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Natural Rubber Materials
Volume 2: Composites and Nanocomposites
Edited by
Sabu Thomas, Hanna J. Maria, Jithin JoyMahatma Gandhi University, Kottayam, India
Email: [email protected], [email protected],
Chin Han Chan
MARA University of Technology, Selangor, MalaysiaEmail: [email protected]
and
Laly A. Pothen
Bishop Moore College, Mavelikkara, India
Email: [email protected]
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