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Cellulose Based Composites: New Green Nanomaterials

ISBN: 978-3-527-32719-5
328 pages
May 2014
Cellulose Based Composites: New Green Nanomaterials (3527327193) cover image
Aimed at researchers involved in this emerging field in both academia and industry, this book is unique in its focus on cellulose nanofibers, especially nano-composites, nanomoities and other plant based-resins and their composites. Despite its concise presentation, this handbook and ready reference provides a complete overview, containing such important topics as electrospinning, isolation, characterization and deposition of metallic nanoparticles.
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List of Contributors XIII

Preface XIX

Section I Cellulose Nanofiber- and Microfiber Based Composites 1

1 Cellulose-Nanofiber-Based Materials 3
Antonio Norio Nakagaito and Hiroyuki Yano

1.1 Introduction 3

1.2 The Percolation and Entanglement Phenomena of Cellulose Nanofibers 4

1.3 Cellulose-Nanofiber-Based Materials 7

1.4 Extraction of Cellulose Nanofibers 8

1.5 Cellulose-Nanofiber-Based Materials for Structural and Semistructural Applications 11

1.6 Optically Transparent Materials Reinforced with Cellulose Nanofibers 15

1.7 Green Cellulose-Nanofiber-Based Materials 18

1.8 Future Prospects 21

Abbreviations 22

References 23

2 Fabrication and Evaluation of Cellulose-Nanofiber-Reinforced Green Composites 27
Hitoshi Takagi

2.1 Introduction 27

2.2 Cellulose Nanofiber 27

2.3 Preparation of Cellulose Nanofibers 28

2.3.1 Chemical Extraction Method 28

2.3.2 Enzymatic Extraction Method 29

2.3.3 Physical Extraction Method 29

2.4 Fabrication of Cellulose-Nanofiber-Reinforced Composites 30

2.5 Properties of Cellulose-Nanofiber-Reinforced Composites 31

2.5.1 Mechanical Properties 31

2.5.2 Thermal Properties 34

2.5.3 Optical Properties 38

2.6 Summary 39

Abbreviations 40

References 40

3 Cellulose Microfibrils Isolated from Musaceae Fibrous Residues 43
Robin Zuluaga Gallego, Jean-Luc Putaux, Cristina Castro Herazo, Juan Manuel Vélez, Iñaki Mondragon, Aloña Retegi Miner, and Piedad Gañán Rojo

3.1 Introduction 43

3.2 Vascular Bundles 44

3.3 Isolation and Purification of Cellulose Microfibrils from Vascular Bundles 46

3.4 Chemical Characterization of Cellulose Microfibrils 46

3.4.1 Monosaccharide Composition 46

3.4.2 Infrared Spectroscopy Measurements 48

3.5 Structure and Morphology of Cellulose Microfibrils 50

3.5.1 X-Ray Diffraction Analysis 50

3.5.2 Transmission Electron Microscopy 51

3.5.3 Solid-State Nuclear Magnetic Resonance Studies 52

3.6 Thermal Behavior of Cellulose Microfibrils 53

3.7 Conclusions 54

3.8 Materials and Methods 55

3.8.1 Materials 55

3.8.2 Scanning Electron Microscopy 55

3.8.3 Anion-Exchange Chromatography 55

3.8.4 Attenuated Total Reflection Fourier Transform Infrared Spectroscopy 56

3.8.5 Transmission Electron Microscopy 56

3.8.6 X-Ray Diffraction 56

3.8.7 CP/MAS 13C Nuclear Magnetic Resonance 56

3.8.8 Thermogravimetric Analysis 57

Acknowledgments 57

Abbreviations 57

References 58

4 Nanocomposites Based on Matrices Extracted from Vegetable Oils and Bacterial Cellulose 63
Aloña Retegi Miner, Robin Zuluaga Gallego, Piedad Gañán Rojo, and Iñaki Mondragon

4.1 Introduction 63

4.2 Vegetable Oils 66

4.3 Bacterial Cellulose 69

4.4 Bacterial and Plant-Based Cellulose Nanocomposites with Polymer Matrices 72

4.5 Applications 74

References 75

5 Nano- and Microfiber Composites Reinforced with Cellulose Nanocrystals 79
Maria S. Peresin, Justin O. Zoppe, Maria E. Vallejos, Youssef Habibi, Martin A. Hubbe, and Orlando J. Rojas

5.1 Introduction 79

5.2 Cellulose Nanocrystals 80

5.3 Electrospinning 81

5.4 Cellulose Nanocrystals (CNs) for the Production of Composites 83

5.5 Electrospun Nanofibers Reinforced with CNs 84

5.5.1 CNs in Fibrous Hydrophobic Matrices 84

5.5.1.1 Thermomechanical Properties of Electrospun Composite Microfibers 86

5.5.2 CNs in Poly(ε-Caprolactone) Composite Fibers 87

5.5.2.1 Surface Grafting 87

5.5.2.2 Preparation of Dispersions and Electrospinning 89

5.5.2.3 Production and Characterization of Composite Nanofibers 89

5.5.2.4 Thermomechanical Properties of PCL-Based Fiber Nanocomposites 91

5.5.3 CNs in Composite Cellulose Acetate Fibers 94

5.5.3.1 Preparation of CA Solutions and Electrospinning 95

5.5.3.2 Morphological and Thermal Characterization 95

5.5.4 CNs in Polyvinyl Alcohol Fibers 96

5.5.4.1 Preparation of PVA-CN Suspension 97

5.5.4.2 Electrospinning 97

5.5.4.3 Morphological and Chemical Characterization of CN-Loaded PVA Nanofiber Mats 97

5.5.4.4 Thermal Properties of the PVA-CN Nanofiber Composites 100

5.5.4.5 Mechanical Properties of PVA-CN Nanofiber Composites 102

5.6 Applications of CN-Based Composites 103

5.7 Conclusions 105

Acknowledgments 105

References 105

6 Hydrolytic Degradation of Nanocomposite Fibers Electrospun from Poly(Lactic Acid)/Cellulose Nanocrystals 117
Chunhui Xiang and Margaret W. Frey

6.1 Introduction 117

6.2 Experiments 119

6.2.1 Materials 119

6.2.2 Methods and Techniques 120

6.2.2.1 Elevated Temperature Electrospinning Processing 120

6.2.2.2 Water Contact Angle Measurements 120

6.2.2.3 Hydrolytic Degradation of Electrospun Nanocomposite Fibers 121

6.2.2.4 Microscopy 121

6.2.2.5 Size Exclusion Chromatography (SEC) 121

6.2.2.6 Thermogravimetric Analysis (TGA) 121

6.3 Results and Discussion 122

6.3.1 Distribution of Cellulose Nanocrystals in the Electrospun PLA/Cellulose Nanocomposite Fibers 122

6.3.2 Thermogravimetric Analysis of Electrospun PLA/Cellulose Nanocomposite Fibers 122

6.3.3 Hydrophobicity/Hydrophilicity of Electrospun Non-woven Fabrics 123

6.3.4 Morphologies of the Electrospun PLA/Cellulose Nanocomposite Fibers during Hydrolytic Degradation 126

6.3.5 Molecular Weight Change of PLA in the Electrospun Nanocomposite Fibers during Hydrolytic Degradation 127

6.4 Conclusions 134

Acknowledgment 134

References 135

Section II Cellulose-Fiber-Based Composites 137

7 Environment-Friendly ‘‘Green’’ Resins and Advanced Green Composites 139
Xiaosong Huang and Anil N. Netravali

7.1 Introduction 139

7.2 Experimental 142

7.2.1 Materials 142

7.2.2 Preparation of the Modified SPC 142

7.2.3 Specimen Characterization 143

7.3 Results and Discussion 144

7.3.1 Mechanical Properties of the Modified Resins 144

7.3.2 Characterization of Linen Yarns and LC-Cellulose Fibers 146

7.3.3 Characterization of Linen Yarns and LC-Cellulose-Fiber-Reinforced Composites 148

7.4 Conclusions 153

Acknowledgments 154

Abbreviations 154

References 154

8 Toughening and Strengthening of Natural Fiber Green Composites 157
Koichi Goda and Rie Nakamura

8.1 Introduction 157

8.2 Preloading Effect 157

8.2.1 Experimental 158

8.2.1.1 Test Material and Fiber Tensile Specimen 158

8.2.1.2 Cyclic Loading Treatment and Tensile Fracture Test 159

8.2.1.3 Constant Loading Treatment 160

8.2.1.4 Test Materials, Fabrication, and Tensile Specimen of Green Composites 160

8.2.2 Experimental Results of Single Ramie Fibers 161

8.2.2.1 Cyclic Deformation Behavior of Single Ramie Fibers 161

8.2.2.2 Tensile Properties of Cyclic-Loaded Single Ramie Fibers 162

8.2.2.3 Tensile Properties of Constant-Load-Applied Ramie Fibers 163

8.2.2.4 Discussion 163

8.2.3 Experimental Results of Green Composites 166

8.2.3.1 Tensile Strength 166

8.2.3.2 Young’s modulus 167

8.3 Effect of Alkali Treatment 169

8.3.1 Experimental 169

8.3.1.1 Materials and Alkali Treating Apparatus 169

8.3.1.2 X-ray Diffraction Measurement 170

8.3.1.3 Fabrication of Green Composites Reinforced with Alkali-Treated Ramie Plied Yarns 171

8.3.1.4 Tensile and Impact Tests 172

8.3.2 Tensile Properties of Alkali-Treated Single Ramie Fibers 172

8.3.3 Effect of NaOH Concentration on Ramie Fiber X-ray Analysis 174

8.3.3.1 X-ray Diffraction Diagram 174

8.3.3.2 Crystalline Transition Rate 174

8.3.3.3 Crystallinity Index 175

8.3.4 Relation between Mechanical Properties and Cellulose Microfibrils 176

8.3.5 Tensile Properties of Mercerized Ramie-Fiber-Reinforced Green Composites 178

8.3.6 Impact Properties of Mercerized Ramie-Fiber-Reinforced Green Composites 180

8.4 Conclusion 182

References 182

9 Composites of Nanocellulose and Lignin-like Polymers 185
Justin R. Barone

9.1 Introduction 185

9.2 Experimental 187

9.2.1 Materials 187

9.2.2 Preparation of TEMPO-Oxidized Nanocellulose 187

9.2.3 Enzymatic Polymerization of Phenol and Coniferyl Alcohol 187

9.2.4 Scanning Electron Microscopy (SEM) 188

9.2.5 Fourier Transform Infrared (FTIR) Spectroscopy 188

9.2.6 Differential Scanning Calorimetry (DSC) 188

9.2.7 Thermogravimetric Analysis (TGA) 188

9.2.8 Nanoindentation 188

9.3 Results and Discussion 189

9.3.1 Nanocomposite Morphology 189

9.3.2 Nanocomposite’s Thermal Properties 191

9.3.3 Nanocomposite’s Mechanical Properties 192

9.3.4 Nanocomposite’s Structure 193

9.4 Conclusions 196

Acknowledgments 197

References 197

10 Biodegradable Polymer Materials from Proteins Produced by the Animal Coproducts Industry: Bloodmeal 201
Suraj Sharma, Fehime Vatansever, James N. Hodges, and Igor Luzinov

10.1 Introduction 201

10.2 Materials and Experimental Procedures 203

10.2.1 Materials 203

10.2.2 Specimen Preparation 203

10.2.3 Mechanical Properties and Morphology 203

10.2.4 Thermal Analysis 204

10.2.5 Moisture Testing 204

10.3 Results and Discussion 204

10.3.1 Plastics from Bloodmeal Proteins 204

10.3.2 Mechanical Properties of the Bloodmeal Plastic 206

10.3.3 Fabrication of Plastics from Blends Containing Bloodmeal Proteins 207

10.3.4 Mechanical Properties of Bloodmeal Plastics 209

10.4 Conclusions 213

Acknowledgments 213

References 214

Section III Cellulose and Other Nanoparticles 215

11 Biocomposites Made from Bovine Bone and Crystals of Silver and Platinum 217
Raul Alberto Morales-Luckie, Sergio Gama-Lara, Ignacio Guadalupe Becerril-Juarez, Alfredo Rafael Vilchis-Nestor, Victor Sanchez-Mendieta, and Juan P. Hinestroza

11.1 Introduction 217

11.2 Bovine Bone–Platinum Composites 218

11.3 Bovine Bone–Silver Composites 228

11.4 Conclusions 230

Acknowledgments 230

References 230

12 Bio-Inspired Synthesis of Metal Nanoparticles Using Cellulosic Substrates as Nature Templates 233
Raul Alberto Morales-Luckie, Alfredo Rafael Vilchis-Nestor, Victor Sanchez-Mendieta, and Juan P. Hinestroza

12.1 Introduction 233

12.2 Synthesis of Metal Nanoparticles Using Wood as a Template 234

12.2.1 Nanoparticles of Ruthenium Synthesized on Swietenia macrophylla (Mahogany) and Pinus ayacahuite (Pine) 235

12.2.2 Nanoparticles of Platinum Synthesized on Arce saccharum (Maple) 239

12.2.3 Formation of Silver Nanoparticles Using Bursera simaruba (L) 243

12.3 Summary 246

References 248

13 Conformal Coating of Antimicrobial Silver Nanoparticles on Cationic and Anionic Cellulosic Substrates 249
Hong Dong and Juan P. Hinestroza

13.1 Introduction 249

13.2 Preparation of Anionic and Cationic Cotton Fabrics 250

13.2.1 Synthesis of Ag NPs on Anionic Cotton 251

13.2.2 Assembly of Ag NPs on Cationic Cotton 252

13.2.3 Antibacterial Tests 252

13.2.4 Characterization 253

13.3 Results and Discussion 253

13.3.1 Synthesis of Ag NPs on Anionic Cotton 253

13.3.2 Ag NPs Assembled on Cationic Cotton 255

13.3.3 Antibacterial Activity 257

13.4 Conclusions 258

Acknowledgments 259

References 259

14 Wood/Biopolymer/Nanoclay Composites 261
Daniel De Kee and Qingkai Meng

14.1 Biopolymers 261

14.1.1 Introduction 261

14.1.2 Poly(Lactic Acid) 261

14.2 PLA/Clay Nanocomposites 267

14.2.1 Clay 267

14.2.2 PLA/Clay Nanocomposites 268

14.3 PLA/Wood Flour Composites 275

14.3.1 Wood Flour 275

14.3.2 PLA/Wood Flour Composites 277

14.4 PLA/Clay/Wood Composites 279

14.5 Conclusions 291

Acknowledgments 292

References 292

Index 297

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Juan P. Hinestroza is Associate Professor of Fiber Science and directs the Textiles Nanotechnology Laboratory in the Department of Fiber Science & Apparel Design at the College of Human Ecology of Cornell University. Prior to pursuing doctoral studies, he worked as a process control engineer for The Dow Chemical Company. From 2007-2010, Professor Hinestroza was chair and organizer of sessions on natural and green composites for the Division of Cellulose and Renewable Materials of the American Chemical Society annual meetings. Professor Hinestroza has been the recipient of a many awards including the National Science Foundation CAREER award, the J.D. Watson Young Investigator award from the NY State Foundation for Science Technology and Innovation and the Educator of the Year Award from the Society of Professional Hispanic Engineers.

Anil N. Netravali is Professor of Fiber Science in the Department of Fiber Science & Apparel Design at Cornell University. His main research is in the field of Fiber Reinforced Composites. In recent years he has made significant contributions in the area of sustainable 'Green' composites and materials. He is a member of the American Chemical Society, the American Nano Society and The Fiber Society. He was the recipient of the Fiber Society Founder's Award in 2012. He serves as an adjunct faculty in the Dept. of Materials Science & Engineering at Tuskegee University, Tuskegee, AL and Universidade Federal do Amazonas (UFAM), Manaus, Brazil. He serves on the Editorial Advisory Boards of several research journals including Composites Science and Technology, Journal of Biobased Materials and Bioenergy, Journal of Renewable Materials, Reviews of Adhesion and Adhesives, Fibers, Journal of Engineered Fibers and Fabrics and Textile Research Journal
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