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Rubber-Clay Nanocomposites: Science, Technology, and Applications

ISBN: 978-1-118-09287-3
592 pages
August 2011
Rubber-Clay Nanocomposites: Science, Technology, and Applications (1118092872) cover image

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The one-stop resource for rubber-clay nanocomposite information

The first comprehensive, single-volume book to compile all the most important data on rubber-clay nanocomposites in one place, Rubber-Clay Nanocomposites: Science, Technology, and Applications reviews rubber-clay nanocomposites in an easy-to-reference format designed for R&D professionals.

Including contributions from experts from North America, Europe, and Asia, the book explores the properties of compounds with rubber-clay nanocomposites, including their rheology, curing kinetics, mechanical properties, and many others.

Rubber-clay nanocomposites are of growing interest to the scientific and technological community, and have been shown to improve rubber compound reinforcement and impermeability. These natural mineral fillers are of potential interest for large-scale applications and are already making an impact in several major fields. Packed with valuable information about the synthesis, processing, and mechanics of these reinforced rubbers, the book covers assorted rubber-clay nanocomposites applications, such as in automotive tires and as polymer fillers.

Promoting common knowledge and interpretation of the most important aspects of rubber-clay nanocomposites, and clarifying the main results achieved in the field of rubbers and crosslinked rubbers—something not covered in other books in the field—Rubber-Clay Nanocomposites helps scientists understand morphology, vulcanization, permeability, processing methods, and characterization factors quickly and easily.

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Table of Contents

PREFACE xvii

CONTRIBUTORS xxi

SECTION I CLAYS FOR NANOCOMPOSITES

1 CLAYS AND CLAY MINERALS 3

1.1 What’s in a Name / 3

1.2 Multiscale Organization of Clay Minerals / 6

1.2.1 Dispersion Versus Aggregation / 6

1.2.2 Delamination/Exfoliation Versus Stacking / 6

1.3 Intimate Organization of the Layer / 8

1.3.1 Cationic and Neutral Clay Minerals / 8

1.3.2 Anionic Clay Minerals (O) / 21

1.4 Most Relevant Physicochemical Properties of Clay Mineral / 22

1.4.1 Surface Area and Porosity / 22

1.4.2 Chemical Landscape of the Clay Surfaces / 24

1.4.3 Cation (and Anion) Exchange Capacity / 24

1.4.4 Intercalation and Confinement in the Interlayer Space / 27

1.4.5 Swelling / 30

1.4.6 Rheology / 31

1.5 Availability of Natural Clays and Synthetic Clay Minerals / 33

1.6 Clays and (Modified) Clay Minerals as Fillers / 35

Acknowledgment / 37

References / 37

2 ORGANOPHILIC CLAY MINERALS 45

2.1 Organophilicity/Lipophilicity and the Hydrophilic/Lipophilic Balance (HLB) / 45

2.2 From Clays to Organoclays in Polymer Technology / 47

2.3 Methods of Organoclay Synthesis / 49

2.3.1 Cation Exchange from Solutions / 49

2.3.2 Solid-State Intercalation / 58

2.3.3 Grafting from Solution / 59

2.3.4 Direct Synthesis of Grafted Organoclays / 62

2.3.5 Postsynthesis Modifications of Organoclays: The “PCH” / 64

2.3.6 An Overview of Commercial Organoclays / 64

2.3.7 One-Pot CPN Formation / 66

2.4 Other Types of Clay Modifications for Clay-Based Nanomaterials / 66

2.4.1 Organo-Pillared Clays / 66

2.4.2 Plasma-Treated Clays / 69

2.5 Fine-Tuning of Organoclays Properties / 69

2.5.1 Maximizing the Dispersion of the Filler: Effect

of Surfactant/CEC Ratio / 69

2.5.2 Improving Thermal Stability / 70

2.5.3 Chemical Treatments / 71

2.5.4 Physical Treatments (Freeze-Drying, Sonication, Microwave) / 71

2.6 Some Introductory Reflections on Organoclay Polymer Nanocomposites / 72

References / 75

3 INDUSTRIAL TREATMENTS AND MODIFICATION OF CLAY MINERALS 87

3.1 Bentonite: From Mine to Plant / 87

3.1.1 A Largely Diffused Clay / 87

3.1.2 Geological Occurrence / 89

3.1.3 Mining / 89

3.2 Processing of Bentonite / 90

3.2.1 Modification of Bentonite Properties / 90

3.2.2 Processing Technologies / 91

3.3 Purification of Clay / 93

3.3.1 Influence of Clay Concentration / 94

3.3.2 Influence of Swelling Time / 94

3.3.3 Influence of Temperature / 95

3.4 Reaction of Clay with Organic Substances / 97

3.5 Particle Size Modification / 99

References / 99

4 ALKYLAMMONIUM CHAINS ON LAYERED CLAY MINERAL SURFACES 101

4.1 Structure and Dynamics / 101

4.1.1 Packing Density and Self-Assembly / 102

4.1.2 Dynamics and Diffusion at the Clay–Surfactant Interface / 110

4.1.3 Utility of Molecular Simulation to Obtain Molecular-Level Insight / 111

4.2 Thermal Properties / 111

4.2.1 Reversible Melting Transitions of Alkyl Chains in the Interlayer / 111

4.2.2 Solvent Evaporation and Thermal Elimination of Alkyl Surfactants / 113

4.3 Layer Separation and Miscibility with Polymers / 115

4.3.1 Thermodynamics Model for Exfoliation in Polymer Matrices / 115

4.3.2 Cleavage Energy / 116

4.3.3 Surface Energy / 121

4.4 Mechanical Properties of Clay Minerals / 121

References / 123

5 CHEMISTRY OF RUBBER–ORGANOCLAY NANOCOMPOSITES 127

5.1 Introduction / 127

5.2 Organic Cation Decomposition in Salts, Organoclays and Polymer Nanocomposites / 128

5.2.1 Experimental Techniques / 128

5.2.2 Decomposition of Organoclays Versus Precursor Organic Cation Salts / 133

5.3 Mechanism of Thermal Decomposition of Organoclays / 135

5.4 Role of Organic Cations in Organoclays as Rubber Vulcanization Activators / 137

References / 141

SECTION II PREPARATION AND CHARACTERIZATION OF RUBBER–CLAY NANOCOMPOSITES

6 PROCESSING METHODS FOR THE PREPARATION OF RUBBER–CLAY NANOCOMPOSITES 147

6.1 Introduction / 147

6.2 Latex Compounding Method / 148

6.2.1 Mechanism / 148

6.2.2 Influencing Factors / 149

6.3 Melt Compounding / 157

6.3.1 Mechanism / 157

6.3.2 Influencing Factors / 160

6.4 Solution Intercalation and In Situ Polymerization Intercalation / 170

6.5 Summary and Prospect / 170

Acknowledgment / 171

References / 171

7 MORPHOLOGY OF RUBBER–CLAY NANOCOMPOSITES 181

7.1 Introduction / 181

7.1.1 Focus, Objective and Structure of Chapter 7 / 181

7.1.2 X-Ray Diffraction Analysis for the Investigation of RCN / 182

7.2 Background for the Review of RCN Morphology / 182

7.2.1 Cationic Clays Used for the Preparation of Rubber Nanocomposites / 182

7.2.2 Multiscale Organization of Layered Clays / 184

7.2.3 Clay Distribution and Dispersion / 184

7.2.4 Clay Modification: Intercalation of Low Molecular Mass Substances / 184

7.2.5 Types of Polymer–Clay Composites / 184

7.2.6 Specific Literature on RCN / 186

7.3 Rubber–Clay Nanocomposites with Pristine Clays / 186

7.3.1 Rubber Nanocomposites with Cationic Clays / 187

7.3.2 In a Nutshell / 187

7.3.3 Distribution and Dispersion of a Pristine Clay in a Rubber Matrix / 190

7.3.4 Organization of Aggregated Pristine Clays / 194

7.4 Rubber–Clay Nanocomposites with Clays Modified with Primary Alkenylamines / 197

7.4.1 In a Nutshell / 197

7.4.2 Composites with Montmorillonite and Bentonite / 198

7.4.3 Composites with Fluorohectorite Modified with a Primary Alkenylamine / 202

7.5 Rubber–Clay Nanocomposites with Clays Modified with an Ammonium Cation Having three Methyls and One Long-Chain Alkenyl Substituents / 206

7.5.1 In a Nutshell / 206

7.5.2 Composites with Montmorillonite and Bentonite / 207

7.6 Rubber–Clay Nanocomposites with Montmorillonite Modified with Two Substituents Larger Than Methyl / 212

7.6.1 In a Nutshell / 212

7.6.2 Hydrogenated Tallow and Benzyl Groups as Ammonium Cation Substituents / 213

7.6.3 Hydrogenated Tallow and Ethylhexyl Groups as Ammonium Cation Substituents / 213

7.6.4 Other Long- and Short-Chain Alkenyl Groups as Ammonium Cation Substituents / 215

7.7 Rubber Composites with Montmorillonite Modified with an Ammonium Cation Containing a Polar Group / 215

7.7.1 In a Nutshell / 217

7.7.2 Composites with Diene Rubbers / 217

7.8 Rubber Nanocomposites with Montmorillonite Modified with an Ammonium Cation Containing Two Long-Chain Alkenyl Substituents / 219

7.8.1 In a Nutshell / 220

7.8.2 Composites with Two Talloyl Groups as Ammonium Cation Substituents / 220

7.9 Proposed Mechanisms for the Formation of Rubber–Clay Nanocomposites / 228

7.9.1 Two Mechanisms for the Formation of an Exfoliated Clay / 228

7.9.2 Two Mechanisms for the Formation of an Intercalated Organoclay / 228

7.9.3 Intercalation of Polymer Chains in the Interlayer Space / 229

7.9.4 Intercalation of Low Molecular Mass Substances in the Interlayer Space / 230

Abbreviations / 232

Acknowledgment / 233

References / 233

8 RHEOLOGY OF RUBBER–CLAY NANOCOMPOSITES 241

8.1 Introduction / 241

8.2 Rheological Behavior of Rubber–Clay Nanocomposites / 242

8.2.1 Natural Rubber (NR), Epoxidized Natural Rubber (ENR) and Polyisoprene Rubber (IR)–Clay Nanocomposites / 243

8.2.2 Styrene–Butadiene Rubber (SBR)–Clay Nanocomposites / 246

8.2.3 Polybutadiene Rubber (BR)–Clay Nanocomposites / 247

8.2.4 Acrylonitrile Butadiene Rubber (NBR)–Clay Nanocomposites / 250

8.2.5 Ethylene Propylene Rubber–Clay Nanocomposites / 253

8.2.6 Fluoroelastomer–Clay Nanocomposites / 254

8.2.7 Poly(isobutylene-co-para-methylstyrene) (BIMS) Rubber–Clay Nanocomposites / 257

8.2.8 Poly(ethylene-co-vinylacetate) (EVA) Rubber–Clay Nanocomposites / 257

8.2.9 Polyepichlorohydrin Rubber–Clay Nanocomposites / 259

8.2.10 Thermoplastic Polyurethane (TPU)–Clay Nanocomposites / 261

8.2.11 Styrene–Ethylene–Butylene–Styrene (SEBS) Block Copolymer–Clay Nanocomposites / 262

8.3 General Remarks on Rheology of Rubber–Clay Nanocomposites / 263

8.4 Overview of Rheological Theories of Polymer–Clay Nanocomposites / 269

8.5 Conclusion and Outlook / 270

References / 271

9 VULCANIZATION CHARACTERISTICS AND CURING KINETIC OF RUBBER–ORGANOCLAY NANOCOMPOSITES 275

9.1 Introduction / 275

9.2 Vulcanization Reaction / 276

9.3 Rubber Cross-Linking Systems / 278

9.3.1 Sulfur Vulcanization / 278

9.3.2 Peroxide Vulcanization / 282

9.4 The Role of Organoclay on Vulcanization Reaction / 283

9.4.1 Influence of Organoclay Structural Characteristics on Rubber Vulcanization / 288

9.5 Vulcanization Kinetics of Rubber–Organoclay Nanocomposites / 290

9.6 Conclusions / 297

References / 298

10 MECHANICAL AND FRACTURE MECHANICS PROPERTIES OF RUBBER COMPOSITIONS WITH REINFORCING COMPONENTS 305

10.1 Introduction / 305

10.2 Testing of Viscoelastic and Mechanical Properties of Reinforced Elastomeric Materials / 307

10.2.1 Dynamic–Mechanical Analysis / 307

10.2.2 Tensile Testing / 310

10.2.3 Assessment of Toughness Behavior under Impact-Like Loading Conditions / 313

10.2.4 Hardness Testing / 315

10.2.5 Special Methods / 316

10.3 Characterization of the Fracture Behavior of Elastomers / 319

10.3.1 Fracture Mechanics Concepts / 319

10.3.2 Experimental Methods / 321

10.4 Mechanism of Reinforcement in Rubber–Clay Composites / 328

10.5 Theories and Modeling of Reinforcement / 333

Acknowledgment / 336

References / 336

11 PERMEABILITY OF RUBBER COMPOSITIONS CONTAINING CLAY 343

11.1 Introduction / 343

11.1.1 Butyl Rubbers as Nanocomposite Base Elastomers / 343

11.1.2 Measurement of Tire Innerliner Compound Permeability / 345

11.1.3 Further Improvement in Tire Permeability / 346

11.2 Nanocomposites / 346

11.3 Preparation of Elastomer Nanocomposites / 352

11.4 Temperature and Compound Permeability / 352

11.5 Vulcanization of Nanocomposite Compounds and Permeability / 356

11.6 Thermodynamics and BIMSM Montmorillonite Nanocomposites / 358

11.7 Nanocomposites and Tire Performance / 362

11.8 Summary / 364

References / 364

SECTION III COMPOUNDS WITH RUBBER–CLAY NANOCOMPOSITES

12 RUBBER–CLAY NANOCOMPOSITES BASED ON APOLAR DIENE RUBBER 369

12.1 Introduction / 369

12.2 Preparation Methods / 371

12.2.1 Latex / 371

12.2.2 Solution / 373

12.2.3 Melt Blending / 374

12.3 Cure Characteristics / 377

12.4 Clay Dispersion / 379

12.4.1 Detection / 380

12.4.2 Characterization / 383

12.5 Properties / 387

12.5.1 Mechanical (Dynamic–Mechanical) / 387

12.5.2 Friction/Wear/Abrasion / 392

12.5.3 Barrier / 393

12.5.4 Fire Resistance / 396

12.5.5 Others / 397

12.6 Applications and Future Trends / 398

Acknowledgment / 399

References / 399

13 RUBBER–CLAY NANOCOMPOSITES BASED ON NITRILE

RUBBER 409

13.1 Introduction / 409

13.2 Preparation Methods and Clay

Dispersion / 410

13.2.1 Solution / 410

13.2.2 Latex / 411

13.2.3 Melt Blending / 412

13.3 Cure Characteristics / 414

13.4 Properties / 416

13.4.1 Mechanical (Dynamic–Mechanical) / 416

13.4.2 Friction/Wear / 421

13.4.3 Barrier / 423

13.4.4 Fire Resistance / 424

13.4.5 Others / 425

13.5 Outlook / 425

Acknowledgment / 426

References / 426

xii CONTENTS

FOR SCREEN VIEWING IN DART ONLY

14 RUBBER–CLAY NANOCOMPOSITES BASED ON BUTYL AND

HALOBUTYL RUBBERS 431

14.1 Introduction / 431

14.1.1 Butyl Rubber: Key Properties

and Applications / 431

14.1.2 Butyl Rubber–Clay Nanocomposites / 433

14.2 Types of Clays Useful in Butyl Rubber–Clay

Nanocomposites / 435

14.2.1 Montmorillonite Clays / 435

14.2.2 Hydrotalcite Clays / 435

14.2.3 High Aspect Ratio Talc Fillers / 436

14.2.4 Other Clays / 437

14.3 Compatibilizer Systems for Butyl Rubber–Clay

Nanocomposites / 438

14.3.1 Surfactants and Swelling Agents / 439

14.3.2 Butyl Rubber Ionomers / 439

14.3.3 Maleic Anhydride-Grafted Polymers / 443

14.3.4 Low Molecular Weight Polymers and Resins / 444

14.4 Methods of Preparation of Butyl Rubber–Clay Nanocomposites / 444

14.4.1 Melt Method / 445

14.4.2 Solution Method / 445

14.4.3 Latex Method / 447

14.4.4 In Situ Polymerization / 448

14.5 Properties and Applications of Butyl Rubber–Clay Nanocomposites / 449

14.5.1 Air Barrier Properties / 449

14.5.2 Reinforcement Properties / 452

14.5.3 Vulcanization Properties / 454

14.5.4 Adhesion Properties / 456

14.5.5 Other Properties / 457

14.6 Conclusions / 457

References / 458

15 RUBBER–CLAY NANOCOMPOSITES BASED ON OLEFINIC RUBBERS (EPM, EPDM) 465

15.1 Introduction / 465

15.2 Types of Clay Minerals Useful in EPM–, EPDM–Clay Nanocomposites / 466

15.3 Compatibilizer Systems for Olefinic Rubber–Clay Nanocomposites / 467

15.4 Preparation of EPDM–Clay Nanocomposites by an In Situ Intercalation Method / 469

15.5 Characteristics of EPDM–Clay Nanocomposites / 473

15.5.1 Gas Barrier Properties of EPDM–Clay Nanocomposites / 473

15.5.2 Rheological Properties of EPDM–Clay Nanocomposites / 474

15.5.3 Stability of EPDM–Clay Nanocomposites / 475

15.5.4 Swelling Properties of EPDM–Clay Nanocomposites / 475

15.5.5 Mechanical Properties of EPDM–Clay Nanocomposites / 476

15.6 Preparation and Characteristics of EPM–Clay Nanocomposites / 479

15.6.1 Tensile Properties of EPM–CNs / 480

15.6.2 Temperature Dependence of Dynamic Storage Moduli of EPM–CNs / 481

15.6.3 Creep Properties of EPM–CNs / 482

15.6.4 Swelling Properties of EPM–CNs / 483

15.7 Conclusions / 486

References / 486

16 RUBBER–CLAY NANOCOMPOSITES BASED ON THERMOPLASTIC ELASTOMERS 489

16.1 Introduction / 489

16.2 Selection of Materials / 491

16.2.1 Polymer Resin / 491

16.2.2 Nanoparticles / 493

16.3 Experimental / 493

16.3.1 Processing of Thermoplastic Elastomer Nanocomposites / 493

16.3.2 Morphological Characterization / 494

16.3.3 Thermal Properties Characterization / 495

16.3.4 Flammability Properties Characterization / 495

16.3.5 Thermophysical Properties Characterization / 496

16.4 Numerical / 497

16.4.1 Modeling of Decomposition Kinetics / 497

16.5 Discussion of Results / 501

16.5.1 Nanoparticle Dispersion / 501

16.5.2 Thermal Properties / 503

16.5.3 Flammability Properties / 507

16.5.4 Microstructures of Posttest Specimens / 511

16.5.5 Thermophysical Properties / 512

16.5.6 Kinetic Parameters / 513

16.6 Summary and Conclusions / 516

16.7 Nomenclature / 517

Acknowledgments / 518

References / 518

SECTION IV APPLICATIONS OF RUBBER–CLAY NANOCOMPOSITES

17 AUTOMOTIVE APPLICATIONS OF RUBBER–CLAY NANOCOMPOSITES 525

17.1 Introduction / 525

17.2 Automotive Application of Rubber / 526

17.2.1 Automotive Hose / 527

17.2.2 Automotive Seals / 528

17.2.3 Automotive Belts / 529

17.2.4 Automotive Tubing / 529

17.2.5 Door Seal and Window Channels / 529

17.2.6 Diaphragms and Rubber Boots / 529

17.2.7 Tire, Tube and Flap / 529

17.2.8 Other Miscellaneous Rubber Parts / 531

17.3 Prime Requirement of Different Elastomeric Auto Components from Application Point of View / 531

17.4 Elastomeric Nanocomposites and Rubber Industry / 531

17.5 Superiority of Clay/Clay Mineral in Comparison to Other Nanofillers / 534

17.6 Organo-Modified Clay/Clay Minerals / 534

17.7 Scope of Application of Elastomeric Nanocomposites in Automotive Industry / 534

17.7.1 Lighter Weight and Balanced Mechanical Property / 535

17.7.2 Barrier Property or Air Retention Property / 538

17.7.3 Aging and Ozone Resistance / 539

17.7.4 Solvent Resistance / 541

17.7.5 Better Processability / 542

17.7.6 Elastomeric Polyurethane–Organoclay Nanocomposites / 544

17.7.7 Use of Organoclay Nanocomposites in Tire / 545

17.8 Disadvantages of Use of Organoclay Elastomeric Nanocomposites in Automotive Industry / 548

17.9 Conclusion / 549

Acknowledgment / 550

References / 550

18 NONAUTOMOTIVE APPLICATIONS OF RUBBER–CLAY NANOCOMPOSITES 557

18.1 Water-Based Nanocomposites / 557

18.1.1 Barrier Properties / 557

18.1.2 Comparison with Thermally Processed Elastomers / 566

18.2 Applications / 566

18.2.1 Sports Balls and Other Pneumatic Applications / 566

18.2.2 Breakthrough Time Applications / 571

References / 573

INDEX 575

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Author Information

Maurizio Galimberti is a Professor of Chemistry for Rubber and Composite Materials Technology at Milan Polytechnic, Milan, Italy, and a Visiting Professor at University of Insubria, Como, Italy. He is the former president and a current board member of the Italian Association of Macromolecules; has published over seventy scientific works in international books and journals; and is the author of more than forty patents.
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