Natural Rubber Materials

Volume 2: Composites and Nanocomposites

Edited by

Sabu Thomas, Hanna J. Maria, Jithin JoyMahatma Gandhi University, Kottayam, India

Email: sabuchathukulam@yahoo.co.uk, hannavidhu@gmail.com,

jithinjoyjrf@gmail.com

Chin Han Chan

MARA University of Technology, Selangor, MalaysiaEmail: cchan@salam.uitm.edu.my

and

Laly A. Pothen

Bishop Moore College, Mavelikkara, India

Email: lapothan@gmail.com

Contents

Chapter 1 Natural Rubber-Based Composites and Nanocomposites:State of the Art, New Challenges and Opportunities 1

C. H. Chan, Jithin Joy, Hanna J. Maria and S. Thomas

1.1 Introduction 1

1.2 Supply and Demand of NR as Compared to SR 5

1.3 Challenges and Opportunities for NR Industries 8

1.3.1 Challenges to Increase the Yield of NR Latex 8

1.3.2 Challenges and Opportunities to Promote NR

Industries 10

1.4 NR-Based Composites and Nanocomposites 13

1.5 An Overview of Common Fillers used in NR

Composites 13

1.5.1 Carbon Black 14

1.5.2 Clay 14

1.5.3 Silica 15

1.5.4 Calcium Carbonate 17

1.5.5 Metal Particles 18

1.5.6 Bio-Based Fillers 19

1.5.7 Polyhedral Oligomeric Silsesquioxane 23

1.5.8 Carbon Nanotubes 24

1.6 Applications of NR 26

1.7 Conclusions 27

Acknowledgment 28

References 28

Chapter 2 Nanofillers in Natural Rubber 34

Maurizio Galimberti, Valeria Cipolletti and Vineet Kumar

2.1 Introduction 34

RSC Polymer Chemistry Series No. 8

Natural Rubber Materials, Volume 2: Composites and NanocompositesEdited by Sabu Thomas, Hanna J. Maria, Jithin Joy, Chin Han Chan and Laly A. Pothen

© The Royal Society of Chemistry 2014

Published by the Royal Society of Chemistry, www.rsc.org

vii

viii Contents

2.2 Nanofillers for NR: Structural Features 35

2.2.1 Clays and Organoclays 35

2.2.2 Nano-Graphite 37

2.2.3 Carbon Nanotubes 38

2.3 Processing Methods for the Preparation of

Nanocomposites 39

2.3.1 Dispersion of Clays and Organoclays 39

2.3.2 Dispersion of Nano-Graphite 41

2.3.3 Dispersion of Carbon Nanotubes 41

2.4 Organization of Nanofillers in NR 48

2.4.1 Clays and Organoclays 48

2.4.2 Nano-Graphite 50

2.4.3 Carbon Nanotubes 50

2.5 Interaction between Isoprene Rubber and Nanofiller 51

2.5.1 Clays and Organoclays 51

2.5.2 Carbon Nanotubes 52

2.6 Properties of NR/Clay Nanocomposites 53

2.6.1 Rheological Properties 53

2.6.2 Vulcanization Efficiency 54

2.6.3 Barrier Properties 54

2.6.4 Mechanical Reinforcement 54

2.7 Properties of Isoprene Rubber/Nano-Graphite

Nanocomposites 57

2.8 Properties of NR/CNT Nanocomposites 58

2.8.1 Vulcanization Efficiency 58

2.8.2 Mechanical Properties 58

2.8.3 Electrical Properties 61

2.8.4 Thermal Properties 61

2.9 Nano-silica 62

2.9.1 Sol-Gel Process for the in situ Generation of

Silica 62

2.9.2 Nanocomposites with in situ Silica 63

2.10 Nano Metal Oxides 64

2.11 Nano Calcium Carbonate 64

2.12 Nano Carbon Black 65

References 66

Chapter 3 Theory and Mechanisms of Filler Reinforcement in Natural

Rubber 73

Azemi bin Samsuri

3.1 A General Introduction to Fillers 73

3.2 Reinforcing Fillers 74

3.2.1 Particle Size 75

3.2.2 Aggregates 76

3.2.3 Structure 77

Contents ix

3.2.4 Physical Nature of the Surface 78

3.2.5 Degree of Filler Dispersion in the Rubber

Matrix 78

3.3 Theory and Mechanisms of Reinforcement 79

3.3.1 Blanchard and Parkinson Model of Weak

and Strong Linkage 79

3.3.2 Bueche Model of Load-Sharing Mechanism 80

3.3.3 Dannenberg Model of Slippage at Interface 80

3.3.4 Bound Rubber 80

3.3.5 Detachment of Filler Particles 81

3.3.6 Theory of Reinforcement by Rigid (Fractal)

Aggregates and Agglomerates of Filler

Particles 81

3.3.7 Theory of Filler Reinforcement in Elastomers

Based on Uniform Soft-Sphere Model 84

3.3.8 Mathematical and Computer Models 85

3.3.9 Kluppeland-Schramm Tube Model 85

3.3.10 Fukahori and Seki Model 86

3.3.11 Bergstrom and Boyce Model 86

3.3.12 Hon et al. Micromechanical Model 86

3.3.13 Jha et al. Microstructural Finite Element

Model 87

3.3.14 Electrical and Mechanical Behaviour of Filled

Elastomers under Strain 88

3.4 Mechanism of Reinforcement in Modulus 89

3.4.1 Effect of Pre-Stressing on Young's Modulus

of Silica-Filled Vulcanized NR 95

3.4.2 Effect of Oil Extraction on Elastic Constant 98

3.5 Mechanism of Reinforcement in Tensile Strength 101

3.5.1 Influence of Types of Crosslink and Crosslink

Concentration 101

3.5.2 Effect of Filler Loading on Tensile Strength 104

3.5.3 Dependence of Tensile Strength of Vulcanized

Black-Filled Rubber on Particle Size 105

3.5.4 Effect ofFiller-Rubber Interaction on Tensile

Strength 106

3.5.5 Influence of Filler Dispersion on Tensile

Strength 107

Acknowledgements 109

References 109

Chapter 4 Preparation and Properties of Natural Rubber Composites

and Nanocomposites 112

Dongzhi Chen, Mingjie Hu, Chi Huang and Ruiwen Zhang

4.1 Introduction 112

X Contents

4.2 NR Composites and Nanocomposites based on

Conventional Fillers 113

4.2.1 NR Composites and NanocompositesReinforced with Carbon Black 113

4.2.2 NR Composites and NanocompositesReinforced with Silica 114

4.2.3 NR Composites and Nanocomposites Based

on Carbon Nanotubes 116

4.2.4 NR Composites and Nanocomposites Based

on Graphene 118

4.3 NR Composites and Nanocomposites Based on

Natural Fillers 120

4.3.1 Fibre-Reinforced NR Composites and

Nanocomposites 120

4.3.2 Starch-Reinforced NR Composites and

Nanocomposites 122

4.3.3 NR Composites and NanocompositesReinforced with Natural Mineral Fillers 123

4.4 NR Composites and Nanocomposites Based on Metal

or Metallic Compound Fillers 127

4.5 NR Composites and Nanocomposites Based on

Hybrid Fillers 128

4.6 Summary 131

References 131

Chapter 5 Strength and Durability of Natural Rubber and ChemicallyModified Natural Rubber 136

Azemi bin Samsuri

5.1 Introduction 136

5.2 Tearing Energy Theory of Rivlin and Thomas 138

5.2.1 Experimental Verification of Tear Criterion 139

5.2.2 Types of Test-Pieces 140

5.3 Types of Failure 142

5.4 Dependence ofTearing Energy on Rate and Temperature 143

5.5 Mechanism of Reinforcement in Tear Strength 146

5.5.1 Factors Affecting the Development of Knotty

Tearing 151

5.6 Tearing of Vulcanized NR Latex Film 164

5.6.1 Effect of Filler Loading on Tearing Energy 164

5.6.2 Influence of Particle Size on Tearing Energy of

Filled (at 30 pphr) NR Latex Film 165

5.7 Crack Growth Resistance 166

5.8 Environmental Factors Affecting Strength and

Durability of Rubber 169

5.8.1 Oxidation of Rubber 170

Contents xi

5.8.2 Heat Ageing 170

5.8.3 Ozone Cracking of Rubber 170

5.8.4 Effect of Water Absorption on PhysicalProperties of Vulcanized Elastomers 172

5.8.5 Effect of Heat Ageing, Oil and Water on

Rubber-to-Metal Bonding 173

Acknowledgements 178

References 179

Chapter 6 Carbon Black Reinforcement in Natural Rubber in Micro and

Nano Length 181

Gordana Markovic, Milena Marinovic-Cincovic,

Vojislav Jovanovic, Suzana Samarzija-Jovanovic and

Jaroslava Budinski-Simendic

6.1 Introduction 181

6.2 Nanocomposites 183

6.2.1 Nanoparticles (Methods and Preparation) 186

6.3 Micro Carbon Black as a Filler in Rubber 187

6.4 Carbon Nanotube-Filled Natural Rubber 193

6.4.1 NR/Carbon Nanotube Composites 194

6.4.2 Thermal Stability of NR/CNT Vulcanizates 200

6.5 Conclusions 201

Acknowledgements 202

References 202

Chapter 7 Silica Reinforcement in Natural Rubber in Micro and Nano

Length Scales 205

Azanam S. Hashim and S. K. Ong

7.1 Silica and Silica Reinforcement of Rubbers 205

7.2 NR/Silica Nanocomposites via the in situ Sol-Gel

Silica Process 206

7.3 NR/Silica Nanocomposites via the Latex System 211

7.4 NR/Silica Nanocomposites via Modified Silica 214

7.5 Opportunities in NR and Natural Resource-Based

Silica Nanocomposites 217

References 218

Chapter 8 Clay Reinforcement in Natural Rubber on Micro and Nano

Length Scales 220

Sandip Rooj, Amit Das, Klaus Werner Stockelhuber and

Gert Heinrich

8.1 General Introduction 220

xii Contents

8.2 Clays and Layered Silicates 221

8.2.1 Modified Clay 221

8.3 Natural Rubber-Clay Nanocomposites 227

8.3.1 Natural Rubber-Organo-MontmorilloniteNanocomposites 227

8.3.2 Natural Rubber-Organo-MontmorilloniteNanocomposites in the Presence of External

Compatibilizers 231

8.3.3 Natural Rubber-Expanded Organo-Montmorillonite Nanocomposites 234

8.4 Natural Rubber with Hybrid Filler System

(Carbon Black and Clay) 240

8.5 Conclusions 243

References 243

Chapter 9 Long and Short Glass Fibre Reinforced Natural Rubber

Composites 247

Quazi T. H. Shubhra

9.1 Introduction 247

9.2 Fibre Reinforced Composites (FRCs) 249

9.2.1 Different Types of FRCs 250

9.3 Reinforcing Agents 254

9.3.1 Fibres 255

9.4 Matrix 261

9.4.1 Natural Rubber 261

9.5 Glass Fibre/NR Composites 269

9.5.1 Fabrication of Glass Fibre/NR Composites 271

9.5.2 Mechanical Properties of Glass Fibre/NR

Composites 273

9.5.3 Fibre-Matrix Adhesion 277

9.5.4 Improvement in Strength of Glass Fibre/NRComposites 279

9.5.5 Biodegradation Characteristics of the Matrix 281

9.6 Applications 285

9.7 Conclusions 285

References 286

Chapter 10 Micro and Nano TiOz Reinforced Natural Rubber

Composites 290

Jiji Abraham, Sabu Thomas and Soney C. George

10.1 Introduction 290

10.2 Composites 291

10.3 Fillers 291

10.4 Micro and Nano Ti02 292

Contents xiii

10.5 Synthesis of Ti02 Particles 294

10.5.1 Synthesis of Nano Ti02 Particles 294

10.5.2 Synthesis of Micro Ti02 Particles 294

10.6 Characterization of Ti02 295

10.6.1 XRD 296

10.6.2 TEM 297

10.6.3 FTIR 297

10.6.4 Raman Spectroscopy 298

10.6.5 Energy-Dispersive X-Ray (EDX) Analysis 299

10.7 Fabrication of Ti02-NR Composites 300

10.7.1 Preparation of Ti02 Film-NR Composites 300

10.7.2 Preparation of Ti02-NR Composites 300

10.8 Properties of NR-Ti02 Composites 300

10.9 Photocatalytic Study of Ti02-NR Composites 302

10.10 Applications of Ti02-NR Composites 304

10.11 Conclusions 305

References 305

Chapter 11 Micro and Nano Metal Particle Filled Natural Rubber

Composites 307

Jithin Joy, Anu Tresa Sunny, Lovely Mathew P.,

Laly A. Pothen and Sabu Thomas

11.1 Introduction 307

11.2 Nanocomposites 308

11.3 Metal Particle-Polymer Composite Materials 308

11.4 Metal Particle Natural Rubber Composite Materials 309

11.4.1 Metal Particles Employed in CompositeFabrication 309

11.5 Property Analysis of NR-Metal Composites 310

11.5.1 Structural Properties 310

11.5.2 Mechanical Properties 312

11.5.3 Dielectric Properties 314

11.5.4 Thermal Properties 318

11.5.5 Magnetic Properties 320

11.6 Applications of NR-Metal Composites 321

11.7 Conclusions 322

References 323

Chapter 12 Micro and Nano Zinc Oxide Filled NR Composites 326

Shaji P. Thomas and E. J. Mathew

12.1 Introduction 326

12.2 General Functions of ZnO in Rubber Vulcanization 327

12.3 Additional Advantages of ZnO 328

12.3.1 Biochemical Activity 328

xiv Contents

12.3.2 Dielectric Strength 328

12.3.3 Light Stabilization 328

12.3.4 Pigmentation 328

12.3.5 Heat Stabilization 329

12.3.6 Latex Gelation 329

12.3.7 Reinforcement 329

12.3.8 Rubber-Metal Bonding 329

12.3.9 Tack Retention 329

12.3.10 Application of ZnO in the Plastics

Industry 329

12.4 Advantages of Nano-ZnO over Micro-ZnO 330

12.5 Strategies for Synthesizing Micro and Nano-ZnO 331

12.5.1 Synthesis of Micro-ZnO 331

12.5.2 Synthesis of Surface-Modified Micro-ZnO 331

12.5.3 Synthesis of Nano-ZnO 332

12.5.4 Synthesis of Surface-Modified Nano-ZnO 335

12.6 Characterization of Micro and Nano-ZnO 336

12.6.1 X-Ray Diffraction 336

12.6.2 FTIR Spectroscopy and Electron

Microscopy 337

12.6.3 Optical Studies 338

12.7 Studies of NR Composites Containing Micro

and Nano-ZnO 341

12.8 Comparison of the Properties of Nano- and

Microcomposites of NR 348

12.9 Conclusions 349

References 349

Chapter 13 Green Natural Fibre Reinforced Natural Rubber Composites 353

SA-AD Riyajan

13.1 Introduction 353

13.2 Basic Information about Natural Fibre 354

13.3 Preparation of Natural Fibre 358

13.4 Preparation of Natural Rubber Composites 366

13.4.1 Latex Blending 368

13.4.2 Mechanical Blending 368

13.5 NR Composites Reinforced with Natural Fibre 369

13.5.1 Tea Waste Fibre 370

13.5.2 Oil Palm Ash/Palm Fibre 371

13.5.3 Bagasse Whiskers and Baggage Fibre 371

13.5.4 Coir Fibre/Coconut Fibre (Cofibre) 372

13.5.5 Jute Fibre 374

13.5.6 Chemistry of the Interface Modification and

Characterization 375

Contents xv

13.6 ENR/Biodegradable Polymers Reinforced with

Cellulose Fibre 377

13.7 NR/Synthetic Polymer Blends Reinforced with

Natural Fibre 379

13.7.1 NR/Polystyrene Foam Waste (PSf) Blends 379

13.7.2 PP/NR Blends Reinforced with Cellulose

Fibre 395

13.8 Possible Applications of Rubber Composites 396

13.9 Conclusions 396

Acknowledgements 397

References 397

Chapter 14 Synthesis of Natural Rubber-Based Completely Green

Bionanocomposites 401

Sonal I. Thakore

14.1 Introduction 401

14.1.1 Fillers used in Natural Rubber 402

14.1.2 Synthetic and Natural Fibres 402

14.1.3 Biocomposites 403

14.2 Polysaccharides as Reinforcing Agents 404

14.2.1 Starch 404

14.2.2 Cellulose 404

14.2.3 Chitin 405

14.3 Disadvantages of Polysaccharides as Fillers 406

14.4 Polysaccharides for Nanoreinforcement 407

14.4.1 Chitin Whiskers 407

14.4.2 Cellulose Whiskers 407

14.4.3 Cellulose and Starch Nanocrystals 408

14.5 Nanocomposites and Bionanocomposites 412

14.6 Preparation of Bionanocomposites 413

14.6.1 Casting and Evaporating 413

14.6.2 Freeze Drying and Hot Pressing 414

14.6.3 Non-Aqueous Solvent Dispersion 414

14.6.4 Dry Mixing 414

14.7 Natural Rubber-Polysaccharide Nanocomposites 415

14.7.1 Mechanical and MorphologicalInvestigations 415

14.7.2 Dynamic Mechanical Analysis (DMA) 419

14.7.3 Sorption Properties in Water and other

Organic Solvents 420

14.7.4 Gas Permeability 422

14.8 Reinforcing Mechanisms 424

14.8.1 Payne Effect 424

14.8.2 Mullins Effect 425

14.9 Commercial Avenues 425

xvi Contents

14.10 Comparison of Properties: Bionanocomposites vs

Micro- and Nanocomposites 426

14.11 Summary and Future Challenges 427

References 428

Chapter 15 Magnetic Filler-Reinforced Natural Rubber

Macro- and Nanocomposites 432

Aldo Eloizo Job, Felipe Silva Bellucci, Fldvio Camargo Cabrera,

Alexandre Fioravante de Siqueira, Eduardo Roque Budembergand Leandra Oliveira Salmazo

15.1 Introduction 432

15.2 Magnetic Fillers used in Natural Rubber Matrices 433

15.2.1 Ceramic Fillers: Ferrite 433

15.2.2 Inverse Spinel Structure and the Nickel-Zinc

Ferrite 434

15.2.3 Preparation of Magnetic Fillers for use in

Natural Rubber Matrices 436

15.2.4 Processing of Materials using Physical Routes 436

15.2.5 Processing of Materials by Chemical Routes 438

15.2.6 Methods of Preparing MagneticMacro- and Nanocomposites 438

15.2.7 Method: Dry Mechanical Mixing 439

15.3 Morphological and Spectroscopic Studies of

Magnetic Composites 441

15.3.1 Scanning Electron Microscopy 442

15.3.2 Atomic Force Microscopy 445

15.3.3 Infrared Spectroscopy 445

15.4 Mechanical and Thermal Analysis 445

15.4.1 Thermal Properties 447

15.4.2 Mechanical Properties 450

15.5 Magnetic Analysis 455

15.5.1 Vibrating Sample Magnetometer 456

15.6 Applications of Magnetic Composites 459

15.6.1 Application 1: Intelligent Impact-AbsorptionSystems 459

15.6.2 Application 2: Control of Colonies of

Leishmaniasis Parasites 462

Acknowledgements 464

References 464

Chapter 16 Micro and Nano Calcium Carbonate Filled Natural Rubber

Composites and Nanocomposites 467

Imran Khan and A. H. Bhat

16.1 Introduction 467

Contents xvii

16.2 Global Distribution of Rubber 469

16.3 Calcium Carbonate 470

16.3.1 Nano Calcium Carbonate (NCC) vs Micro

Calcium Carbonate (MCC) 470

16.4 Elastomer Nanocomposites 471

16.4.1 Filler Characteristics 471

16.4.2 Filler Size 471

16.4.3 Particle Structure and Anisometry of Filler

Aggregates 472

16.4.4 Surface Activity 472

16.4.5 Surface Area 473

16.4.6 Porosity 473

16.4.7 Filler Surface Modification 474

16.4.8 Carbon Black vs Silica 474

16.5 Natural Rubber-Based Calcium Carbonate

Nanocomposites 475

16.5.1 Swelling Properties 475

16.5.2 Mechanical Properties 476

16.5.3 Morphological Studies 477

16.5.4 Dynamic Mechanical Analysis 477

16.6 Comparative Study of Acrylonitrile Butadiene

Rubber (NBR) and Natural Rubber-Based Calcium

Carbonate Nanocomposites 478

16.6.1 Mechanical Properties 478

16.6.2 Morphological Studies 479

16.7 Comparative Study of SBR and NR Based Calcium

Carbonate Nanocomposites 479

16.7.1 Swelling Index 481

16.7.2 Mechanical Properties 481

16.7.3 Morphological Studies 482

16.7.4 Flame Retardancy 482

16.7.5 Applications 483

16.8 Conclusions 483

Abbreviation 484

References 484

Chapter 17 Preparation and Characterization of Natural Rubber

Reinforced with Carbon Nanotubes 488

Mou'ad A. Tarawneh and Sahrim Hj. Ahmad

17.1 Introduction 488

17.2 Experimental Details 492

17.3 Results and Discussion 493

17.3.1 Mechanical Properties 493

17.3.2 Thermal Conductivity 495

17.3.3 Morphological Examination 497

xviii Contents

17.4 Conclusions 500

Acknowledgements 501

References 501

Chapter 18 Metal Oxide Filled Micro and Nano Natural Rubber

Composites 504

Suneel Kumar Srivastava

18.1 Introduction 504

18.2 Metal Oxides as Reinforcing Fillers in Natural

Rubber 505

18.2.1 Si02 506

18.2.2 ZnO 506

18.2.3 Ti02 507

18.2.4 A1203 507

18.2.5 Fe203 507

18.2.6 BaTi03 and PbTi03 508

18.2.7 Mn,_xZnxFe204, BaFe,20i9 and

Ni,_xZnxFe204 508

18.3 Structure and Morphology of Metal Oxide Filled NR

Composites 508

18.4 Properties of NR and NR/Nanocomposites 515

18.4.1 Mechanical Properties 515

18.4.2 Dynamical Mechanical Thermal Analysis(DMTA) 529

18.4.3 Thermal Properties 533

18.4.4 Electrical Properties 535

18.4.5 Magnetic Properties 535

18.4.6 Thermal Conductivity and Thermal

Diffusivity 538

18.4.7 UV Resistance Properties 539

18.4.8 Antibacterial Properties 539

18.5 Curing Characteristics of NR and Metal Oxide NR

Composites 540

18.6 Conclusions and Future Direction of Work 542

References 542

Chapter 19 Mechanical Properties of Natural Rubber Composites Filled

with Macro- and Nanofillers 550

Azura A. Rashid and Siti Rohana Yahya

19.1 Introduction 550

19.2 Macro- and Nanofiller Reinforcements in Rubber

Composites 551

19.2.1 Particle Size and Surface Area of Fillers 551

Contents xix

19.2.2 Structure of Filler Particles 552

19.2.3 Surface Activities 552

19.3 Effects of Macro- and Nanofillers on Mechanical

Properties of Rubber Composites 553

19.3.1 Effects of Macrosized Fillers on Mechanical

Properties of Natural Rubber Composites 553

19.3.2 Effects of Nanosized Fillers on Mechanical

Properties of Natural Rubber Composites 558

19.3.3 Effects of Hybrid Fillers on Mechanical

Properties of Natural Rubber Composites 565

19.4 Conclusions 571

References 571

Chapter 20 Linear and Non-Linear Viscoelastic Behaviour of Natural

Rubber Composites from Micro- to Nanoscales 574

Robert A. Shanks

20.1 Introduction 574

20.2 Theory 576

20.2.1 Viscoelasticity 576

20.3 Time-Temperature Superposition 579

20.4 Creep and Recovery 580

20.5 Thermodynamics 581

20.6 Non-Linear Viscoelasticity 581

20.7 Natural Rubber 583

20.7.1 Structure 583

20.7.2 Crosslinking 583

20.7.3 Natural Rubber Non-Linearity 584

20.8 Natural Rubber Blends 585

20.9 Natural Rubber Composites 586

20.9.1 Mineral Fillers (Kaolin, Calcite, Talc) 586

20.9.2 Silica 586

20.9.3 Carbon Black 586

20.10 Natural Rubber Nanocomposites 587

20.10.1 Nanolayered Clay 587

20.10.2 Nano-Silica and Carbon Black 587

20.10.3 Nano-Cellulose and Starch 589

20.10.4 Carbon Nanotubes 590

20.10.5 Graphene 592

20.11 Filler Aggregates and Agglomerates 593

20.11.1 Payne Effect 593

20.11.2 Mullins Effect 594

20.12 Applications 594

20.12.1 Auto Tyre Performance 595

20.12.2 Belt Drives and Conveyors 595

XX Contents

20.13 Conclusions 595

References 595

Chapter 21 Rheological Behaviour of Natural Rubber Based Compositesand Nanocomposites 599

Runcy Wilson and Sabu Thomas

21.1 Introduction 599

21.2 Rheological Properties of Natural Rubber

Composites 601

21.2.1 Mica-Filled Composites 601

21.2.2 Silica-Filled Composites and

Nanocomposites 602

21.2.3 Clay-Filled Nanocomposites 607

21.2.4 Fly Ash-Filled Composites 609

21.2.5 Other Inorganic Composites and

Nanocomposites 610

21.2.6 Carbon Nanotube-Filled

Nanocomposites 612

21.2.7 Bio-Based Composites 615

21.3 Conclusions 617

21.4 Challenges 618

References 618

Chapter 22 X-Ray, Light and Neutron Scattering Studies on Natural

Rubber Composites and Nanocomposites 622

Jini Varghese, Cintil Jose Chirayil, Lakshmipriya Somasekharan

and Sabu Thomas

22.1 Introduction 622

22.2 X-Ray Scattering Studies 623

22.2.1 Small-Angle X-Ray Scattering and

Wide-Angle X-Ray Scattering 623

22.2.2 Characterization of Rubber

Nanocomposites 624

22.3 Light Scattering 635

22.3.1 Dynamic Light Scattering 635

22.3.2 Static Light Scattering or Classic Light

Scattering 636

22.3.3 Phase Analysis Light Scattering and Forced

Rayleigh Light Scattering 637

22.3.4 Resonance Light Scattering 637

22.3.5 Light Scattering in Soft and Bulk

Materials 637

Contents xxi

22.3.6 Technological Processes and LightScattering 638

22.3.7 Use of Small-Angle Light Scattering in

Phase Behaviour Studies 639

22.4 Neutron Scattering Studies 640

22.4.1 Natural Rubber Structure Analysis 642

22.4.2 Natural Rubber Composites 643

22.5 Conclusions 645

References 645

Chapter 23 Microscopy of Natural Rubber Composites and

Nanocomposites 649

Lucia Conzatti and Maurizio Galimberti

23.1 Introduction 649

23.2 Fillers for Rubber Composites 650

23.3 Nanofillers for Rubber Nanocomposites 652

23.4 Microscopic Techniques for the Characterization of

Filler Dispersion 653

23.4.1 Optical Microscopy 654

23.4.2 Scanning Electron Microscopy 655

23.4.3 Atomic Force Microscopy 655

23.4.4 Transmission Electron Microscopy 657

23.5 Morphology of Natural Rubber Composites 658

23.5.1 Microcomposites 659

23.5.2 Nanocomposites 662

References 673

Chapter 24 NMR Studies of Natural Rubber Composites from Macro- to

Nanoscales - A Review 683

Deepalekshtni Ponnamma, Kishor Kumar Sadasivuni and

Sabu Thomas

24.1 Introduction 683

24.2 Basic Theory of NMR Spectroscopy and

Instrumentation 684

24.2.1 Spin-Spin Relaxation and Spin Echo 687

24.2.2 Pulsed Gradient Spin Echo Diffusion 688

24.3 Solid-State Study of Elastomer Nanocomposites 689

24.3.1 Structure and Dynamics 690

24.3.2 Filler Dispersion 692

24.4 Conclusions 699

Acknowledgements 699

References 700

xxii Contents

Chapter 25 ESR Studies of Natural Rubber Composites and

Nanocomposites 703

Aruna Kumar Barick and Young- Wook Chang

25.1 Application of ESR in Polymer Systems 703

25.1.1 Introduction 703

25.1.2 Theoretical Background 705

25.2 ESR Studies of Natural Rubber Composites and

Nanocomposites 707

25.2.1 ESR Studies of NR 707

25.2.2 ESR Studies of NR Composites 716

25.2.3 ESR Studies of NR Nanocomposites 733

25.3 Summary and Future Scope 738

Acknowledgements 739

References 739

Chapter 26 Applications of Natural Rubber Composites and

Nanocomposites 742

Aldo E. Job, Fldvio C. Cabrera, Leandra O. Salmazo,

Miguel A. Rodriguez-Perez, Alberto Lopez Gil,

Alexandre F. de Siqueira and Felipe S. Bellucci

26.1 Leishmania brasiliensis Promastigotes and Natural

Rubber Membranes 742

26.1.1 Introduction 742

26.1.2 Latex Extraction 743

26.1.3 Preparation of Natural Rubber Membranes 743

26.1.4 Studying the Influence of NR/AuComposites on the Physiology of Leishmania

brasiliensis Promastigotes 745

26.2 Thermoplastic Starch and Natural Rubber Blends 750

26.2.1 Introduction 750

26.2.2 Production of Vulcanized TPS-NR Blends 751

26.2.3 Characterization of Vulcanized TPS-NR

Blends 753

26.2.4 Conclusions 757

26.3 Production and Characterization of Dry Natural

Rubber Foams 758

26.3.1 Introduction 758

26.3.2 Production of Vulcanized Natural Rubber

Foams 760

26.3.3 Characterization of Vulcanized Natural

Rubber Foams 763

26.3.4 Conclusions 767

Acknowledgements 768

References 768

Contents xxiii

Chapter 27 Diffusion and Transport of Liquids, Vapours and Gases

Through Natural Rubber Composites and Nanocomposites 772

Thanaporn Amnuaikit

27.1 Fundamental Theories of Diffusion and Transport of

Liquids, Vapours and Gases 772

27.2 Testing of Diffusion and Transport of Liquids,

Vapours and Gases through Rubber 778

27.2.1 Standard Methods or Procedures 779

27.2.2 Modified Techniques and ExperimentalStudies 783

27.3 Diffusion and Transport Profiles of Various Rubber

Types 784

27.3.1 Natural Rubber 785

27.3.2 Natural Rubber Composites 787

27.3.3 Natural Rubber Nanocomposites 790

27.4 Effect of Temperature on Diffusion and TransportParameters 792

27.5 Application of Improved Barrier Property Rubbers 795

27.6 Conclusions 795

References 796

Subject Index 800