List of Contributors XIII

Foreword XV

Preface XVII

1 Polysaccharide Nanocrystals: Current Status and Prospects in Material Science 1
Jin Huang, Peter R. Chang, and Alain Dufresne

1.1 Introduction to Polysaccharide Nanocrystals 1

1.2 Current Application of Polysaccharide Nanocrystals in Material Science 3

1.3 Prospects for Polysaccharide Nanocrystal-Based Materials 8

List of Abbreviations 9

References 9

2 Structure and Properties of Polysaccharide Nanocrystals 15
Fei Hu, Shiyu Fu, Jin Huang, Debbie P. Anderson, and Peter R. Chang

2.1 Introduction 15

2.2 Cellulose Nanocrystals 16

2.2.1 Preparation of Cellulose Nanocrystals 16

2.2.1.1 Acid Hydrolysis Extraction of Cellulose Nanocrystals 16

2.2.1.2 Effects of Acid Type 19

2.2.1.3 Effects of Pretreatment 24

2.2.2 Structure and Properties of Cellulose Nanocrystals 26

2.2.2.1 Structure and Rigidity of Cellulose Nanocrystals 26

2.2.2.2 Physical Properties of Cellulose Nanocrystals 32

2.3 Chitin Nanocrystals 41

2.3.1 Preparation of Chitin Nanocrystals 41

2.3.1.1 Extraction of Chitin Nanocrystals by Acid Hydrolysis 41

2.3.1.2 Extraction of Chitin Nanocrystals by TEMPO Oxidation 42

2.3.2 Structure and Properties of Chitin Nanocrystals 43

2.3.2.1 Structure and Rigidity of Chitin Nanocrystals 43

2.3.2.2 Properties of Chitin Nanocrystal Suspensions 45

2.4 Starch Nanocrystals 47

2.4.1 Preparation of Starch Nanocrystals 47

2.4.1.1 Extraction of Starch Nanocrystals by Acid Hydrolysis 47

2.4.1.2 Effect of Ultrasonic Treatment 49

2.4.1.3 Effect of Pretreatment 50

2.4.2 Structure and Properties of Starch Nanocrystals 50

2.4.2.1 Structure of Starch Nanocrystals 50

2.4.2.2 Properties of Starch Nanocrystal Suspensions 51

2.5 Conclusion and Prospects 52

List of Abbreviations 53

References 54

3 Surface Modification of Polysaccharide Nanocrystals 63
Ning Lin and Alain Dufresne

3.1 Introduction 63

3.2 Surface Chemistry of Polysaccharide Nanocrystals 63

3.2.1 Surface Hydroxyl Groups 63

3.2.2 Surface Groups Originating from Various Extraction Methods 65

3.3 Approaches and Strategies for Surface Modification 66

3.3.1 Purpose and Challenge of Surface Modification 66

3.3.2 Comparison of Different Approaches and Strategies of Surface Modification 67

3.4 Adsorption of Surfactant 70

3.4.1 Anionic Surfactant 70

3.4.2 Cationic Surfactant 71

3.4.3 Nonionic Surfactant 71

3.5 Hydrophobic Groups Resulting from Chemical Derivatization 72

3.5.1 Acetyl and Ester Groups with Acetylation and Esterification 72

3.5.2 Carboxyl Groups Resulting from TEMPO-Mediated Oxidation 77

3.5.3 Derivatization with Isocyanate Carboamination 79

3.5.4 Silyl Groups Resulting from Silylation 79

3.5.5 Cationic Groups Resulting from Cationization 81

3.6 Polymeric Chains from Physical Absorption or Chemical Grafting 81

3.6.1 Hydrophilic Polymer 82

3.6.2 Polyester 83

3.6.3 Polyolefin 85

3.6.4 Block Copolymer 90

3.6.5 Polyurethane andWaterborne Polyurethane 91

3.6.6 Other Hydrophobic Polymer 92

3.7 Advanced Functional Groups and Modification 92

3.7.1 Fluorescent and Dye Molecules 94

3.7.2 Amino Acid and DNA 95

3.7.3 Self-Cross-linking of Polysaccharide Nanocrystals 95

3.7.4 Photobactericidal Porphyrin Molecule 96

3.7.5 Imidazolium Molecule 97

3.7.6 Cyclodextrin Molecule and Pluronic Polymer 97

3.8 Concluding Remarks 98

List of Abbreviations 98

References 100

4 Preparation of Polysaccharide Nanocrystal-Based Nanocomposites 109
Hou-Yong Yu, Jin Huang, Youli Chen, and Peter R. Chang

4.1 Introduction 109

4.2 Casting/Evaporation Processing 110

4.2.1 Solution Casting/Evaporation Processing 110

4.2.2 Solution Casting in Aqueous Medium 111

4.2.2.1 Dispersion Stability of Polysaccharide Nanocrystals in Aqueous Medium 111

4.2.2.2 Blending with Hydrophilic Polymers 112

4.2.2.3 Blending with Hydrophobic Polymers 116

4.2.3 Solution Casting in Organic Medium 117

4.2.3.1 Dispersion Stability of Polysaccharide Nanocrystals in Organic Medium 117

4.2.3.2 Blending with Polymers in Organic Solvent 118

4.3 Thermoprocessing Methods 121

4.3.1 Thermoplastic Materials Modified with Polysaccharide Nanocrystals 121

4.3.2 Influence of Surface Modification of Polysaccharide Nanocrystals on NanocompositeThermoprocessing 122

4.4 Preparation of Nanofibers by Electrospinning Technology 127

4.4.1 Electrospinning Technology 127

4.4.1.1 Concepts 127

4.4.1.2 Formation Process of Nanofibers 128

4.4.1.3 Basic Electrospinning Parameters and Devices 129

4.4.1.4 Newly Emerging Electrospinning Techniques 130

4.4.2 Nanocomposite Nanofibers Filled with Polysaccharide Nanocrystals 132

4.4.2.1 Electrospun Nanofibers in Aqueous Medium 132

4.4.2.2 Electrospun Nanofibers in Non-aqueous Medium 134

4.5 Sol–Gel Method 135

4.5.1 Concepts of Sol–Gel Process 135

4.5.2 Polysaccharide Nanocrystal-Based or -Derived Nanocomposites Prepared by Sol–Gel Method 136

4.5.3 Chiral Nanocomposites Using Cellulose Nanocrystal Template 137

4.5.3.1 Inorganic Chiral Materials Based on Cellulose Nanocrystal Template 137

4.5.3.2 Chiral Porous Materials 138

4.5.3.3 Chiral Porous Carbon Materials 141

4.5.3.4 Metal Nanoparticle-Decorated Chiral Nematic Materials 143

4.6 Self-Assembly Method 144

4.6.1 Overview of Self-Assembly Method 144

4.6.2 Self-Assembly Method Toward Polysaccharide Nanocrystal-Modified Materials 145

4.6.2.1 Self-Assembly of Polysaccharide Nanocrystals in Aqueous Medium 145

4.6.2.2 Self-Assembly of Polysaccharide Nanocrystals in Organic Medium 148

4.6.2.3 Self-Assembly of Polysaccharide Nanocrystals in Solid Film 148

4.6.3 Polysaccharide Nanocrystal-Modified Materials Prepared by LBL Method 150

4.7 Other Methods and Prospects 152

List of Abbreviations 153

References 154

5 Polysaccharide Nanocrystal-Reinforced Nanocomposites 165
Hanieh Kargarzadeh and Ishak Ahmad

5.1 Introduction 165

5.2 Rubber-Based Nanocomposites 166

5.3 Polyolefin-Based Nanocomposites 175

5.4 Polyurethane andWaterborne Polyurethane-Based Nanocomposites 178

5.5 Polyester-Based Nanocomposites 192

5.6 Starch-Based Nanocomposites 200

5.7 Protein-Based Nanocomposites 204

5.8 Concluding Remarks 211

List of Abbreviations 211

References 213

6 Polysaccharide Nanocrystals-Based Materials for Advanced Applications 219
Ning Lin, Jin Huang, and Alain Dufresne

6.1 Introduction 219

6.2 Surface Characteristics Induced Functional Nanomaterials 220

6.2.1 Active Groups 220

6.2.1.1 Importing Functional Groups or Molecules 220

6.2.1.2 Template for Synthesizing Inorganic Nanoparticles 222

6.2.2 Surface Charges and Hydrophilicity 225

6.2.2.1 Emulsion Nanostabilizer 225

6.2.2.2 High-Efficiency Adsorption 226

6.2.2.3 Permselective Membrane 226

6.2.3 Nanoscale and High Surface Area 227

6.2.3.1 Surface Cell Cultivation 227

6.2.3.2 Water Decontamination 227

6.3 Nano-Reinforcing Effects in Functional Nanomaterials 228

6.3.1 Soft Matter 229

6.3.1.1 Hydrogel 229

6.3.1.2 Sponge, Foam, Aerogel, and Tissue-Engineering Nanoscaffold 231

6.3.2 Special Mechanical Materials 233

6.3.3 Self-Healable and Shape-Memory Materials 236

6.3.4 Polymeric Electrolytes and Battery 237

6.3.5 Semi-conducting Material 238

6.4 Optical Materials Derived from Liquid Crystalline Property 239

6.5 Special Films and Systems Ascribed to Barrier Property 241

6.5.1 Drug Delivery – Barrier for Drug Molecules 242

6.5.2 Barrier Nanocomposites – Barrier forWater and Oxygen 244

6.6 Other Functional Applications 244

6.7 Concluding Remarks 244

List of Abbreviations 245

References 246

7 Characterization of Polysaccharide Nanocrystal-Based Materials 255
Alain Dufresne and Ning Lin

7.1 Introduction 255

7.2 Mechanical Properties of Polysaccharide Nanocrystals 256

7.2.1 Intrinsic Mechanical Properties of Polysaccharide Nanocrystals 256

7.2.2 Mechanical Properties of Polysaccharide Nanocrystal Films 259

7.3 Dispersion of Polysaccharide Nanocrystals 261

7.3.1 Observation of Polysaccharide Nanocrystals in Matrix 263

7.3.2 Three-Dimensional Network of Polysaccharide Nanocrystals 266

7.4 Mechanical Properties of Polysaccharide Nanocrystal-Based Materials 269

7.4.1 Influence of the Morphology and Dimensions of the Nanocrystals 273

7.4.2 Influence of the Processing Method 274

7.5 Polysaccharide Nanocrystal/Matrix Interfacial Interactions 276

7.6 Thermal Properties of Polysaccharide Nanocrystal-Based Materials 281

7.6.1 Thermal Properties of Polysaccharide Nanocrystals 281

7.6.2 Glass Transition of Polysaccharide Nanocrystal-Based Nanocomposites 282

7.6.3 Melting/Crystallization Temperature of Polysaccharide Nanocrystal-Based Nanocomposites 283

7.6.4 Thermal Stability of Polysaccharide Nanocrystal-Based Nanocomposites 284

7.7 Barrier Properties of Polysaccharide Nanocrystal-Based Materials 284

7.7.1 Barrier Properties of Polysaccharide Nanocrystal Films 285

7.7.2 Swelling and Sorption Properties of Polysaccharide Nanocrystal-Based Nanocomposites 286

7.7.3 Water Vapor Transfer and Permeability of Polysaccharide Nanocrystal-Based Nanocomposites 287

7.7.4 Gas Permeability of Polysaccharide Nanocrystal-Based Nanocomposites 288

7.8 Concluding Remarks 289

List of Abbreviations 290

References 291

Index 301

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