Cellulose nanocrystals : properties, production, and applications

326 Pages·2017·8.923 MB·English

by  Hamad, Wadood Y

Cellulose Nanocrystals
Wiley Series
in
Renewable Resources
Series Editor
Christian V. Stevens—Faculty of Bioscience Engineering, Ghent University, Ghent, Belgium
Titles in the Series
Wood Modification—Chemical, Thermal and Other Processes
Callum A. S. Hill
Renewables—Based Technology—Sustainability Assessment
Jo Dewulf and Herman Van Langenhove
Introduction to Chemicals from Biomass
James H. Clark and Fabien E. I. Deswarte
Biofuels
Wim Soetaert and Erick Vandamme
Handbook of Natural Colorants
Thomas Bechtold and Rita Mussak
Surfactants from Renewable Resources
Mikael Kjellin and Ingegard Johansson
Industrial Application of Natural Fibres—Structure, Properties and Technical
Applications
Jorg Mussig
Thermochemical Processing of Biomass—Conversion into Fuels, Chemicals and
Power
Robert C. Brown
Biorefinery Co‐Products: Phytochemicals, Primary Metabolites and Value‐Added
Biomass Processing
Chantal Bergeron, Danielle Julie Carrier, and Shri Ramaswamy
Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion
to Fuels and Chemicals
Charles E. Wyman
Bio‐Based Plastics: Materials and Applications
Stephan Kabasci
Introduction to Wood and Natural Fiber Composites
Douglas Stokke, Qinglin Wu, and Guangping Han
Cellulosic Energy Cropping Systems
Douglas L. Karlen
Introduction to Chemicals from Biomass, Second Edition
James Clark and Fabien Deswarte
Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and
Applications
Francisco G. Calvo‐Flores, Jose A. Dobado, Joaquin Isac‐Garcia, and Francisco J.
Martin‐Martinez
Sustainability Assessment of Renewables‐Based Products: Methods and Case Studies
Jo Dewulf, Steven De Meester, and Rodrigo Alvarenga
Forthcoming Titles
Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic
Waste
Erik Meers and Gerard Velthof
Bio‐Based Solvents
Francois Jerome and Rafael Luque
Fuels, Chemicals and Materials from the Oceans and Aquatic Sources
Francesca M. Kerton and Ning Yan
Nanoporous Catalysts for Biomass Conversion
Feng‐Shou Xiao
Cellulose Nanocrystals
Properties, Production,
and Applications
WADooD Y. HAMAD
Cellulosic Biomaterials, FPInnovations, Vancouver, Canada
Department of Chemistry, University of British Columbia, Vancouver, Canada
This edition first published 2017
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Library of Congress Cataloging‐in‐Publication Data
Names: Hamad, Wadood.
Title: Cellulose nanocrystals : properties, production, and applications / Wadood Y. Hamad.
Description: Chichester, West Sussex : John Wiley & Sons, Inc., 2017. |
Includes bibliographical references and index.
Identifiers: LCCN 2016036141| ISBN 9781119968160 (cloth) | ISBN 9781118675700 (epub)
Subjects: LCSH: Cellulose–Chemistry. | Cellulose nanocrystals. | Nanocrystals.
Classification: LCC TP248.65.C45 H36 2017 | DDC 661/.802–dc23
LC record available at https://lccn.loc.gov/2016036141
A catalogue record for this book is available from the British Library.
Set in 10/12pt Times by SPi Global, Pondicherry, India
10 9 8 7 6 5 4 3 2 1
For Dima, Reemo, and Seby—lovingly inspiring, par excellence
Contents
Series Preface xiii
Foreword xv
Prologue xviii
1 New Frontiers for Material Development and the
Challenge of Nanotechnology 1
1.1 Perspectives on Nanotechnology 1
1.2 Societal Ramifications of Nanotechnology 3
1.3 Bio‐inspired Material Development: The Case for Cellulose
Nanocrystals 5
1.4 A Glance at Bio‐inspired Hierarchical Materials 9
1.5 Concluding Thoughts 13
Notes 13
2 Assembly and Structure in Native Cellulosic Fibers 16
2.1 Physical and Chemical Characteristics of the Cellulose Molecule 16
2.1.1 The Origin of Cellulose 16
2.1.2 The Chemistry of Cellulose 18
2.1.3 The Physics of Cellulose 20
2.2 Morphology and Structure of Native Cellulosic Fibers 22
2.3 Physical and Mechanical Properties of Native Cellulosic Fibers 25
2.3.1 Anisotropy of the Fiber Cell Wall 25
2.3.2 Mechanical Properties of Cellulosic Fibers 29
Notes 32
3 Hydrolytic Extraction of Cellulose Nanocrystals 33
3.1 Introduction 33
3.2 The Liberation of CNCs Using Acid Hydrolysis 35
x Contents
3.3 Reaction Kinetics of CNC Extraction 38
3.3.1 Effects of HSO Hydrolysis Conditions and 
2 4
Sulfation on CNC Yield of Extraction 38
3.3.2 HSO Hydrolysis Reproducibility and 
2 4
Yield Optimization 46
3.3.3 Commentary on Hydrochloric Acid‐Hydrolyzed CNCs 48
3.3.4 CNC Stability and Post HSO‐Hydrolysis Aging 49
2 4
3.4 Processing Considerations for Sustainable and
Economical Manufacture of CNCs 50
3.5 Micro/Nano Cellulosics Other Than CNCs 53
3.5.1 Microfibrillated Cellulose 53
3.5.2 Microcrystalline Cellulose 57
3.5.3 Bacterial Cellulose 60
Notes 62
4 Properties of Cellulose Nanocrystals 65
4.1 Morphological Characteristics of CNCs 65
4.2 Structural Organization of CNCs 68
4.3 Solid‐State Characteristics of CNCs 74
4.3.1 X‐Ray Diffractometric Analysis of CNCs 76
4.3.2 CNCs Phase Structure Based on SS‐NMR 81
4.3.3 Concluding Remarks 87
4.4 CNCs Chiral Nematic Phase Properties 87
4.4.1 Ionic Strength Effect on Chiral Phase Separation 88
4.4.2 Temperature Effect on Chiral Phase Separation 91
4.4.3 Suspension Concentration Effect on Chiral
Phase Separation 92
4.4.4 Magnetic Field Effect on Chiral Phase Separation 94
4.4.5 Sonication Effect on Physicochemical Properties 94
4.5 Shear Rheology of CNC Aqueous Suspensions 95
4.5.1 Basic Rheological Behavior of CNC
Aqueous Suspensions 95
4.5.2 Sonication Effects on the Microstructure and
Rheological Properties of CNCs Suspensions 98
4.5.3 Concentration Effects on the Microstructure and
Rheological Properties of CNC Suspensions 100
4.5.4 Temperature Effects on the Microstructure and
Rheological Properties of CNC Suspensions 106
4.5.5 CNCs Surface Charge Effects on the Microstructure and
Rheological Properties of CNC Suspensions 112
4.5.6 Ionic Strength Effects on the Microstructure and
Rheological Properties of CNC Suspensions 118
Contents xi
4.5.7 Aging and Yielding Characteristics of CNC
Suspensions 123
4.5.8 Concluding Remarks 128
4.6 Thermal Stability of CNCs 129
Notes 134
5 Applications of Cellulose Nanocrystals 138
5.1 Prelude 138
5.2 The Reinforcing Potential of CNCs in Polymer
Nanocomposites 140
5.2.1 Basic Concepts in Composites 140
5.2.2 Generic Methods for Surface Functionalization 142
5.2.3 Why CNCs for Reinforcement? 147
5.2.4 Performance of CNCs in Compatible Polymer Systems 150
5.2.5 Nanocomposites Prepared by Postpolymerization
Compounding of CNCs and Thermoplastic Polymers 154
5.2.6 Controlling Nanocomposite Crystallinity and
Plasticity via In Situ Polymerization Methodologies
in the Presence of CNCs 165
5.2.7 CNCs in Thermosetting Polymers: Tailoring
Cross‐Linking Density and Toughness 172
5.2.8 Comments on Modeling the Mechanical Response
of CNC‐Reinforced Nanocomposites 177
5.2.9 Conclusions and Critical Insights 181
5.3 CNC‐Stabilized Emulsions, Gels, and Hydrogels 184
5.3.1 Pickering Emulsions 184
5.3.2 High Internal Phase Emulsions 187
5.3.3 pH‐Responsive Gels and Flocculants 189
5.3.4 Hydrogels 190
5.4 Controlled Self‐Assembly of Functional Cellulosic Materials 194
5.4.1 Flexible CNC Films with Tunable Optical Properties 194
5.4.2 Mesoporous Photonic Cellulose Films 197
5.5 Toward Bio‐inspired Photonic and Electronic Materials 202
5.5.1 Mesoporous Photonic Materials from Cellulose
Nanomaterial Liquid Crystal Templates 202
5.5.2 Actuators and Sensors 217
5.5.3 Sustainable Electronics Based on CNCs 225
5.5.4 Conclusions and Outlook 232
5.6 CNCs in Biomedicine and Pharmaceuticals 233
5.7 Environmental, Health, and Safety Considerations of CNCs 235
5.8 Perspectives and Challenges 238
Notes 239
xii Contents
Epilogue—The Never‐Ending Evolution of Scientific Insights 248
Bibliography 252
Subject Index 288