The Science and Technology of Rubber

The 3rd edition of The Science and Technology of Rubber provides a broad survey of elastomers with special emphasis on materials with a rubber-like elasticity. As in the 2nd edition, the emphasis remains on a unified treatment of the material; exploring topics from the chemical aspects such as elastomer synthesis and curing, through recent theoretical developments and characterization of equilibrium and dynamic properties, to the final applications of rubber, including tire engineering and manufacturing. Many advances have been made in polymer and elastomers research over the past ten years since the 2nd edition was published. Updated material stresses the continuous relationship between the ongoing research in synthesis, physics, structure and mechanics of rubber technology and industrial applications. Special attention is paid to recent advances in rubber-like elasticity theory and new processing techniques for elastomers. This new edition is comprised of 20% new material, including a new chapter on environmental issues and tire recycling. Provides the most comprehensive survey of elastomers for engineers and researchers in a unified treatment: the text moves from the chemical aspects such as elastomer synthesis and curing, through recent theoretical developments and characterization of equilibrium and dynamic properties, to the final applications of rubber, including tire engineering and manufacturing. Contains important updates to several chapters, including elastomer synthesis, characterization, viscoelastic behavior, rheology, reinforcement, tire engineering and recycling Includes a new chapter on the burgeoning field of bioelastomers The Science and Technology of Rubber, Fourth Edition (2013) 801pp 978-0-12-394584-6 Cover 1 Half Title 2 Title Page 4 Copyright 5 Contents 6 Rubber Elasticity: Basic Concepts and Behavior 16 1.1 Introduction 16 1.2 Elasticity of a Single Molecule 16 1.3 Elasticity of a Three-Dimensional Network of Polymer Molecules 20 1.4 Comparison with Experiment 24 1.5 Continuum Theory of Rubber Elasticity 26 1.5.1 Stress-Strain Relations 27 (i) Strain-Hardening at Large Strains 28 (ii) Inflation of a Thin-Walled Tube 29 (iii) Inflation of a Thin-Walled Spherical Balloon 30 (iv) Inflation of a Thick-Walled Spherical Shell 31 (v) Surface Instability of Compressed or Bent Blocks 32 (vi) Resistance of a Compressed Block to Indentation 33 (vii) Torsional Instability of Stretched Rubber Rods (Gent and Hua 2004) 33 1.6 Second-Order Stresses 34 1.7 Elastic Behavior Under Small Deformations 36 1.8 Some Unsolved Problems in Rubber Elasticity 39 Acknowledgments 40 References 40 Polymerization: Elastomer Synthesis 42 2.1 Introduction 42 2.2 Classification of Polymerization Reactions and Kinetic Considerations 43 2.2.1 Polyaddition/Polycondensation 44 2.2.2 Chain Polymerization 46 2.3 Polyaddition/Polycondensation 47 2.4 Chain Polymerization by Free Radical Mechanism 49 2.4.1 General Kinetics 49 2.4.2 Molecular Weight Distribution 53 2.4.3 Special Case of Diene Polymerization 54 2.4.4 Controlled Radical Polymerization 55 2.5 Emulsion Polymerization 58 2.5.1 Mechanism and Kinetics 58 2.5.2 Styrene-Butadiene Rubber 62 (i) Kinetics and Molecular Weights 62 (ii) Chain Microstructure 66 2.5.3 Emulsion Polymerization of Chloroprene 66 (i) Kinetics 66 (ii) Chain Structure 68 2.6 Copolymerization 69 2.6.1 Kinetics 69 2.6.2 Emulsion Copolymerization of Dienes 72 (i) Styrene-Butadiene (SBR) 72 (ii) Butadiene-Acrylonitrile (Nitrile Rubber) 74 (iii) Chloroprene 74 2.7 Chain Polymerization by Cationic Mechanism 75 2.7.1 Mechanism and Kinetics 75 2.7.2 Butyl Rubber 79 2.7.3 Living Cationic Polymerizations 80 2.7.4 Other Cationic Polymerizations: Heterocyclic Monomers 81 2.8 Chain Polymerization by Anionic Mechanism 83 2.8.1 Mechanism and Kinetics 83 2.8.2 Chain Microstructure of Polydienes 90 2.8.3 Copolymers of Butadiene 92 2.8.4 Terminally Functional Polydienes 93 2.9 Stereospecific Chain Polymerization and Copolymerization by Coordination Catalysts 94 2.9.1 Mechanism and Kinetics 94 2.9.2 Ethylene-Propylene Rubbers 98 2.9.3 Polydienes 100 2.9.4 Polyalkenamers 101 2.10 Graft and Block Copolymerization * 104 2.10.1 Graft Copolymerization by Conventional Free Radical Reactions 104 (i) Chemical Initiation 105 (ii) Other Methods 107 2.10.2 Block Copolymers by Controlled Radical Mechanisms 107 2.10.3 Block Copolymers by Anionic Mechanism 108 2.10.4 Block Copolymers by Cationic Mechanism 112 2.10.5 Block Copolymers by Ziegler-Natta (Insertion) Mechanism 113 References 115 Structure Characterization in the Science and Technology of Elastomers 130 3.1 Introduction 130 3.2 Chemical Composition 131 3.3 Sequence Distribution of Repeat Units 134 3.4 Chain Architecture 137 3.4.1 Molecular Weight and Its Distribution 137 3.4.2 Branching 150 3.4.3 Gel 153 3.5 Glass Transition and Secondary Relaxation Processes 155 3.6 Morphology 160 3.6.1 Orientation 160 3.6.2 Blends 163 3.6.3 Crystallinity 169 3.6.4 Defects 172 Acknowledgments 174 References 174 The Molecular Basis of Rubberlike Elasticity 182 4.1 Introduction 182 4.2 Structure of a Typical Network 183 4.3 Elementary Molecular Theories 184 4.3.1 Elasticity of the Single Chain 185 4.3.2 The Elastic Free Energy of the Network 188 4.3.3 The Reduced Stress and the Elastic Modulus 189 4.4 More Advanced Molecular Theories 192 4.4.1 The Constrained Junction Model 192 4.4.2 Entanglement Models 194 4.4.3 Contribution of Trapped Entanglements to the Modulus 196 4.5 Phenomenological Theories and Molecular Structure 197 4.6 Swelling of Networks and Responsive Gels 198 4.7 Enthalpic and Entropic Contributions to Rubber Elasticity: The Force-Temperature Relations 200 4.8 Direct Determination of Molecular Dimensions 202 4.9 Single-Molecule Elasticity 203 4.9.1 Gaussian Versus Non-Gaussian Effects 203 References 205 The Viscoelastic Behavior of Rubber and Dynamics of Blends 208 5.1 Introduction 208 5.2 Definitions of Measured Quantities, J(t), G(t), and G(ω); and Spectra L(logλ) and H(logτ) 213 5.2.1 Creep and Recovery 213 5.2.2 Stress Relaxation 214 5.2.3 Dynamic Mechanical Measurements 214 (i) Tensile and Bulk Moduli: Tensile and Bulk Compliance 216 5.3 The Glass Temperature 217 5.4 Viscoelastic Behavior Above Tg 218 5.4.1 Isothermal Measurements of Time or Frequency Dependence 218 5.4.2 Temperature Dependence 219 5.4.3 The Equilibrium Compliance Je 222 5.5 Viscoelastic Behavior Of Other Model Elastomers 222 5.5.1 Fluorinated Hydrocarbon Elastomers (``Viton'') 222 (i) Creep Compliance Data 223 (ii) Temperature Dependence of the Shift Factors 223 (iii) Retardation Spectra 224 (iv) Derived Dynamic Mechanical Properties 225 5.5.2 Urethane-Crosslinked Polybutadiene Elastomers (Plazek et al., 1988) 228 5.5.3 Comparisons Between Different Elastomers 230 5.5.4 Other Viscoelastic Measurements 231 5.6 Theoretical Interpretation of Viscoelastic Mechanisms and Anomalies 232 5.6.1 Breakdown of Thermorheological Simplicity of Low Molecular Weight Polymer 232 (i) The Coupling Model 234 (ii) Explanation of Thermorheological Complexity 236 5.6.2 Thermorheological Simplicity of Elastomers 239 5.6.3 Changes of the Segmental Relaxation Time and the Johari-Goldstein Relaxation Time with Crosslink Density 240 5.6.4 Junction Dynamics 240 (i) Experimental Data 240 (ii) Coupling Model Explanation (Roland and Ngai 1991; Ngai et al. 1993a) 241 (iii) Similarity of Flory's Constrained Junction Model for Elasticity to the Coupling Model for Junction Dynamics 242 5.7 Component Dynamics of Highly Asymmetric Polymer Blends 244 5.7.1 Intermolecularly Coupled Segmental Relaxation and Interchain Coupled Chain Dynamics in Highly Asymmetric Polymer Blends 244 5.7.2 Anomalous Component Dynamics of Polymer Blends 248 (i) Segmental and Global Chain Dynamics of PEO in Blends with PMMA 248 5.7.3 Explanation of Properties (i)–(ix) 275 (i) Explanation of Property (i) 276 (ii) Explanation of Property (ii) 282 (iii) Explanation of Property (iii) 285 (iv) Explanation of Property (iv) 285 (v) Explanation of Property (v) 287 (vi) Explanation of Property (vi) 289 (vii) Explanation of Property (vii) 291 (viii) Explanation of Properties (viii) and (viii') 292 (ix) Explanation of Property (ix) 293 5.7.4 Summary 294 References 294 Rheological Behavior and Processing of Unvulcanized Rubber 300 6.1 Rheology 300 6.1.1 Introduction 300 6.1.2 Basic Concepts 301 6.2 Linear Viscoelasticity 304 6.2.1 Material Constants 304 6.2.2 Boltzmann Superposition Principle 309 6.2.3 Time-Temperature Equivalence 312 (i) Superposition Principle 312 (ii) Density Scaling 316 6.2.4 Molecular Weight Dependences 318 6.2.5 Stress Birefringence 322 6.3 Nonlinear Viscoelasticity 325 6.3.1 Shear Thinning Flow 325 6.3.2 Particulate Fillers 326 (i) Payne Effect 327 (ii) Mullins Effect 328 (iii) Nanofillers 330 6.3.3 Blends 332 6.4 Engineering Analysis 334 6.4.1 Dimensionless Quantities 334 (i) Reynolds Number 335 (ii) Deborah Number 335 (iii) Weissenberg Number 335 (iv) Capillary Number 335 (v) Weber Number 336 (vi) Brinkman Number 336 (vii) Bingham Number 336 (viii) Elasticity Number 336 6.4.2 Empirical Rules 337 (i) Cox-Merz Rule (Cox and Merz, 1958) 337 (ii) Laun Relations (Laun, 1986) 337 (iii) Gleissle Equations (Gleissle, 1980) 338 (iv) Lodge-Meissner Rule (Lodge and Meissner, 1972) 339 (v) Boyer-Spencer (Boyer and Spencer, 1944) and Simha-Boyer (Simha and Boyer, 1962) Rules 339 6.5 Practical Processing Considerations 340 6.5.1 Mixing 340 6.5.2 Die Swell 342 6.5.3 Tack 344 Acknowledgment 345 References 345 Vulcanization 352 7.1 Introduction 352 7.2 Definition of Vulcanization 353 7.3 Effects of Vulcanization on Vulcanizate Properties 354 7.4 Characterization of the Vulcanization Process 355 7.5 Vulcanization by Sulfur without Accelerator 358 7.6 Accelerated-Sulfur Vulcanization 360 7.6.1 The Chemistry of Accelerated-Sulfur Vulcanization 366 7.6.2 Delayed-Action Accelerated Vulcanization 368 7.6.3 The Role of Zinc in Benzothiazole-Accelerated Vulcanization 370 7.6.4 Achieving Specified Vulcanization Characteristics 371 7.6.5 Effects on Adhesion to Brass-Plated Steel 372 7.6.6 The Effect on Vulcanizate Properties 373 7.6.7 Accelerated-Sulfur Vulcanization of Various Unsaturated Rubbers 378 7.6.8 Selected Accelerated-Sulfur System Recipes 379 7.7 Vulcanization by Phenolic Curatives, Benzoquinone Derivatives, or Bismaleimides 379 7.8 Vulcanization by the Action of Metal Oxides 383 7.9 Vulcanization by the Action of Organic Peroxides 385 7.9.1 Peroxide Vulcanization of Unsaturated Hydrocarbon Elastomers 386 7.9.2 Peroxide Vulcanization of Saturated Hydrocarbon Elastomers 388 7.9.3 Peroxide Vulcanization of Silicone Rubbers 389 7.9.4 Peroxide Vulcanization of Urethane Elastomers 390 7.9.5 Recipes for Peroxide Vulcanization 391 7.10 Dynamic Vulcanization 391 7.10.1 EPDM-Polyolefin Compositions 392 7.10.2 NBR-Nylon Compositions 392 7.10.3 Other Elastomeric Compositions Prepared by Dynamic Vulcanization 393 7.10.4 Technological Applications 393 7.10.5 Extra-High-Performance TPVs 394 References 394 Reinforcement of Elastomers by Particulate Fillers 398 8.1 Introduction 398 8.2 Preparation of Fillers 399 8.2.1 Nonreinforcing Fillers 399 8.2.2 Reinforcing Fillers 399 (i) Carbon Black 399 (ii) Silicas 400 (iii) New Reinforcing Fillers 401 8.3 Morphological and Physicochemical Characterization of Fillers 401 8.3.1 Filler Morphology Characterization 401 (i) Filler Morphology 401 (ii) Surface Area 403 (iii) Structure 404 (iv) Aggregate Size Distribution 406 8.3.2 Dispersibility 407 (i) Reflectivity 407 (ii) Laser Granulometry 407 8.3.3 Filler Physicochemistry 408 (i) Surface Energy 408 (ii) Surface Chemistry 409 8.4 The Mix: A Nanocomposite of Elastomer and Filler 412 8.4.1 Dispersion, Aggregate Sizes, and Distances 412 (i) Dispersion 412 (ii) Object Sizes in the Mix 413 (iii) Distances 414 8.4.2 Filler-Elastomer Interactions 415 (i) Carbon Black 415 (ii) Silica 416 8.5 Mechanical Properties of Filled Rubbers 417 8.5.1 Mechanical Properties in Green State 417 (i) Viscosity 418 (ii) Occluded Rubber 418 (iii) Shear Dependence of Viscosity, Non-Newtonian Behavior 418 8.5.2 Mechanical Properties in Vulcanized State 419 (i) Small-Strain Properties, Dynamic Viscoelastic Measurements 419 8.5.3 Applications 426 References 428 The Science of Rubber Compounding 432 9.1 Introduction 432 9.2 Polymers 433 9.2.1 Natural Rubber 433 9.2.2 Synthetic Elastomers 435 9.3 Filler Systems 446 9.3.1 Carbon Black Properties 446 9.3.2 Silica and Silicates 453 9.3.3 Chemistry of Silane Coupling Agents 455 9.3.4 Other Filler Systems 458 9.4 Stabilizer Systems 459 9.4.1 Degradation of Rubber 459 9.4.2 Antidegradant Use 461 9.4.3 Antidegradant Types 462 9.5 Vulcanization System 464 9.5.1 Activators 465 9.5.2 Vulcanizing Agents 469 9.5.3 Accelerators 469 9.5.4 Retarders and Antireversion Agents 470 9.6 Special Compounding Ingredients 472 9.6.1 Processing Oils 472 9.6.2 Plasticizers 474 9.6.3 Chemical Peptizers 475 9.6.4 Resins 476 9.6.5 Short Fibers 476 9.7 Compound Development 477 9.8 Compound Preparation 478 9.9 Environmental Requirements in Compounding 480 9.10 Summary 484 References 485 Strength of Elastomers 488 Strength of Elastomers 488 10.1 Introduction 488 10.2 Initiation of Fracture 489 10.2.1 Flaws and Stress Raisers 489 10.2.2 Stress and Energy Criteria for Rupture 491 10.2.3 Tensile Test Piece 493 10.2.4 Tear Test Piece 495 10.3 Threshold Strengths and Extensibilities 496 10.4 Crack Propagation 500 10.4.1 Overview 500 10.4.2 Viscoelastic Elastomers 500 10.4.3 Strain-Crystallizing Elastomers 503 10.4.4 Reinforcement with Fillers 504 10.4.5 Repeated Stressing: Dynamic Crack Propagation 506 10.4.6 Thermoplastic Elastomers 509 10.5 Tensile Rupture 509 10.5.1 Effects of Rate and Temperature 509 10.5.2 The Failure Envelope 511 10.5.3 Effect of Degree of Crosslinking 512 10.5.4 Strain-Crystallizing Elastomers 514 10.5.5 Energy Dissipation and Strength 515 10.6 Repeated Stressing: Mechanical Fatigue 516 10.7 Failure Under Multiaxial Stresses 519 10.7.1 Critical Plane Hypothesis 519 10.7.2 Energy Density Available for Driving Growth of Crack Precursors 520 10.7.3 Compression and Shear 521 10.7.4 Equibiaxial Tension 521 10.7.5 Triaxial Tension 522 10.8 surface Cracking by Ozone 523 10.9 Abrasive Wear 524 10.9.1 Mechanics of Wear 524 10.9.2 Chemical Effects 527 10.10 Computational Approaches to Failure Modeling 527 Acknowledgments 528 Further Reading 40 References 528 The Chemical Modification of Polymers 532 11.1 Introduction 532 11.2 Chemical Modification of Polymers Within Backbone and Chain Ends 533 11.3 Esterification, Etherification, and Hydrolysis of Polymers 535 11.4 The Hydrogenation of Polymers 538 11.5 Dehalogenation, Elimination, and Halogenation Reactions in Polymers 539 11.5.1 Dehydrochlorination of Poly(vinyl chloride) 539 11.5.2 Thermal Elimination 540 11.5.3 Halogenation of Polymers 541 11.5.4 Cyclization of Polymers 542 11.6 Other Addition Reactions to Double Bonds 543 11.6.1 Ethylene Derivatives 543 11.6.2 The Prins Reaction 545 11.7 Oxidation Reactions of Polymers 545 11.8 Functionalization of Polymers 546 11.9 Miscellaneous Chemical Reactions of Polymers 546 11.10 Block and Graft Copolymerization 547 11.10.1 Effects on Structure and Properties of Polymers 547 11.10.2 Block Copolymer Synthesis 549 11.10.3 Examples 549 11.10.4 Other Methods of Effecting Mechanicochemical Reactions 550 11.10.5 Ionic Mechanisms 551 (i) Three-Stage Process with Monofunctional Initiators 551 (ii) Two-Stage Process with Difunctional Initiators 552 (iii) Monofunctional Initiation and Coupling 552 (iv) Tapered Block Copolymers 552 11.10.6 Graft Copolymer Synthesis 552 (i) Polymer Transfer 553 (ii) Copolymerization via Unsaturated Groups 553 (iii) Redox Polymerization 554 (iv) High-Energy Radiation Techniques 556 (v) Photochemical Synthesis 557 (vi) Metallation Using Activated Organolithium with Chelating Diamines 558 11.10.7 Base Polymer Properties 559 References 560 Elastomer Blends 562 12.1 Introduction 562 12.2 Thermodynamics and Solubility Parameters 567 12.2.1 Flory-Huggins Model 568 12.2.2 Solubility and Interaction Parameters 569 12.2.3 Other Models 571 12.3 Preparation 573 12.4 Miscible Elastomer Blends 574 12.4.1 Thermodynamics 574 12.4.2 Analysis 574 (i) Glass Transition 574 (ii) Magnetic Resonance Imaging 575 (iii) Crystallinity 575 (iv) Interdiffusion 576 (v) Mechanical Properties 577 12.4.3 Compositional Gradient Copolymers 577 12.4.4 Distinct Polymers 580 (i) IR–BR Blends 580 (ii) Epoxidized PI-CPE Blends 581 12.4.5 Reactive Elastomers 581 12.5 Immiscible Elastomer Blends 582 12.5.1 Formation 582 12.5.2 Kinetics of Blend Morphology 582 12.5.3 Analysis 582 (i) Microscopy 582 (ii) Glass Transition Temperature 584 (iii) Magnetic Resonance Imaging 584 (iv) Light, X-ray, and Neutron Scattering 585 (v) Freezing Point Depression 586 12.5.4 Interphase Distribution of Filler, Curatives, and Plasticizers 586 (i) Curative and Plasticizer Migration in Elastomer Blends 586 (ii) Cure Compatibility 587 (iii) Interphase Filler Transfer 589 12.5.5 Analysis of Interphase Transfer 591 (i) Microscopy 591 (ii) Differential Swelling 591 (iii) Staining 591 (iv) Differential Pyrolysis 591 (v) GC Analysis of Bound Rubber 591 (vi) Mechanical Damping 591 12.5.6 Compatibilization 592 12.5.7 Properties of Immiscible Blends 594 (i) Processing 594 (ii) Modulus 595 (iii) Tack and Adhesion 595 (iv) Hysteresis 595 (v) Failure 596 12.5.8 Applications 597 (i) Unsaturated Elastomer Blends 597 (ii) Saturated and Unsaturated Elastomer Blends 597 12.6 Conclusion 598 Appendix 1: Acronyms for Common Elastomers 599 References 600 Thermoplastic Elastomers 606 13.1 Introduction 606 13.2 Synthesis of Thermoplastic Elastomers 612 13.2.1 Step-Growth Polymerization: Polyurethanes, Polyether-esters, Polyamides 612 13.2.2 Anionic Polymerization: Styrene-Diene Copolymers 614 13.2.3 Catalytic Polymerization 615 13.2.4 Free Radical Polymerization 615 13.2.5 Molecular Weight and Chain Structure 616 13.3 Morphology of Thermoplastic Elastomers 619 13.3.1 General Characteristics 619 13.3.2 Studies of Morphology 622 (i) Transmission Electron Microscopy (TEM) 622 (ii) Infrared and Raman Spectroscopy 623 (iii) Wide Angle X-ray Scattering (WAXS) 627 (iv) Small-Angle X-ray Scattering (SAXS) 629 (v) Small-Angle Neutron Scattering (SANS) 632 (vi) Nuclear Magnetic Resonance (NMR) 634 13.4 Properties and Effect of Structure 635 13.4.1 General Characteristics 635 13.4.2 Mechanical Properties 638 13.4.3 Thermal and Chemical Properties 642 13.5 Thermodynamics of Phase Separation 643 13.6 Thermoplastic Elastomers at Surfaces 648 13.6.1 General Characteristics 648 13.6.2 Studies of Surfaces 650 (i) Scanning Electron Microscopy (SEM) 650 (ii) Attenuated Total Internal Reflection Infrared Spectroscopy (ATR) 651 (iii) X-Ray Photoelectron Spectroscopy (XPS) 652 (iv) Secondary Ion Mass Spectroscopy (SIMS) 653 (v) Atomic Force Microscopy 654 13.7 Rheology and Processing 656 13.8 Applications 659 References 662 Tire Engineering 668 14.1 Introduction 668 14.2 Tire Types and Performance 668 14.3 Basic Tire Design 671 14.3.1 Tire Construction 671 14.3.2 Tire Components 671 14.4 Tire Engineering 673 14.4.1 Tire Nomenclature and Dimensions 673 14.4.2 Tire Mold Design 676 14.4.3 Cord Tension 681 14.4.4 Tread Design Patterns 682 14.5 Tire Materials 686 14.5.1 Tire Reinforcement 686 14.5.2 Steel Cord 687 14.5.3 Mechanism of Rubber: Brass Wire Adhesion 689 14.5.4 Rayon 692 14.5.5 Nylon 692 14.5.6 Polyester 693 14.5.7 Fiberglass 694 14.5.8 Aramid 694 14.5.9 Tire Cord Construction 695 14.5.10 Fabric Processing 696 14.5.11 Function of Adhesive 698 14.5.12 Rubber Compounding 699 14.6 Tire Testing 700 14.6.1 Laboratory Testing 700 14.6.2 Proving Grounds 703 14.6.3 Commercial Evaluation 703 14.7 Tire manufacturing 703 14.7.1 Compound Processing 704 14.7.2 Calendering 706 14.7.3 Extrusion 706 14.7.4 Tire Building 707 14.7.5 Final Tire Inspection 708 14.8 Summary 709 References 709 Recycling of Rubbers 712 15.1 Introduction 712 15.2 Retreading of Tires 715 15.3 Recycling of Rubber Vulcanizates 715 15.3.1 Reclaiming Technology 715 15.3.2 Surface Treatment 718 15.3.3 Grinding and Pulverization Technology 719 15.3.4 Devulcanization Technology 723 (i) Microwave Method 723 (ii) Ultrasonic Method 724 15.4 Use of Recycled Rubber 737 15.4.1 General Remarks 737 15.4.2 Use in New Tires 738 15.4.3 Rubber-Recycled Rubber Blends 738 15.4.4 Thermoplastic-Recycled Rubber Blend 745 15.4.5 Concrete Modified by Recycled Rubber 757 15.4.6 Asphalt Modified by Recycled Rubber 760 15.4.7 Use of Crumb Rubber in Soil 765 15.4.8 Products Made from Recycled Rubber 766 (i) Industrial Products 766 (ii) Absorbents 766 15.5 Pyrolysis and Incineration of Rubber 768 15.5.1 Recovery of Hydrocarbon Liquid and Carbon Black 768 15.5.2 Tire-Derived Fuel 770 15.6 Concluding Remarks 770 Acknowledgment 771 References 771 Index 780 A 780 B 780 C 781 D 784 E 784 F 786 G 787 H 788 I 788 J 789 K 789 L 789 M 789 N 790 O 791 P 791 R 792 S 795 T 797 U 799 V 799 W 801 X 801 Y 801 Z 801 Cover ......Page 1 Half Title......Page 2 Title Page......Page 4 Copyright......Page 5 Contents......Page 6 1.2 Elasticity of a Single Molecule......Page 16 1.3 Elasticity of a Three-Dimensional Network of Polymer Molecules......Page 20 1.4 Comparison with Experiment......Page 24 1.5 Continuum Theory of Rubber Elasticity......Page 26 1.5.1 Stress-Strain Relations......Page 27 (i) Strain-Hardening at Large Strains......Page 28 (ii) Inflation of a Thin-Walled Tube......Page 29 (iii) Inflation of a Thin-Walled Spherical Balloon......Page 30 (iv) Inflation of a Thick-Walled Spherical Shell......Page 31 (v) Surface Instability of Compressed or Bent Blocks......Page 32 (vii) Torsional Instability of Stretched Rubber Rods (Gent and Hua 2004)......Page 33 1.6 Second-Order Stresses......Page 34 1.7 Elastic Behavior Under Small Deformations......Page 36 1.8 Some Unsolved Problems in Rubber Elasticity......Page 39 Further Reading......Page 40 2.1 Introduction......Page 42 2.2 Classification of Polymerization Reactions and Kinetic Considerations......Page 43 2.2.1 Polyaddition/Polycondensation......Page 44 2.2.2 Chain Polymerization......Page 46 2.3 Polyaddition/Polycondensation......Page 47 2.4.1 General Kinetics......Page 49 2.4.2 Molecular Weight Distribution......Page 53 2.4.3 Special Case of Diene Polymerization......Page 54 2.4.4 Controlled Radical Polymerization......Page 55 2.5.1 Mechanism and Kinetics......Page 58 (i) Kinetics and Molecular Weights......Page 62 (i) Kinetics......Page 66 (ii) Chain Structure......Page 68 2.6.1 Kinetics......Page 69 (i) Styrene-Butadiene (SBR)......Page 72 (iii) Chloroprene......Page 74 2.7.1 Mechanism and Kinetics......Page 75 2.7.2 Butyl Rubber......Page 79 2.7.3 Living Cationic Polymerizations......Page 80 2.7.4 Other Cationic Polymerizations: Heterocyclic Monomers......Page 81 2.8.1 Mechanism and Kinetics......Page 83 2.8.2 Chain Microstructure of Polydienes......Page 90 2.8.3 Copolymers of Butadiene......Page 92 2.8.4 Terminally Functional Polydienes......Page 93 2.9.1 Mechanism and Kinetics......Page 94 2.9.2 Ethylene-Propylene Rubbers......Page 98 2.9.3 Polydienes......Page 100 2.9.4 Polyalkenamers......Page 101 2.10.1 Graft Copolymerization by Conventional Free Radical Reactions......Page 104 (i) Chemical Initiation......Page 105 2.10.2 Block Copolymers by Controlled Radical Mechanisms......Page 107 2.10.3 Block Copolymers by Anionic Mechanism......Page 108 2.10.4 Block Copolymers by Cationic Mechanism......Page 112 2.10.5 Block Copolymers by Ziegler-Natta (Insertion) Mechanism......Page 113 References......Page 115 3.1 Introduction......Page 130 3.2 Chemical Composition......Page 131 3.3 Sequence Distribution of Repeat Units......Page 134 3.4.1 Molecular Weight and Its Distribution......Page 137 3.4.2 Branching......Page 150 3.4.3 Gel......Page 153 3.5 Glass Transition and Secondary Relaxation Processes......Page 155 3.6.1 Orientation......Page 160 3.6.2 Blends......Page 163 3.6.3 Crystallinity......Page 169 3.6.4 Defects......Page 172 References......Page 174 4.1 Introduction......Page 182 4.2 Structure of a Typical Network......Page 183 4.3 Elementary Molecular Theories......Page 184 4.3.1 Elasticity of the Single Chain......Page 185 4.3.2 The Elastic Free Energy of the Network......Page 188 4.3.3 The Reduced Stress and the Elastic Modulus......Page 189 4.4.1 The Constrained Junction Model......Page 192 4.4.2 Entanglement Models......Page 194 4.4.3 Contribution of Trapped Entanglements to the Modulus......Page 196 4.5 Phenomenological Theories and Molecular Structure......Page 197 4.6 Swelling of Networks and Responsive Gels......Page 198 4.7 Enthalpic and Entropic Contributions to Rubber Elasticity: The Force-Temperature Relations......Page 200 4.8 Direct Determination of Molecular Dimensions......Page 202 4.9.1 Gaussian Versus Non-Gaussian Effects......Page 203 References......Page 205 5.1 Introduction......Page 208 5.2.1 Creep and Recovery......Page 213 5.2.3 Dynamic Mechanical Measurements......Page 214 (i) Tensile and Bulk Moduli: Tensile and Bulk Compliance......Page 216 5.3 The Glass Temperature......Page 217 5.4.1 Isothermal Measurements of Time or Frequency Dependence......Page 218 5.4.2 Temperature Dependence......Page 219 5.5.1 Fluorinated Hydrocarbon Elastomers (``Viton'')......Page 222 (ii) Temperature Dependence of the Shift Factors......Page 223 (iii) Retardation Spectra......Page 224 (iv) Derived Dynamic Mechanical Properties......Page 225 5.5.2 Urethane-Crosslinked Polybutadiene Elastomers (Plazek et al., 1988)......Page 228 5.5.3 Comparisons Between Different Elastomers......Page 230 5.5.4 Other Viscoelastic Measurements......Page 231 5.6.1 Breakdown of Thermorheological Simplicity of Low Molecular Weight Polymer......Page 232 (i) The Coupling Model......Page 234 (ii) Explanation of Thermorheological Complexity......Page 236 5.6.2 Thermorheological Simplicity of Elastomers......Page 239 (i) Experimental Data......Page 240 (ii) Coupling Model Explanation (Roland and Ngai 1991; Ngai et al. 1993a)......Page 241 (iii) Similarity of Flory's Constrained Junction Model for Elasticity to the Coupling Model for Junction Dynamics......Page 242 5.7.1 Intermolecularly Coupled Segmental Relaxation and Interchain Coupled Chain Dynamics in Highly Asymmetric Polymer Blends......Page 244 (i) Segmental and Global Chain Dynamics of PEO in Blends with PMMA......Page 248 5.7.3 Explanation of Properties (i)–(ix)......Page 275 (i) Explanation of Property (i)......Page 276 (ii) Explanation of Property (ii)......Page 282 (iv) Explanation of Property (iv)......Page 285 (v) Explanation of Property (v)......Page 287 (vi) Explanation of Property (vi)......Page 289 (vii) Explanation of Property (vii)......Page 291 (viii) Explanation of Properties (viii) and (viii')......Page 292 (ix) Explanation of Property (ix)......Page 293 References......Page 294 6.1.1 Introduction......Page 300 6.1.2 Basic Concepts......Page 301 6.2.1 Material Constants......Page 304 6.2.2 Boltzmann Superposition Principle......Page 309 (i) Superposition Principle......Page 312 (ii) Density Scaling......Page 316 6.2.4 Molecular Weight Dependences......Page 318 6.2.5 Stress Birefringence......Page 322 6.3.1 Shear Thinning Flow......Page 325 6.3.2 Particulate Fillers......Page 326 (i) Payne Effect......Page 327 (ii) Mullins Effect......Page 328 (iii) Nanofillers......Page 330 6.3.3 Blends......Page 332 6.4.1 Dimensionless Quantities......Page 334 (iv) Capillary Number......Page 335 (viii) Elasticity Number......Page 336 (ii) Laun Relations (Laun, 1986)......Page 337 (iii) Gleissle Equations (Gleissle, 1980)......Page 338 (v) Boyer-Spencer (Boyer and Spencer, 1944) and Simha-Boyer (Simha and Boyer, 1962) Rules......Page 339 6.5.1 Mixing......Page 340 6.5.2 Die Swell......Page 342 6.5.3 Tack......Page 344 References......Page 345 7.1 Introduction......Page 352 7.2 Definition of Vulcanization......Page 353 7.3 Effects of Vulcanization on Vulcanizate Properties......Page 354 7.4 Characterization of the Vulcanization Process......Page 355 7.5 Vulcanization by Sulfur without Accelerator......Page 358 7.6 Accelerated-Sulfur Vulcanization......Page 360 7.6.1 The Chemistry of Accelerated-Sulfur Vulcanization......Page 366 7.6.2 Delayed-Action Accelerated Vulcanization......Page 368 7.6.3 The Role of Zinc in Benzothiazole-Accelerated Vulcanization......Page 370 7.6.4 Achieving Specified Vulcanization Characteristics......Page 371 7.6.5 Effects on Adhesion to Brass-Plated Steel......Page 372 7.6.6 The Effect on Vulcanizate Properties......Page 373 7.6.7 Accelerated-Sulfur Vulcanization of Various Unsaturated Rubbers......Page 378 7.7 Vulcanization by Phenolic Curatives, Benzoquinone Derivatives, or Bismaleimides......Page 379 7.8 Vulcanization by the Action of Metal Oxides......Page 383 7.9 Vulcanization by the Action of Organic Peroxides......Page 385 7.9.1 Peroxide Vulcanization of Unsaturated Hydrocarbon Elastomers......Page 386 7.9.2 Peroxide Vulcanization of Saturated Hydrocarbon Elastomers......Page 388 7.9.3 Peroxide Vulcanization of Silicone Rubbers......Page 389 7.9.4 Peroxide Vulcanization of Urethane Elastomers......Page 390 7.10 Dynamic Vulcanization......Page 391 7.10.2 NBR-Nylon Compositions......Page 392 7.10.4 Technological Applications......Page 393 References......Page 394 8.1 Introduction......Page 398 (i) Carbon Black......Page 399 (ii) Silicas......Page 400 (i) Filler Morphology......Page 401 (ii) Surface Area......Page 403 (iii) Structure......Page 404 (iv) Aggregate Size Distribution......Page 406 (ii) Laser Granulometry......Page 407 (i) Surface Energy......Page 408 (ii) Surface Chemistry......Page 409 (i) Dispersion......Page 412 (ii) Object Sizes in the Mix......Page 413 (iii) Distances......Page 414 (i) Carbon Black......Page 415 (ii) Silica......Page 416 8.5.1 Mechanical Properties in Green State......Page 417 (iii) Shear Dependence of Viscosity, Non-Newtonian Behavior......Page 418 (i) Small-Strain Properties, Dynamic Viscoelastic Measurements......Page 419 8.5.3 Applications......Page 426 References......Page 428 9.1 Introduction......Page 432 9.2.1 Natural Rubber......Page 433 9.2.2 Synthetic Elastomers......Page 435 9.3.1 Carbon Black Properties......Page 446 9.3.2 Silica and Silicates......Page 453 9.3.3 Chemistry of Silane Coupling Agents......Page 455 9.3.4 Other Filler Systems......Page 458 9.4.1 Degradation of Rubber......Page 459 9.4.2 Antidegradant Use......Page 461 9.4.3 Antidegradant Types......Page 462 9.5 Vulcanization System......Page 464 9.5.1 Activators......Page 465 9.5.3 Accelerators......Page 469 9.5.4 Retarders and Antireversion Agents......Page 470 9.6.1 Processing Oils......Page 472 9.6.2 Plasticizers......Page 474 9.6.3 Chemical Peptizers......Page 475 9.6.5 Short Fibers......Page 476 9.7 Compound Development......Page 477 9.8 Compound Preparation......Page 478 9.9 Environmental Requirements in Compounding......Page 480 9.10 Summary......Page 484 References......Page 485 10.1 Introduction......Page 488 10.2.1 Flaws and Stress Raisers......Page 489 10.2.2 Stress and Energy Criteria for Rupture......Page 491 10.2.3 Tensile Test Piece......Page 493 10.2.4 Tear Test Piece......Page 495 10.3 Threshold Strengths and Extensibilities......Page 496 10.4.2 Viscoelastic Elastomers......Page 500 10.4.3 Strain-Crystallizing Elastomers......Page 503 10.4.4 Reinforcement with Fillers......Page 504 10.4.5 Repeated Stressing: Dynamic Crack Propagation......Page 506 10.5.1 Effects of Rate and Temperature......Page 509 10.5.2 The Failure Envelope......Page 511 10.5.3 Effect of Degree of Crosslinking......Page 512 10.5.4 Strain-Crystallizing Elastomers......Page 514 10.5.5 Energy Dissipation and Strength......Page 515 10.6 Repeated Stressing: Mechanical Fatigue......Page 516 10.7.1 Critical Plane Hypothesis......Page 519 10.7.2 Energy Density Available for Driving Growth of Crack Precursors......Page 520 10.7.4 Equibiaxial Tension......Page 521 10.7.5 Triaxial Tension......Page 522 10.8 surface Cracking by Ozone......Page 523 10.9.1 Mechanics of Wear......Page 524 10.10 Computational Approaches to Failure Modeling......Page 527 References......Page 528 11.1 Introduction......Page 532 11.2 Chemical Modification of Polymers Within Backbone and Chain Ends......Page 533 11.3 Esterification, Etherification, and Hydrolysis of Polymers......Page 535 11.4 The Hydrogenation of Polymers......Page 538 11.5.1 Dehydrochlorination of Poly(vinyl chloride)......Page 539 11.5.2 Thermal Elimination......Page 540 11.5.3 Halogenation of Polymers......Page 541 11.5.4 Cyclization of Polymers......Page 542 11.6.1 Ethylene Derivatives......Page 543 11.7 Oxidation Reactions of Polymers......Page 545 11.9 Miscellaneous Chemical Reactions of Polymers......Page 546 11.10.1 Effects on Structure and Properties of Polymers......Page 547 11.10.3 Examples......Page 549 11.10.4 Other Methods of Effecting Mechanicochemical Reactions......Page 550 (i) Three-Stage Process with Monofunctional Initiators......Page 551 11.10.6 Graft Copolymer Synthesis......Page 552 (ii) Copolymerization via Unsaturated Groups......Page 553 (iii) Redox Polymerization......Page 554 (iv) High-Energy Radiation Techniques......Page 556 (v) Photochemical Synthesis......Page 557 (vi) Metallation Using Activated Organolithium with Chelating Diamines......Page 558 11.10.7 Base Polymer Properties......Page 559 References......Page 560 12.1 Introduction......Page 562 12.2 Thermodynamics and Solubility Parameters......Page 567 12.2.1 Flory-Huggins Model......Page 568 12.2.2 Solubility and Interaction Parameters......Page 569 12.2.3 Other Models......Page 571 12.3 Preparation......Page 573 (i) Glass Transition......Page 574 (iii) Crystallinity......Page 575 (iv) Interdiffusion......Page 576 12.4.3 Compositional Gradient Copolymers......Page 577 (i) IR–BR Blends......Page 580 12.4.5 Reactive Elastomers......Page 581 (i) Microscopy......Page 582 (iii) Magnetic Resonance Imaging......Page 584 (iv) Light, X-ray, and Neutron Scattering......Page 585 (i) Curative and Plasticizer Migration in Elastomer Blends......Page 586 (ii) Cure Compatibility......Page 587 (iii) Interphase Filler Transfer......Page 589 (vi) Mechanical Damping......Page 591 12.5.6 Compatibilization......Page 592 (i) Processing......Page 594 (iv) Hysteresis......Page 595 (v) Failure......Page 596 (ii) Saturated and Unsaturated Elastomer Blends......Page 597 12.6 Conclusion......Page 598 Appendix 1: Acronyms for Common Elastomers......Page 599 References......Page 600 13.1 Introduction......Page 606 13.2.1 Step-Growth Polymerization: Polyurethanes, Polyether-esters, Polyamides......Page 612 13.2.2 Anionic Polymerization: Styrene-Diene Copolymers......Page 614 13.2.4 Free Radical Polymerization......Page 615 13.2.5 Molecular Weight and Chain Structure......Page 616 13.3.1 General Characteristics......Page 619 (i) Transmission Electron Microscopy (TEM)......Page 622 (ii) Infrared and Raman Spectroscopy......Page 623 (iii) Wide Angle X-ray Scattering (WAXS)......Page 627 (iv) Small-Angle X-ray Scattering (SAXS)......Page 629 (v) Small-Angle Neutron Scattering (SANS)......Page 632 (vi) Nuclear Magnetic Resonance (NMR)......Page 634 13.4.1 General Characteristics......Page 635 13.4.2 Mechanical Properties......Page 638 13.4.3 Thermal and Chemical Properties......Page 642 13.5 Thermodynamics of Phase Separation......Page 643 13.6.1 General Characteristics......Page 648 (i) Scanning Electron Microscopy (SEM)......Page 650 (ii) Attenuated Total Internal Reflection Infrared Spectroscopy (ATR)......Page 651 (iii) X-Ray Photoelectron Spectroscopy (XPS)......Page 652 (iv) Secondary Ion Mass Spectroscopy (SIMS)......Page 653 (v) Atomic Force Microscopy......Page 654 13.7 Rheology and Processing......Page 656 13.8 Applications......Page 659 References......Page 662 14.2 Tire Types and Performance......Page 668 14.3.2 Tire Components......Page 671 14.4.1 Tire Nomenclature and Dimensions......Page 673 14.4.2 Tire Mold Design......Page 676 14.4.3 Cord Tension......Page 681 14.4.4 Tread Design Patterns......Page 682 14.5.1 Tire Reinforcement......Page 686 14.5.2 Steel Cord......Page 687 14.5.3 Mechanism of Rubber: Brass Wire Adhesion......Page 689 14.5.5 Nylon......Page 692 14.5.6 Polyester......Page 693 14.5.8 Aramid......Page 694 14.5.9 Tire Cord Construction......Page 695 14.5.10 Fabric Processing......Page 696 14.5.11 Function of Adhesive......Page 698 14.5.12 Rubber Compounding......Page 699 14.6.1 Laboratory Testing......Page 700 14.7 Tire manufacturing......Page 703 14.7.1 Compound Processing......Page 704 14.7.3 Extrusion......Page 706 14.7.4 Tire Building......Page 707 14.7.5 Final Tire Inspection......Page 708 References......Page 709 15.1 Introduction......Page 712 15.3.1 Reclaiming Technology......Page 715 15.3.2 Surface Treatment......Page 718 15.3.3 Grinding and Pulverization Technology......Page 719 (i) Microwave Method......Page 723 (ii) Ultrasonic Method......Page 724 15.4.1 General Remarks......Page 737 15.4.3 Rubber-Recycled Rubber Blends......Page 738 15.4.4 Thermoplastic-Recycled Rubber Blend......Page 745 15.4.5 Concrete Modified by Recycled Rubber......Page 757 15.4.6 Asphalt Modified by Recycled Rubber......Page 760 15.4.7 Use of Crumb Rubber in Soil......Page 765 (ii) Absorbents......Page 766 15.5.1 Recovery of Hydrocarbon Liquid and Carbon Black......Page 768 15.6 Concluding Remarks......Page 770 References......Page 771 B......Page 780 C......Page 781 E......Page 784 F......Page 786 G......Page 787 I......Page 788 M......Page 789 N......Page 790 P......Page 791 R......Page 792 S......Page 795 T......Page 797 V......Page 799 Z......Page 801 The 4th edition of The Science and Technology of Rubber provides a broad survey of elastomers with special emphasis on materials with a rubber-like elasticity. As in the 3rd edition, the emphasis remains on a unified treatment of the material; exploring topics from the chemical aspects such as elastomer synthesis and curing, through recent theoretical developments and characterization of equilibrium and dynamic properties, to the final applications of rubber, including tire engineering and manufacturing. Many advances have been made in polymer and elastomers research over the past ten years since the 3rd edition was published. Updated material stresses the continuous relationship between the ongoing research in synthesis, physics, structure, and mechanics of rubber technology and industrial applications. Special attention is paid to recent advances in rubber-like elasticity theory and new processing techniques for elastomers. This new edition is comprised of 20% new material, including a new chapter on environmental issues and tire recycling. Provides the most comprehensive survey of elastomers for engineers and researchers in a unified treatment: the text moves from the chemical aspects such as elastomer synthesis and curing, through recent theoretical developments and characterization of equilibrium and dynamic properties, to the final applications of rubber, including tire engineering and manufacturing. Contains important updates to several chapters, including elastomer synthesis, characterization, viscoelastic behavior, rheology, reinforcement, tire engineering, and recyclingIncludes a new chapter on the burgeoning field of bioelastomers. The 4e of The Science and Technology of Rubber provides a broad survey of elastomers with special emphasis on materials with a rubber-like elasticity. As in previous editions, the emphasis remains on a unified treatment of the material, exploring chemical aspects such as elastomer synthesis and curing, through recent theoretical developments and characterization of equilibrium and dynamic properties, to the final applications of rubber, including tire engineering and manufacturing. Updated material stresses the continuous relationship between ongoing research in synthesis, physics, structure and mechanics of rubber technology and industrial applications. Special attention is paid to recent advances in rubber-like elasticity theory and new processing techniques for elastomers. Exciting new developments in green tire manufacturing and tire recycling are covered.

• Provides a complete survey of elastomers for engineers and researchers in a unified treatment: from chemical aspects like elastomer synthesis and curing to the final applications of rubber, including tire engineering and manufacturing
• Contains important updates to several chapters, including elastomer synthesis, characterization, viscoelastic behavior, rheology, reinforcement, tire engineering, and recycling
• Includes a new chapter on the burgeoning field of bioelastomers