Functional Properties (CRC Press Publication) and Handbook of Food
Process Design (Wiley-Blackwell). Dr. Ahmed is one of the editors of the International Journal of
Food Properties.
Dr. Brijesh K. Tiwari is a lecturer in food engineering at Manchester Metropolitan University
(MMU), United Kingdom, and a senior consultant at Manchester Food Research Centre, United
Kingdom. Prior to joining MMU, he was a lecturer in biosystems engineering at University College
Dublin, Ireland. Dr. Tiwari served the Indian Institute of Crop Processing Technology as a research
scientist (2004–2006), where he was actively involved in developing a research portfolio in grain
processing. He was also responsible for numerous consultancy assignments, technology transfer
projects, and the management of a number of industry-focused research projects. His main research
accomplishments are in the areas of novel food processing and preservation technologies, grain
processing, and mathematical modeling of food processes. To date he has contributed about 50 peerreviewed Science Citation Index–listed journal publications and 20 chapters published in books by
leading publishers; he has also presented over 30 refereed conference papers at key international
research conferences. Dr. Tiwari is a coeditor of four books: Pulse Foods: Quality, Technology, and
Nutraceutical Application (Elsevier); Ozone in Food Processing (Wiley-Blackwell, in development);
Novel Thermal and Non-Thermal Technologies for Fluid Foods (Elsevier); and the Handbook of
Phytochemicals: Sources, Stability and Extraction (Wiley-Blackwell). He is also the book series
editor for IFST Food Processing Technology.
Dr. Syed H. Imam is a senior research chemist at the United States Department of Agriculture,
Albany. He conductsresearch to enhance the utilization of agriculturally derived renewable polymers
for nonfood applications as an alternative to petroleum chemicals and provides fundamental knowledge in the development of polymer-based materials of tailored properties. With over 25 years of
research experience, Dr. Imam is internationally recognized for his accomplishments and contributions in the field. He has authored or coauthored over 130 publications in peer-reviewed professional
journals, delivered over 180 invited talks at national and international meetings, and has numerous
patents to his credit. He has served on the ASTM-D20 Committee on Biodegradable Polymers
and currently serves as a U.S. representative on the UNIDO–ICS Expert Panel on Biodegradable
Polymers and Materials. He is a member of the editorial boards of the Journal of Polymers and
the Environment and the International Journal of Biochemistry and Biotechnology and serves as
an associate editor of the Journal of Bioenergy and Biomaterials. He is a chief editor of the ACS
book titled Biopolymers: Natures Advanced Materials published in 1998 by the Oxford University
Press. He is also a coeditor of another book titled Produce Degradation: Reaction Pathways and
Prevention published in 2005 by CRC Press.
Dr. M.A. Rao is an emeritus professor at Cornell University, Geneva, New York. His main research
interest is in rheological properties of foods: principles, measurement, and applications. He is a
fellow of the Institute of Food Technologists, the Association of Food Scientists and Technologists
x Editors
(India), and the International Academy of Food Science and Technology. He was conferred the
Lifetime Achievement Award by the International Association of Engineering and Food in 2011,
the Scott Blair Award for his contributions to food rheology by the American Association of Cereal
Chemists in 2000, and an honorary membership by the Brazilian Association of Rheology in 2011.
He has also been chosen as a distinguished food engineer by the Food Process Engineering Institute
of the American Society of Agricultural Engineers in 2003. Dr. Rao was awarded Fulbright–Hays
senior scholarships to Brazil, 1980–1981, and to Portugal, 1988–1989. He has contributed about
250 journal papers and book chapters on food rheology and food engineering. He is the editor
of the book Rheology of Fluid and Semisolid Foods: Principles and Applications, second edition, Springer, New York, 2007, and a coeditor of Engineering Properties of Foods, third edition,
Taylor & Francis, Boca Raton, Florida, 2005. He is also a scientific editor of the Food Engineering
and Physical Properties section of the Journal of Food Science.
xi
Contributors
Mohamed A. Abdelwahab
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
and
Department of chemistry and Industrial
Chemistry
University of Pisa
Pisa, Italy
and
University of Tanta
Tanta, Egypt
Jasim Ahmed
Food and Nutrition Program
Kuwait Institute for Scientific Research
Safat, Kuwait
Debbie P. Anderson
Bioproducts and Bioprocesses National Science
Program
Agriculture and Agri-Food Canada
Saskatoon, Saskatchewan, Canada
G. Astray
Department of Physical Chemistry
University of Vigo at Ourense
Ourense, Spain
Charles Brennan
Department of Wine, Food and Molecular
Biosciences
Lincoln University
Lincoln Christchurch, New Zealand
David Bressler
Department of Agricultural, Food and
Nutritional Science
University of Alberta
Edmonton, Alberta, Canada
Peter R. Chang
Bioproducts and Bioprocesses National Science
Program
Agriculture and Agri-Food Canada
and
Department of Chemical and Biological
Engineering
University of Saskatchewan
Saskatoon, Saskatchewan, Canada
Bor-Sen Chiou
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
A. Cid
Department of Physical Chemistry
University of Vigo at Ourense
Ourense, Spain
Anitha R. Dudhani
Department of Pharmacy Practice
Monash Institute of Pharmaceutical Sciences
Monash University
and
School of Biomedical and Health Sciences
Victoria University
and
Healthline Pharmacy
Melbourne, Victoria, Australia
Gregory M. Glenn
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
xii Contributors
C. González-Barreiro
Department of Analytical and Food Chemistry
University of Vigo at Ourense
Ourense, Spain
Sherald H. Gordon
Plant Polymer Research Unit
National Center for Agricultural Utilization
Research
Agricultural Research Service
United States Department of Agriculture
Peoria, Illinois
Mahesh Gupta
School of Food Science and Environmental
Health
Dublin Institute of Technology
Dublin, Ireland
R.E. Harry-O’kuru
Bio-Oils Research Unit
National Center for Agricultural Utilization
Research
Agricultural Research Service
United States Department of Agriculture
Peoria, Illinois
Kevin Holtman
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
Ratnajothi Hoover
Department of Biochemistry
Memorial University of Newfoundland
St. John’s, Newfoundland, Canada
Syed H. Imam
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
Jihong Li
Department of Agricultural, Food and
Nutritional Science
University of Alberta
Edmonton, Alberta, Canada
Hung-Ju Liao
Department of Food Science
National Chiayi University
Chiayi City, Taiwan
Sathya B. Kalambur
Frito Lay
Plano, Texas
and
Department of Food Sciences
Cornell University
Ithaca, New York
Xiaofei Ma
Department of Chemistry
School of Science
Tianjin University
Tianjin, China
A.V. Machado
Institute of Polymers and Composites/I3N
University of Minho
Guimarães, Portugal
J.A. Manso
Department of Physical Chemistry
University of Vigo at Ourense
Ourense, Spain
J.C. Mejuto
Department of Physical Chemistry
University of Vigo at Ourense
Ourense, Spain
J. Morales
Department of Physical Chemistry
University of Vigo at Ourense
Ourense, Spain
Contributors xiii
I. Moura
Institute of Polymers and Composites/I3N
University of Minho
Guimarães, Portugal
William J. Orts
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
M.A. Rao
Department of Food Science
Cornell University
Geneva, New York
R. Rial-Otero
Department of Analytical and Food
Chemistry
University of Vigo at Ourense
Ourense, Spain
Randal L. Shogren
National Center for Agricultural Utilization
Research
Agricultural Research Service
United States Department of Agriculture
Peoria, Illinois
J. Simal-Gándara
Department of Analytical and Food
Chemistry
University of Vigo at Ourense
Ourense, Spain
Preeti Singh
Department of Material Development
Fraunhofer Institute for Process Engineering
and Packaging
and
Food Packaging Technology
Technical University of Munich
Freising, Germany
Jirarat Tattiyakul
Department of Food Technology
Chulalongkorn University
Bangkok, Thailand
Brijesh K. Tiwari
School of Food and Consumer Technology
Manchester Metropolitan University
Manchester, United Kingdom
Thava Vasanthan
Department of Agricultural, Food and
Nutritional Science
University of Alberta
Edmonton, Alberta, Canada
Ali Abas Wani
Department of Process Development for Plant
Raw Materials
Fraunhofer Institute for Process Engineering
and Packaging
and
Food Packaging Technology
Technical University of Munich
Freising, Germany
Tina G. Williams
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
Delilah F. Wood
Bioproduct Chemistry and Engineering
Research
Western Regional Research Center
Agricultural Research Service
United States Department of Agriculture
Albany, California
Shan-Jing Yao
Department of Chemical and Biological
Engineering
Zhejiang University
Hangzhou, China
xiv Contributors
Jiugao Yu
Department of Chemistry
School of Science
Tianjin University
Tianjin, China
Jun Zhao
Department of Chemical and Biological
Engineering
Zhejiang University
Hangzhou, China
and
Department of Bioengineering and
Biotechnology
College of Chemical Engineering
Huaqiao University
Xiamen, China