Polymer Composites, Biocomposites, Volume 3 Biocomposites Polymer Composites Series

Polymer composites are materials in which the matrix polymer is reinforced with organic/inorganic fillers of a definite size and shape, leading to enhanced performance of the resultant composite. These materials find a wide number of applications in such diverse fields as geotextiles, building, electronics, medical, packaging, and automobiles.

This first systematic reference on the topic emphasizes the characteristics and dimension of this reinforcement. The authors are leading researchers in the field from academia, government, industry, as well as private research institutions across the globe, and adopt a practical approach here, covering such aspects as the preparation, characterization, properties and theory of polymer composites.

The book begins by discussing the state of the art, new challenges, and opportunities of various polymer composite systems. Interfacial characterization of the composites is discussed in detail, as is the macro- and micromechanics of the composites. Structure-property relationships in various composite systems are explained with the help of theoretical models, while processing techniques for various macro- to nanocomposite systems and the influence of processing parameters on the properties of the composite are reviewed in detail. The characterization of microstructure, elastic, viscoelastic, static and dynamic mechanical, thermal, tribological, rheological, optical, electrical and barrier properties are highlighted, as well as their myriad applications.

Divided into three volumes: Vol. 1. Macro- and Microcomposites; Vol. 2. Nanocomposites; and Vol. 3. Biocomposites.

The Editors XIX

List of Contributors XXI

1 Advances in Polymer Composites: Biocomposites –State of the Art, New Challenges, and Opportunities 1
Koichi Goda, Meyyarappallil Sadasivan Sreekala, Sant Kumar Malhotra, Kuruvilla Joseph, and Sabu Thomas

1.1 Introduction 1

1.2 Development of Biocomposite Engineering 3

1.3 Classification of Biocomposites 5

References 8

2 Synthesis, Structure, and Properties of Biopolymers (Natural and Synthetic) 11
Raju Francis, Soumya Sasikumar, and Geethy P. Gopalan

2.1 Introduction 11

2.2 Classification 13

2.3 Natural Biopolymers 13

2.3.1 Proteins 14

2.3.2 Polysaccharides 27

2.3.3 Polysaccharides from Marine Sources 34

2.3.4 Low Molecular Weight Biopolymers 39

2.3.5 Microbial Synthesized Biopolymers 42

2.3.6 Natural Poly(Amino Acids) 46

2.3.7 Nucleic Acids 50

2.4 Synthetic Biopolymers 54

2.4.1 Poly(Glycolide) PGA or Poly(Glycolic Acid) 55

2.4.2 Poly(Lactic Acid) (PLA) 55

2.4.3 Poly(Lactide-co-Glycolide) 56

2.4.4 Polycaprolactone (PCL) 57

2.4.5 Poly(p-Dioxanone) (PDO) 57

2.4.6 Poly(Trimethylene Carbonate) (PTMC) 58

2.4.7 Poly-β-Hydroxybutyrate (PHB) 58

2.4.8 Poly(Glycerol Sebacic Acid) (PGS) 58

2.4.9 Poly(Propylene Fumarate) (PPF) 59

2.4.10 Poly(Anhydrides) (PAs) 60

2.4.11 Poly(Orthoesters) (POEs) 60

2.4.12 Poly(Phosphazene) 61

2.4.13 Poly(Vinyl Alcohol) (PVA) 62

2.4.14 Poly(Hydroxyalkanoates) (PHAs) 63

2.4.15 Poly(Ester Amides) (PEAs) 63

2.5 Need for Biopolymers 64

2.6 Exceptional Properties of Biopolymers 65

2.7 Biomedical Polymers 65

2.7.1 Chitosan 66

2.7.2 Poly(Lactic Acid) (PLA) 67

2.7.3 Collagen 67

2.7.4 Polycaprolactone (PCL) 68

2.7.5 Poly(2-Hydroxyethyl Methacrylate) (PHEMA) 68

2.7.6 Carbohydrate-Based Vaccines 69

2.7.7 Chitin 69

2.7.8 Albumin 69

2.7.9 Fibrin 70

2.7.10 Hyaluronic Acid (HA) 70

2.7.11 Chondroitin Sulfate (CS) 70

2.7.12 Alginic Acid 70

2.7.13 Poly(Anhydrides) 70

2.8 Composite Material 71

2.9 Blends 71

2.10 Applications of Biopolymers 72

2.10.1 Medical Applications 72

2.10.2 Agricultural Applications 76

2.10.3 Packaging 77

2.11 Partially Biodegradable Packaging Materials 80

2.12 Nonbiodegradable Biopolymers 80

2.12.1 Poly(Thioesters) 80

2.12.1.1 Poly(3-Mercaptopropionate) (Poly(3MP)) 81

2.13 Conversion of Nonbiodegradable to Biodegradable Polymers 82

2.14 Current Research Areas in Biopolymers and Bioplastics 82

2.15 General Findings and Future Prospects 83

Acknowledgments 83

Abbreviations 84

References 84

3 Preparation, Microstructure, and Properties of Biofibers 109
Takashi Nishino

3.1 Introduction 109

3.2 Structure of Natural Plant Fibers 110

3.2.1 Microstructure 110

3.2.2 Crystal Structure 114

3.3 Ultimate Properties of Natural Fibers 117

3.3.1 Elastic Modulus 117

3.3.2 Tensile Strength 120

3.4 Mechanical and Thermal Properties of Cellulose Microfibrils and Macrofibrils 121

3.5 All-Cellulose Composites and Nanocomposites 126

3.6 Conclusions 129

References 129

4 Surface Treatment and Characterization of Natural Fibers: Effects on the Properties of Biocomposites 133
Donghwan Cho, Hyun-Joong Kim, and Lawrence T. Drzal

4.1 Introduction 133

4.2 Why Is Surface Treatment of Natural Fibers Important in Biocomposites? 134

4.3 What Are the Surface Treatment Methods of Natural Fibers? 137

4.3.1 Chemical Treatment Methods 138

4.3.2 Physical Treatment Methods 145

4.4 How Does the Surface Treatment Influence the Properties of Biocomposites? 149

4.4.1 Chemical Changes of Natural Fibers 149

4.4.2 Morphological and Structural Changes of Natural Fibers 150

4.4.3 Mechanical Changes of Natural Fibers 151

4.4.4 Interfacial Properties of Biocomposites 153

4.4.5 Mechanical Properties of Biocomposites 157

4.4.6 Impact Properties of Biocomposites 160

4.4.7 Dynamic Mechanical Properties of Biocomposites 161

4.4.8 Thermal Properties of Biocomposites 164

4.4.9 Water Absorption Behavior of Biocomposites 166

4.5 Concluding Remarks 168

References 169

5 Manufacturing and Processing Methods of Biocomposites 179

5.1 Processing Technology of Natural Fiber-Reinforced Thermoplastic Composite 179
Tatsuya Tanaka

5.1.1 Background 179

5.1.2 NF- Reinforced PLA Resin Composite Material 181

5.1.3 Pellet Production Technology of Continuation Fiber-Reinforced Thermoplastic Resin Composite Material 181

5.1.4 Pellet Manufacturing Technology of the Continuous Natural Fiber–Reinforced Thermoplastic Resin Composite Material 183

5.1.5 Pellet Manufacturing Technology of the Distributed Type Natural Fiber–Reinforced Thermoplastic Resin Composites 189

5.1.6 Future Outlook 197

5.2 Processing Technology of Wood Plastic Composite (WPC) 197
Hirokazu Ito

5.2.1 Raw Materials 198

5.2.2 Compounding Process 203

5.2.3 Molding Process 207

5.2.4 The Future Outlook for WPC in Industry 209

References 209

6 Biofiber-Reinforced Thermoset Composites 213
Masatoshi Kubouchi, Terence P. Tumolva, and Yoshinobu Shimamura

6.1 Introduction 213

6.2 Materials and Fabrication Techniques 213

6.2.1 Thermosetting Resins 213

6.2.2 Natural Fibers 215

6.2.3 Fabrication Techniques 217

6.3 Biofiber-Reinforced Synthetic Thermoset Composites 220

6.3.1 Polyester-Based Composites 220

6.3.2 Epoxy-Based Composites 222

6.3.3 Vinyl Ester-Based Composites 223

6.3.4 Phenolic Resin-Based Composites 224

6.3.5 Other Thermoset-Based Composites 225

6.4 Biofiber-Reinforced Biosynthetic Thermoset Composites 225

6.4.1 Lignin-Based Composites 225

6.4.2 Protein-Based Composites 226

6.4.3 Tannin-Based Composites 227

6.4.4 Triglyceride-Based Composites 228

6.4.5 Other Thermoset-Based Composites 229

6.5 End-of-Life Treatment of NFR Thermoset Composites 231

6.5.1 Recycling as Composite Fillers 231

6.5.2 Pyrolysis 232

6.5.3 Chemical Recycling 232

6.5.4 Energy Recovery 233

6.6 Conclusions 233

References 234

7 Biofiber-Reinforced Thermoplastic Composites 239
Susheel Kalia, Balbir Singh Kaith, Inderjeet Kaur, and James Njuguna

7.1 Introduction 239

7.2 Source of Biofibers 240

7.3 Types of Biofibers 241

7.3.1 Annual Biofibers 241

7.3.2 Perennial Biofibers (Wood Fibers) 245

7.4 Advantages of Biofibers 248

7.5 Disadvantages of Biofibers 248

7.6 Graft Copolymerization of Biofibers 250

7.7 Surface Modifications of Biofibers Using Bacterial Cellulose 252

7.8 Applications of Biofibers as Reinforcement 255

7.8.1 Composite Boards 256

7.8.2 Biofiber-Reinforced Thermoplastic Composites 259

7.9 Biofiber Graft Copolymers Reinforced Thermoplastic Composites 271

7.10 Bacterial Cellulose and Bacterial Cellulose-Coated, Biofiber-Reinforced, Thermoplastic Composites 274

7.11 Applications of Biofiber-Reinforced Thermoplastic Composites 277

7.12 Conclusions 278

References 279

8 Biofiber-Reinforced Natural Rubber Composites 289
Parambath Madhom Sreekumar, Preetha Gopalakrishnan, and Jean Marc Saiter

8.1 Introduction 289

8.2 Natural Rubber (NR) 289

8.3 Biofibers 290

8.4 Processing 292

8.5 Biofiber-Reinforced Rubber Composites 292

8.5.1 Cure Characteristics 293

8.5.2 Mechanical Properties 294

8.5.3 Viscoelastic Properties 300

8.5.4 Diffusion and Swelling Properties 302

8.5.5 Dielectric Properties 304

8.5.6 Rheological and Aging Characteristics 305

8.6 Approaches to Improve Fiber–Matrix Adhesion 307

8.6.1 Mercerization 307

8.6.2 Benzoylation 308

8.6.3 Coupling Agents 308

8.6.4 Bonding Agents 309

8.7 Applications 312

8.8 Conclusions 312

References 312

9 Improvement of Interfacial Adhesion in Bamboo Polymer Composite Enhanced with Microfibrillated Cellulose 317
Kazuya Okubo and Toru Fujii

9.1 Introduction 317

9.2 Materials 318

9.2.1 Matrix 318

9.2.2 Bamboo Fibers 318

9.2.3 Microfibrillated cellulose (MFC) 319

9.3 Experiments 320

9.3.1 Fabrication Procedure of Developed Composite Using PLA, BF, and MFC (PLA/BF/MFC Composite) 320

9.3.2 Three-Point Bending Test 321

9.3.3 Microdrop Test 321

9.3.4 Fracture Toughness Test 321

9.3.5 Bamboo Fiber Embedded Test 322

9.4 Results and Discussion 322

9.4.1 Internal State of PLA/BF/MFC Composite 322

9.4.2 Bending Strength of PLA/BF/MFC Composite 322

9.4.3 Fracture Toughness of PLA/BF/MFC Composite 325

9.4.4 Crack Propagation Behavior 325

9.5 Conclusion 328

Acknowledgments 328

References 328

10 Textile Biocomposites 331

10.1 Elastic Properties of Twisted Yarn Biocomposites 331
Koichi Goda and Rie Nakamura

10.1.1 Introduction 331

10.1.2 Classical Theories of Yarn Elastic Modulus 332

10.1.3 Orthotropic Theory for Twisted Yarn-Reinforced Composites 335

10.1.4 Conclusion 344

10.2 Fabrication Process for Textile Biocomposites 345
Asami Nakai and Louis Laberge Lebel

10.2.1 Introduction 345

10.2.2 Intermediate Materials for Continuous Natural Fiber-Reinforced Thermoplastic Composites 345

10.2.3 Braid-Trusion of Jute/Polylactic Acid Composites 349

10.2.4 Conclusion 358

References 358

11 Bionanocomposites 361
Eliton S. Medeiros, Amélia S.F. Santos, Alain Dufresne, William J. Orts, and Luiz H. C. Mattoso

11.1 Introduction 361

11.2 Bionanocomposites 362

11.2.1 Bionanocomposite Classification 362

11.2.2 Reinforcements Used in Bionanocomposites 364

11.2.3 Matrices for Bionanocomposites 369

11.2.4 Mixing, Processing, and Characterization of Bionanocomposites 380

11.2.5 Polysaccharide Bionanocomposites 383

11.2.6 Protein Bionanocomposites 391

11.2.7 Bionanocomposites Using Biodegradable Polymers from Microorganisms and Biotechnology 399

11.2.8 Bionanocomposites Using Biodegradable Polymers from Petrochemical Products 406

11.2.9 Other Biodegradable Polymers 416

11.3 Final Remarks 419

References 420

12 Fully Biodegradable ‘‘Green’’ Composites 431
Rie Nakamura and Anil N. Netravali

12.1 Introduction 431

12.2 Soy Protein-Based Green Composites 434

12.2.1 Introduction 434

12.2.2 Fiber/Soy Protein Interfacial Properties 435

12.2.3 Effect of Soy Protein Modification on the Properties of Resins and Composites 437

12.3 Starch-Based Green Composites 441

12.3.1 Introduction 441

12.3.2 Fiber Treatments 442

12.3.3 Cellulose Nanofiber-Reinforced ‘‘Green’’ Composites 446

12.3.4 Evaluation of Mechanical Properties of Green Composites 447

12.4 Biodegradation of ‘‘Green’’ Composites 450

12.4.1 Biodegradation of PHBV 451

12.4.2 Effect of Soy Protein Modification on Its Biodegradation 455

12.4.3 Biodegradation of Starch-Based Green Composites 458

References 460

13 Applications and Future Scope of ‘‘Green’’ Composites 465
Hyun-Joong Kim, Hyun-Ji Lee, Taek-Jun Chung, Hyeok-Jin Kwon, Donghwan Cho, and William Tai Yin Tze

13.1 Introduction 465

13.1.1 Biodegradable Plastics versus Traditional Plastics 466

13.2 Applications of Biocomposites (Products/Applications/Market) 467

13.2.1 Survey of Technical Applications of Natural Fiber Composites 467

13.2.2 Automotive Applications 469

13.2.3 Structural Applications 472

13.3 Future Scope 476

13.3.1 Choice of Materials and Processing Methods 477

13.4 Conclusion 478

References 479

14 Biomedical Polymer Composites and Applications 483
Dionysis E. Mouzakis

14.1 Introduction 483

14.2 Biocompatibility Issues 485

14.3 Natural Matrix Based Polymer Composites 488

14.3.1 Silk Biocomposites 488

14.3.2 Chitin and Chitosan as Matrices 489

14.3.3 Mammal Protein-Based Biocomposites 490

14.3.4 Hyaluronic Acid Composites 491

14.3.5 Other Natural Polymer Matrices 493

14.4 Synthetic Polymer Matrix Biomedical Composites 494

14.4.1 Biodegradable Polymer Matrices 495

14.4.2 Synthetic Polymer Composites 499

14.5 Smart Polymers and Biocomposites 502

14.6 Polymer-Nanosystems and Nanocomposites in Medicine 504

14.7 Conclusions 506

14.8 Outlook 507

References 507

15 Environmental Effects, Biodegradation, and Life Cycle Analysis of Fully Biodegradable ‘‘Green’’ Composites 515
Ajalesh Balachandran Nair, Palanisamy Sivasubramanian, Preetha Balakrishnan, Kurungattu Arjunan Nair Ajith Kumar, and Meyyarappallil Sadasivan Sreekala

15.1 Introduction 515

15.2 Environmental Aspects 518

15.3 Environmental Impacts of Green Composite Materials 520

15.4 Choice of Impact Categories 521

15.4.1 Global Warming 521

15.4.2 Acidification 521

15.4.3 Abiotic Depletion 521

15.5 Environmental Impact of Polylactide 522

15.6 Environmental Effect of Polyvinyl Alcohol (PVA) 523

15.7 Potential Positive Environmental Impacts 526

15.7.1 Composting 526

15.7.2 Landfill Degradation 526

15.7.3 Energy Use 526

15.8 Potential Negative Environmental Impacts 526

15.8.1 Pollution of Aquatic Environments 527

15.8.2 Litter 528

15.9 Biodegradation 529

15.9.1 Biodegradability Test 530

15.10 Advantages of Green Composites over Traditional Composites 532

15.11 Disadvantages of Green Composites 532

15.12 Application and End-Uses 532

15.12.1 Automobiles 533

15.12.2 Aircrafts and Ships 533

15.12.3 Mobile Phones 533

15.12.4 Decorative Purposes 534

15.12.5 Uses 534

15.13 Biodegradation of Polyvinyl Alcohol (PVA) under Different Environmental Conditions 534

15.13.1 Biodegradation of Polyvinyl Alcohol under Composting Conditions 535

15.13.2 Biodegradation of Polyvinyl Alcohol in Soil Environment 535

15.13.3 Anaerobic Biodegradation of Polyvinyl Alcohol in Aqueous Environments 536

15.14 Biodegradation of Polylactic Acid 536

15.15 Biodegradation of Polylactic Acid and Its Composites 537

15.16 Biodegradation of Cellulose 539

15.17 Cellulose Fiber-Reinforced Starch Biocomposites 539

15.18 Life Cycle Assessment (LCA) 541

15.18.1 Methods 542

15.18.2 Green Design Metrics 543

15.18.3 Decision Matrix 545

15.19 Life Cycle Assessment Results 546

15.20 Green Principles Assessment Results 548

15.21 Comparison 548

15.22 Life Cycle Inventory Analysis of Green Composites 551

15.22.1 Fiber Composites 551

15.22.2 Natural Fibers 552

15.22.3 Life Cycle Analysis of Polylactide (PLA) 552

15.23 Life Cycle Analysis of Poly(hydroxybutyrate) 556

15.24 Life Cycle Analysis of Cellulose Fibers 556

15.25 Conclusions 558

Abbreviations 559

References 561

Index 569