Eco-friendly Polymer Nanocomposites (eBook)

Dr. Vijay Kumar Thakur has been working as Research Faculty (Staff Scientist) in the School of Mechanical and Materials Engineering at Washington State University, U.S.A, since September 2013. His former appointments include being a Research Scientist in Temasek Laboratories at Nanyang Technological University, Singapore, and a Visiting Research Fellow in the Department of Chemical and Materials Engineering at LHU-Taiwan. His research interests include the synthesis and processing of biobased polymers, nanomaterials, polymer micro/nanocomposites, nanoelectronic materials, novel high dielectric constant materials, electrochromic materials for energy storage, green synthesis of nanomaterials, and surface functionalization of polymers/nanomaterials. He did his Post doctorate in Materials Science at Iowa State University and his Ph.D. in Polymer Science (2009) at the National Institute of Technology. In his academic career, he has published more than 80 SCI journal research articles in the field of polymers/materials science and holds one United States patent. He has also published 12 books and thirty book chapters on the advanced state-of-the-art of polymers/materials science with numerous publishers. He is an editorial board member of several international journals and also is member of scientific bodies around the world. In addition to being on the editorial board of journals, he also serves as the guest editor for the Journal of Nanomaterials, International Journal of Polymer Science, Journal of Chemistry, and American Journal of Applied Chemistry.Dr. Manju Kumar Thakur has been working as an Assistant Professor of Chemistry at the Division of Chemistry, Govt. Degree College Sarkaghat Himachal Pradesh University – Shimla, INDIA since June 2010. She received her B.Sc. in Chemistry, Botany and Zoology; M.Sc., M. Phil; in Organic Chemistry and Ph.D. in Polymer Chemistry from the Chemistry Department at Himachal Pradesh University – Shimla, INDIA. She has rich experience in the field of organic chemistry, bio- polymers, composites/ nanocomposites, hydrogels, applications of hydrogels in the removal of toxic heavy metal ions, drug delivery etc. She has published more than 30 research papers in several international journals, co-authored three books and has also published 25 book chapters in the field of polymeric materials.

Preface 7
Contents 9
About the Editors 11
1 Eco-Friendly Polymer-Layered Silicate Nanocomposite--Preparation, Chemistry, Properties, and Applications 13
Abstract 13
1 Introduction 15
2 Polymer Nanocomposites 19
2.1 Polymer Layered Silicate Nanocomposites 19
3 Nanoclays--Structure, Properties, and Modifications 20
3.1 Layered Silicates 20
3.2 Nanoclay Modifications 22
4 Polymer--Clay Nanocoposite Types, Chemistry, and Mechanism 25
4.1 Types of Nanocomposites 25
4.2 Chemistry and Mechanism 26
5 Nanocomposite Synthesis 28
5.1 Direct Intercalation 28
5.2 In Situ Intercalative Polymerization 28
5.3 Ultrasound Irradiation 28
5.4 Solution Polymerization 29
5.5 Emulsion Polymerization 29
5.6 Melt Blending (Compounding) 29
6 Green Nanocomposites 30
6.1 Cellulose--Clay Nanocomposite 30
6.2 Natural Rubber--Clay Nanocomposites 33
6.2.1 Natural Rubber 33
6.2.2 Types of Clays for Rubber Nanocompoiste 34
6.2.3 Method of Preparation of Rubber--Clay Nanocomposite 35
6.2.4 Natural Rubber--Clay Nanocomposite (Dry Rubber Process) 36
6.2.5 Hybrid Natural Rubber-Clay Nanocmoposite 37
6.2.6 Natural Rubber--Clay-Carbon Black Nanocomposite 38
6.2.7 Natural Rubber--Carbon Black-Silica-Clay Nanocomposite 39
6.2.8 Natural Rubber--Clay Nanocomposites: Solution or Latex Route 40
Solution Route 40
Latex Route 40
6.2.9 Effect of Clay on Microstructure 42
7 Physical Properties of Natural Rubber-Clay Nanocomposite 43
7.1 Without Compatibilizer 43
7.2 With Compatibilizer 46
8 Applications of Green Polymer-Clay Nanocomposite 47
9 Conclusion 49
References 49
2 Hydrogels Nanocomposites Based on Crystals, Whiskers and Fibrils Derived from Biopolymers 55
Abstract 55
1 Introduction 56
1.1 Biopolymers 57
2 Crystals, Whiskers and Fibrils Derived from Biopolymers 58
2.1 Starch 59
2.2 Cellulose 60
2.3 Chitin and Chitosan 63
3 Hydrogels Nanocomposites 65
3.1 Based on Cellulose Nanocrystals 66
3.2 Based on Chitin Nanocrystals 70
3.3 Based on Starch Nanocrystals 72
4 Conclusions and Future Trends 73
References 74
3 Fabrication, Property, and Application of Lignin-Based Nanocomposites 84
Abstract 84
1 Introduction 84
2 Lignin-Biopolymer Nanocomposites 86
2.1 Lignin-Polysaccharides Nanocomposites 86
2.2 Other Lignin-Biopolymer Nanocomposites 88
3 Lignin-Synthetic Polymer Nanocomposites 88
3.1 Lignin-PLA Nanocomposites 89
3.2 Lignin-Polyaniline Derivatives Nanocomposites 89
3.3 Other Lignin-Synthetic Polymer Nanocomposites 91
4 Lignin-Based Metallic Nanocomposites 92
4.1 Lignin-Based Precious Metal Nanocomposites 93
4.2 Other Lignin-Based Metallic Nanocomposites 94
5 Lignin-Based Carbonaceous Nanocomposites 98
5.1 Lignin-Based Carbon Nanotubes Nanocomposites 98
5.2 Other Lignin-Based Carbon Nanocomposites 100
6 Other Lignin-Based Nanocomposites 102
7 Conclusions 104
References 105
4 Nanocellulose and Its Application for Shape-Memory Materials 111
Abstract 111
1 Introduction 111
2 Isolation, Structure, and Properties of Nanocellulose 113
2.1 Isolation of Nanocellulose 113
2.1.1 Acid Hydrolysis 114
2.1.2 Mechanical Treatments 115
2.1.3 Enzymatic Treatment 116
2.2 Structure and Properties of Nanocellulose 117
2.2.1 Morphology and Geometrical Dimensions 117
2.2.2 Stiffness and Crystalline Characters 118
2.2.3 Active Hydroxyl Groups for Functionalization 119
2.2.4 Dispersibility of NCs in Different Solvents 120
3 Chemical Modification of Nanocellulose 121
4 Application of NCs in Shape-Memory Materials 124
4.1 Shape-Memory Effects (SME) of SMPs 124
4.1.1 Thermally Induced SMEs 125
4.1.2 Athermally Induced SMEs 127
4.2 Shape-Memory Polyurethane (SMPU) 128
4.3 Nanocellulose/Shape-Memory Polymer (NC/SMP) Nanocomposites 130
4.3.1 Processing Methods of NC/SMP Nanocomposites 131
4.3.2 Thermally Induced NC/SMP Nanocomposites 132
Thermomechanical and Crystalline Properties of the NC/SMP Nanocomposites 133
Reinforcement of NCs and SMEs of NC/SMP Nanocomposites 134
4.3.3 Water-Response NC/SMP Nanocomposites 135
4.3.4 Other NC/SMP Materials and Multi-material Systems 137
5 Conclusions 138
References 139
5 Nanotechnologies for Production of High Performance Cellulosic Paper 146
Abstract 146
1 General Introduction 146
2 Scope Survey of Nanoparticles in Paper Manufacturing 148
2.1 Nanomaterials Containing Cellulosic Paper Sheets 148
2.2 Production Methods of Nanoscale Materials 150
2.2.1 Methods of Production Nanoscale Inorganic Materials 150
2.2.2 Methods of Production Nanocelluloses (NC) 151
2.3 Characterization Techniques for Nanomaterials 152
3 Fluorescence-Active Pyridinecarbonitriles as Security Marker in Safety Paper Production and Its Nanoparticle Characteristics 154
3.1 Synthesis of Fluorescence Active Pyridinedicarbonitriles and Studying Their Application in Functional Paper (41, 42) 155
3.1.1 Objective 155
3.1.2 Materials and Methods 155
Synthesis and Characterization of Fluorescence Materials 155
Paper Sheets Formation and Tests 158
3.1.3 Results and Discussion 158
Chemistry of Heterocyclic Compounds 158
Absorption and Fluorescence Properties of the Prepared Compounds 159
Evaluation of Papermaking 159
3.2 Preparation and Optical Properties of 2-Amino-6-Ethoxy-4-[4-(4-Morpholinyl)Phenyl]-3,5-Pyridinedicarbonitrile Fluorescent Nanoparticles: A Security Marker for Paper Documents (Mauro et al. 2012) [39] 164
3.2.1 Objective 164
3.2.2 Experimental Methods 165
Synthesis of AEMP Molecules and Nanoparticles 165
Morphology of AEMP Nanoparticles 165
Absorption and Photoluminescence Spectra 165
3.2.3 Results and Discussion 166
Production and Morphology of AEMP Nanoparticles 166
Absorption and Photoluminescence Spectra 170
4 Conclusions and Future Prospective 176
5 Acknowledgment 176
References 176
6 A Review on Bionanocomposites Based on Chitosan and Its Derivatives for Biomedical Applications 182
Abstract 182
1 Introduction 183
1.1 Properties of Chitosan 184
1.1.1 Physicochemical Properties 184
1.1.2 Biological Properties 185
1.2 Chitosan Limitations 187
2 Modifications of Chitosan 188
2.1 Chitosan Derivatives 188
2.2 Chitosan Composites 191
2.3 Chitosan-Based Nanocomposites 192
3 Biomedical Applications of Chitosan-Based Nanocomposites 195
3.1 Tissue Engineering 195
3.2 Wound Dressing 200
3.3 Drug Delivery 203
3.3.1 Cancer-Targeted Drug Delivery System 204
3.3.2 Oral Drug Delivery System 206
3.4 Biosensors 208
4 Conclusion and Future Perspective 210
References 211
7 Graphene-Based Polymer Nanocomposites: Chemistry and Applications 218
Abstract 218
1 Introduction 218
2 Graphene 220
2.1 Discovery, History, and Chemistry 221
2.2 Synthesis and Characterization Methods 223
2.2.1 Exfoliation 223
2.2.2 Chemical Vapor Deposition 224
2.2.3 Miscellaneous Methods 224
2.3 Surface-Modified Graphenes 225
2.4 Biofunctionalization of Graphene-Based Nanomaterials 226
2.5 Porous Graphene 227
3 Graphene--Polymer Nanocomposites 228
3.1 Preparation of Polymer Nanocomposites 228
3.2 Polymer Matrices 229
3.2.1 Epoxy 229
3.2.2 Polystyrene 231
3.2.3 Polyaniline 232
3.2.4 Poly(Vinyl Alcohol) 232
3.3 Polyurethane 233
3.4 Poly(Vinylidene Fluoride) 234
4 Biocompatibility Graphene-Based Materials 234
5 Preparation and Characterization of Graphene Oxide 235
6 Potential Applications of Graphene-Based Polymer Nanocomposites 236
7 Conclusions and Outlook 237
References 238
8 Natural Nano-based Polymers for Packaging Applications 247
Abstract 247
1 Introduction 248
2 Natural Nanocomposite Materials and Food Packaging 252
2.1 Inorganic Nanocomposite Materials 255
2.1.1 Nanoclay 256
2.1.2 Nanosilver 258
2.1.3 Other Examples 259
2.2 Organic Nanocomposite Materials 260
2.2.1 Polysaccharides 261
Nanocellulose 261
Nanochitosan 262
2.2.2 Proteins 263
Zein 263
Gelatin 264
2.2.3 Lipids 265
2.3 Hybrid Inorganic/Organic Nanocomposite Materials 266
3 Quality Control or Assessments of Prepared Nanobiocomposites 268
3.1 Film Thickness 269
3.2 Mechanical Properties 270
3.3 Water Vapor Permeability (WVP) 270
3.4 Barrier Properties 270
3.5 Electron Microscopy 271
3.6 Nuclear Magnetic Resonance (NMR) Spectroscopy 272
3.7 Fourier Transform Infrared (FTIR) Spectroscopic Analysis 272
3.8 Atomic Force Microscopy (AFM) 273
3.9 X-Ray Diffraction (XRD) 273
3.10 Flame Retardancy 273
3.11 Optical Microscopy 273
3.12 Thermal Stability 274
3.12.1 Thermo Gravimetric Analysis (TGA) 274
3.12.2 Differential Scanning Calorimetric (DSC) 275
3.13 Microbiology 277
3.14 Migration 277
3.15 Statistical Analysis 278
4 Conclusions and Future Perspective 278
References 279
9 Bionanocomposites for Magnetic Removal of Water Pollutants 286
Abstract 286
1 Introduction 286
2 Magnetic Polysaccharide Composites 287
2.1 Preparation Techniques of Magnetic Bionanocomposites 288
2.1.1 Inorganic Nanoparticles 288
Co-precipitation 289
Thermolysis of Precursors 290
Microemulsions 290
Hydrothermal Reactions 290
2.1.2 Magnetic Bionanocomposites 291
In situ preparation of magnetic bionanocomposites 291
Blending of magnetic nanoparticles with biopolymers 294
3 Magnetism Aspects on Water Treatment Separation Technologies 296
3.1 General Principles of Magnetic Separation 296
3.2 Magnetic Nanoparticles for Separation Technologies 299
4 Application of Magnetic Bionanocomposites in Water Treatment 302
4.1 Modeling the Adsorption Process 303
4.2 Removal of Metal Ions 305
4.3 Removal of Dyes 308
4.4 Removal of Anions 310
5 Conclusions and Future Perspectives 311
Acknowledgments 312
References 312
10 Magnetite Nanocomposites Thin Coatings Prepared by MAPLE to Prevent Microbial Colonization of Medical Surfaces 318
Abstract 318
1 Introduction 319
2 Microbial Colonization of Medical Surfaces 320
2.1 Structures, Biomolecules, and Filamentous Appendages Involved in Adhesion to the Inert Substratum 321
2.2 The Kinetics of Microbial Adhesion and Biofilm Formation 322
2.3 Mechanisms of Pathogenesis in Infections Associated with Medical Devices 324
2.4 Foreign Body-Related Infections 325
3 Matrix-Assisted Pulsed Laser Evaporation Customized Surfaces 329
4 Magnetite Nanoparticles with Antimicrobial Loadings 330
5 Bioevaluation of Magnetite Nanoparticles and Magnetic MAPLE Deposited Surfaces 332
5.1 In Vitro Evaluation 333
5.2 In Vivo Evaluation and Biodistribution 336
6 Conclusions and Perspectives 339
Acknowledgments 340
References 340
11 Eco-Friendly Chitosan-Based Nanocomposites: Chemistry and Applications 347
Abstract 347
1 Introduction 347
2 Chitosan as Biopolymer 349
3 Preparation and Characterization of Bio-nanocomposites Containing Layered Silicates 351
3.1 In Situ Polymerization 353
3.2 Solvent Intercalation Process 353
3.3 Melt Intercalation Process 354
4 Chitosan/Clay Nanocomposites 356
4.1 Mechanical and Thermal Properties of Chitosan-Based Nanocomposites 363
4.1.1 Mechanical Performance of the Chitosan-Based Nanocomposites 363
4.1.2 Thermal Properties of Chitosan/Clay Nanocomposites 368
4.2 Barrier Properties 370
4.3 Antibacterial Properties of CS/Clay Nanocomposites 371
4.4 Mucoadhesive Properties 374
4.5 Biodegradation of Chitosan-Based Nanocomposites 375
5 Applications of Chitosan/Clay Nanocomposites 378
5.1 CS/Clay Nanocomposites as Adsorbent for Removal of Dyes and Heavy Metals 378
5.2 CS/Clay Nanocomposites in Food Packaging Applications 379
5.3 Chitosan-Based Nanocomposites in Drug Delivery 380
5.4 Chitosan/Clay Nanocomposites in Tissue Engineering 383
6 Conclusion and Future Perspective 384
Acknowledgments 384
References 385
12 Environmental Applications of Polypyrrole---and Polyaniline--Bacterial Extracellular Polysaccharide Nanocomposites 393
Abstract 393
1 Introduction 394
2 Synthesis and Properties of Pn--EPS and PPy--EPS Nanocomposites 396
2.1 Extraction of EPS 396
2.2 Pn--EPS Nanocomposite 396
2.3 PPy--EPS Nanocomposite 397
3 Application of Pn--EPS and PPy--EPS Nanocomposites for the Treatment of Simulated Remazol Dye Effluent 398
4 Application of Pn--EPS and PPy--EPS Nanocomposites for the Removal of Cr(VI) from Aqueous Solution 399
5 Conclusion 400
References 400
13 Synthesis, Chemistry, and Medical Application of Bacterial Cellulose Nanocomposites 404
Abstract 404
1 Introduction 405
2 History of BC and BC Composites 406
3 Synthesis of Bacterial Cellulose 408
4 Development of Various Approaches for BC Production 408
4.1 Static Cultures 408
4.2 Submerged (Agitated) Fermentation 409
5 Various Bioreactors Designed for BC Production 410
5.1 Bioreactor with Spin Filters 410
5.2 Bioreactor with Silicone Membranes 411
5.3 Airlift Bioreactor 411
5.4 Rotating Disk Bioreactor 411
5.5 Cell Immobilization and Biofilm Reactors 412
6 BC Synthetic Pathway 412
7 Self-Assembly and Crystallization of Cellulose Chains 413
8 Chemical Structure of BC 414
9 BC Composites 415
10 Necessity of BC Composites 416
11 Synthetic Approaches for BC Composites 416
11.1 In Situ BC Composite Synthesis 418
12 Ex Situ BC Composites Synthesis 420
12.1 BC Composites Through Solution Blending 421
13 Applications of BC Composites 422
14 Medical Applications of BC and BC Composites 422
14.1 Skin/Tissue Regeneration 423
14.2 Wound Healing 426
14.3 Artificial Blood Vessels 427
14.4 Scaffolding 428
14.5 Bone and Cartilage Regeneration 429
14.6 Other Medical Applications 430
15 Applications of BC in Other Fields 430
15.1 Applications in the Food Industry 430
15.2 Separation and Waste Purifications 432
15.3 Conductive Materials and Electrical Devices 432
15.4 Industrial Applications 433
16 Conclusion and Future Prospects 434
Acknowledgment 434
References 434
14 Chitin-Based Nanocomposites: Biomedical Applications 443
Abstract 443
1 Introduction 443
2 Chitin: Structure and Properties 445
3 Chitin Nanofibrils 447
3.1 Synthesis and Characterization of Chitin Nanofibrils 447
3.2 Chitin Nanofibrils for Biomedical Applications 448
4 Conclusions 458
Acknowledgments 458
References 458
15 Eco-Friendly Cellulose--Polymer Nanocomposites: Synthesis, Properties and Applications 462
Abstract 462
1 Introduction 464
1.1 Biopolymers 464
1.2 Cellulose 466
1.3 Functionalization of Cellulose 468
1.3.1 Coating 468
1.3.2 Plasma Etching 468
1.3.3 Surface Modification by Nanoparticle Growth 469
1.3.4 Grafting 469
1.3.5 Chemical Vapour Deposition 470
2 Superhydrophobicity 471
2.1 Methods of Preparation 471
2.2 Functionalization with Low Surface Energy 471
2.3 Creation of Nanoroughness 473
2.4 Polymerization 473
3 Oil--Water Separation 476
3.1 Siloxane Functionalization 479
3.2 Metal Nanoparticles 479
3.3 Nanocellulose 480
4 Conductivity 481
4.1 Conducting Polymers 482
4.1.1 Polypyrrole 482
Effect of Dopants 482
Effect of Oxidant 483
Effect of Metal Nanoparticles 483
4.1.2 Polyaniline 483
Polyaniline with Nanoparticles 485
4.1.3 PEDOT:PSS 485
4.2 Nanoparticles Coating 486
4.3 Carbon Derivatives 487
4.4 Applications 488
5 Drug Delivery 489
5.1 Nanoparticles 489
5.2 Drug Molecules 490
6 Conclusion and Future Perspective 493
Acknowledgments 493
References 494
16 Recent Development of Chitosan Nanocomposites with Multiple Potential Uses 500
Abstract 500
1 Introduction 501
1.1 Biopolymers: Bio-Based Matrix Material 501
1.2 Starch-Based Polymers and Composites 501
1.3 Poly(lactide) (PLA) 503
1.4 Polycaprolactone (PCL) 505
1.5 Lignin 507
1.6 Cellulose 510
1.7 Cellulose Chemical Composition 510
1.8 Cellulosic Chemical Features Versus Their Incorporation into Composites 510
1.9 Cellulose--Chitosan Composites 512
1.10 Chitosan Films 514
2 Conclusions 530
References 530
17 Gold Nanoparticle-Reinforced Eco-friendly Polymer Nanocomposites and Their Applications 535
Abstract 535
1 Introduction 536
2 Polymer Nanocomposites 537
2.1 Natural Polymer-Based Nanocomposites 537
3 Nanofillers Used in Polymer Nanocomposites 538
4 Gold Nanoparticles (GNPs) 538
4.1 Synthesis of GNPs 539
4.2 Applications of GNPs 541
5 Polymer/GNP Nanocomposites 543
6 Polymer/GNP Nanocomposites with Wide Application Potential 545
6.1 Applications in Light Emitting Diode (LED) 545
6.2 Energy Storage Applications 548
6.3 Application as Supporters and Carriers 550
6.4 Optical and Electronic Applications 551
6.5 Applications as Diagnostic Probes or Drug Delivery Vehicles 552
6.6 Applications in the Fields of Catalysis and Sensors 552
6.7 Application as Potential Gate Dielectrics in Electronic Industry 553
6.8 Application as Nonenzymatic Glucose Voltammetric Sensor 555
6.9 Application as Materials Which Can Engineer Polymers at Relatively Low Temperatures 557
6.10 Application in Biosensing 558
7 Environmental Effects of GNPs 559
7.1 GNPs in Water 559
7.2 GNPs in Soil 560
7.3 GNPs in Air 561
8 Prospects for the Future 561
References 561
18 Structure and Properties of Rubbers With Silica Nanoparticles as Petroleum-Free Fillers 565
Abstract 565
1 Introduction 565
2 Nucleating Ability of Silica for Butadiene Rubber 566
3 Interphase Transfer of Silica Nanoparticles 570
4 Conclusion and Future Perspective 574
Acknowledgments 574
References 574
Index 577