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PREFACE xvii <p>CONTRIBUTORS xxi</p> <p>SECTION I CLAYS FOR NANOCOMPOSITES</p> <p>1 CLAYS AND CLAY MINERALS 3</p> <p>1.1 What’s in a Name / 3</p> <p>1.2 Multiscale Organization of Clay Minerals / 6</p> <p>1.2.1 Dispersion Versus Aggregation / 6</p> <p>1.2.2 Delamination/Exfoliation Versus Stacking / 6</p> <p>1.3 Intimate Organization of the Layer / 8</p> <p>1.3.1 Cationic and Neutral Clay Minerals / 8</p> <p>1.3.2 Anionic Clay Minerals (O) / 21</p> <p>1.4 Most Relevant Physicochemical Properties of Clay Mineral / 22</p> <p>1.4.1 Surface Area and Porosity / 22</p> <p>1.4.2 Chemical Landscape of the Clay Surfaces / 24</p> <p>1.4.3 Cation (and Anion) Exchange Capacity / 24</p> <p>1.4.4 Intercalation and Confinement in the Interlayer Space / 27</p> <p>1.4.5 Swelling / 30</p> <p>1.4.6 Rheology / 31</p> <p>1.5 Availability of Natural Clays and Synthetic Clay Minerals / 33</p> <p>1.6 Clays and (Modified) Clay Minerals as Fillers / 35</p> <p>Acknowledgment / 37</p> <p>References / 37</p> <p>2 ORGANOPHILIC CLAY MINERALS 45</p> <p>2.1 Organophilicity/Lipophilicity and the Hydrophilic/Lipophilic Balance (HLB) / 45</p> <p>2.2 From Clays to Organoclays in Polymer Technology / 47</p> <p>2.3 Methods of Organoclay Synthesis / 49</p> <p>2.3.1 Cation Exchange from Solutions / 49</p> <p>2.3.2 Solid-State Intercalation / 58</p> <p>2.3.3 Grafting from Solution / 59</p> <p>2.3.4 Direct Synthesis of Grafted Organoclays / 62</p> <p>2.3.5 Postsynthesis Modifications of Organoclays: The “PCH” / 64</p> <p>2.3.6 An Overview of Commercial Organoclays / 64</p> <p>2.3.7 One-Pot CPN Formation / 66</p> <p>2.4 Other Types of Clay Modifications for Clay-Based Nanomaterials / 66</p> <p>2.4.1 Organo-Pillared Clays / 66</p> <p>2.4.2 Plasma-Treated Clays / 69</p> <p>2.5 Fine-Tuning of Organoclays Properties / 69</p> <p>2.5.1 Maximizing the Dispersion of the Filler: Effect</p> <p>of Surfactant/CEC Ratio / 69</p> <p>2.5.2 Improving Thermal Stability / 70</p> <p>2.5.3 Chemical Treatments / 71</p> <p>2.5.4 Physical Treatments (Freeze-Drying, Sonication, Microwave) / 71</p> <p>2.6 Some Introductory Reflections on Organoclay Polymer Nanocomposites / 72</p> <p>References / 75</p> <p>3 INDUSTRIAL TREATMENTS AND MODIFICATION OF CLAY MINERALS 87</p> <p>3.1 Bentonite: From Mine to Plant / 87</p> <p>3.1.1 A Largely Diffused Clay / 87</p> <p>3.1.2 Geological Occurrence / 89</p> <p>3.1.3 Mining / 89</p> <p>3.2 Processing of Bentonite / 90</p> <p>3.2.1 Modification of Bentonite Properties / 90</p> <p>3.2.2 Processing Technologies / 91</p> <p>3.3 Purification of Clay / 93</p> <p>3.3.1 Influence of Clay Concentration / 94</p> <p>3.3.2 Influence of Swelling Time / 94</p> <p>3.3.3 Influence of Temperature / 95</p> <p>3.4 Reaction of Clay with Organic Substances / 97</p> <p>3.5 Particle Size Modification / 99</p> <p>References / 99</p> <p>4 ALKYLAMMONIUM CHAINS ON LAYERED CLAY MINERAL SURFACES 101</p> <p>4.1 Structure and Dynamics / 101</p> <p>4.1.1 Packing Density and Self-Assembly / 102</p> <p>4.1.2 Dynamics and Diffusion at the Clay–Surfactant Interface / 110</p> <p>4.1.3 Utility of Molecular Simulation to Obtain Molecular-Level Insight / 111</p> <p>4.2 Thermal Properties / 111</p> <p>4.2.1 Reversible Melting Transitions of Alkyl Chains in the Interlayer / 111</p> <p>4.2.2 Solvent Evaporation and Thermal Elimination of Alkyl Surfactants / 113</p> <p>4.3 Layer Separation and Miscibility with Polymers / 115</p> <p>4.3.1 Thermodynamics Model for Exfoliation in Polymer Matrices / 115</p> <p>4.3.2 Cleavage Energy / 116</p> <p>4.3.3 Surface Energy / 121</p> <p>4.4 Mechanical Properties of Clay Minerals / 121</p> <p>References / 123</p> <p>5 CHEMISTRY OF RUBBER–ORGANOCLAY NANOCOMPOSITES 127</p> <p>5.1 Introduction / 127</p> <p>5.2 Organic Cation Decomposition in Salts, Organoclays and Polymer Nanocomposites / 128</p> <p>5.2.1 Experimental Techniques / 128</p> <p>5.2.2 Decomposition of Organoclays Versus Precursor Organic Cation Salts / 133</p> <p>5.3 Mechanism of Thermal Decomposition of Organoclays / 135</p> <p>5.4 Role of Organic Cations in Organoclays as Rubber Vulcanization Activators / 137</p> <p>References / 141</p> <p>SECTION II PREPARATION AND CHARACTERIZATION OF RUBBER–CLAY NANOCOMPOSITES</p> <p>6 PROCESSING METHODS FOR THE PREPARATION OF RUBBER–CLAY NANOCOMPOSITES 147</p> <p>6.1 Introduction / 147</p> <p>6.2 Latex Compounding Method / 148</p> <p>6.2.1 Mechanism / 148</p> <p>6.2.2 Influencing Factors / 149</p> <p>6.3 Melt Compounding / 157</p> <p>6.3.1 Mechanism / 157</p> <p>6.3.2 Influencing Factors / 160</p> <p>6.4 Solution Intercalation and In Situ Polymerization Intercalation / 170</p> <p>6.5 Summary and Prospect / 170</p> <p>Acknowledgment / 171</p> <p>References / 171</p> <p>7 MORPHOLOGY OF RUBBER–CLAY NANOCOMPOSITES 181</p> <p>7.1 Introduction / 181</p> <p>7.1.1 Focus, Objective and Structure of Chapter 7 / 181</p> <p>7.1.2 X-Ray Diffraction Analysis for the Investigation of RCN / 182</p> <p>7.2 Background for the Review of RCN Morphology / 182</p> <p>7.2.1 Cationic Clays Used for the Preparation of Rubber Nanocomposites / 182</p> <p>7.2.2 Multiscale Organization of Layered Clays / 184</p> <p>7.2.3 Clay Distribution and Dispersion / 184</p> <p>7.2.4 Clay Modification: Intercalation of Low Molecular Mass Substances / 184</p> <p>7.2.5 Types of Polymer–Clay Composites / 184</p> <p>7.2.6 Specific Literature on RCN / 186</p> <p>7.3 Rubber–Clay Nanocomposites with Pristine Clays / 186</p> <p>7.3.1 Rubber Nanocomposites with Cationic Clays / 187</p> <p>7.3.2 In a Nutshell / 187</p> <p>7.3.3 Distribution and Dispersion of a Pristine Clay in a Rubber Matrix / 190</p> <p>7.3.4 Organization of Aggregated Pristine Clays / 194</p> <p>7.4 Rubber–Clay Nanocomposites with Clays Modified with Primary Alkenylamines / 197</p> <p>7.4.1 In a Nutshell / 197</p> <p>7.4.2 Composites with Montmorillonite and Bentonite / 198</p> <p>7.4.3 Composites with Fluorohectorite Modified with a Primary Alkenylamine / 202</p> <p>7.5 Rubber–Clay Nanocomposites with Clays Modified with an Ammonium Cation Having three Methyls and One Long-Chain Alkenyl Substituents / 206</p> <p>7.5.1 In a Nutshell / 206</p> <p>7.5.2 Composites with Montmorillonite and Bentonite / 207</p> <p>7.6 Rubber–Clay Nanocomposites with Montmorillonite Modified with Two Substituents Larger Than Methyl / 212</p> <p>7.6.1 In a Nutshell / 212</p> <p>7.6.2 Hydrogenated Tallow and Benzyl Groups as Ammonium Cation Substituents / 213</p> <p>7.6.3 Hydrogenated Tallow and Ethylhexyl Groups as Ammonium Cation Substituents / 213</p> <p>7.6.4 Other Long- and Short-Chain Alkenyl Groups as Ammonium Cation Substituents / 215</p> <p>7.7 Rubber Composites with Montmorillonite Modified with an Ammonium Cation Containing a Polar Group / 215</p> <p>7.7.1 In a Nutshell / 217</p> <p>7.7.2 Composites with Diene Rubbers / 217</p> <p>7.8 Rubber Nanocomposites with Montmorillonite Modified with an Ammonium Cation Containing Two Long-Chain Alkenyl Substituents / 219</p> <p>7.8.1 In a Nutshell / 220</p> <p>7.8.2 Composites with Two Talloyl Groups as Ammonium Cation Substituents / 220</p> <p>7.9 Proposed Mechanisms for the Formation of Rubber–Clay Nanocomposites / 228</p> <p>7.9.1 Two Mechanisms for the Formation of an Exfoliated Clay / 228</p> <p>7.9.2 Two Mechanisms for the Formation of an Intercalated Organoclay / 228</p> <p>7.9.3 Intercalation of Polymer Chains in the Interlayer Space / 229</p> <p>7.9.4 Intercalation of Low Molecular Mass Substances in the Interlayer Space / 230</p> <p>Abbreviations / 232</p> <p>Acknowledgment / 233</p> <p>References / 233</p> <p>8 RHEOLOGY OF RUBBER–CLAY NANOCOMPOSITES 241</p> <p>8.1 Introduction / 241</p> <p>8.2 Rheological Behavior of Rubber–Clay Nanocomposites / 242</p> <p>8.2.1 Natural Rubber (NR), Epoxidized Natural Rubber (ENR) and Polyisoprene Rubber (IR)–Clay Nanocomposites / 243</p> <p>8.2.2 Styrene–Butadiene Rubber (SBR)–Clay Nanocomposites / 246</p> <p>8.2.3 Polybutadiene Rubber (BR)–Clay Nanocomposites / 247</p> <p>8.2.4 Acrylonitrile Butadiene Rubber (NBR)–Clay Nanocomposites / 250</p> <p>8.2.5 Ethylene Propylene Rubber–Clay Nanocomposites / 253</p> <p>8.2.6 Fluoroelastomer–Clay Nanocomposites / 254</p> <p>8.2.7 Poly(isobutylene-co-para-methylstyrene) (BIMS) Rubber–Clay Nanocomposites / 257</p> <p>8.2.8 Poly(ethylene-co-vinylacetate) (EVA) Rubber–Clay Nanocomposites / 257</p> <p>8.2.9 Polyepichlorohydrin Rubber–Clay Nanocomposites / 259</p> <p>8.2.10 Thermoplastic Polyurethane (TPU)–Clay Nanocomposites / 261</p> <p>8.2.11 Styrene–Ethylene–Butylene–Styrene (SEBS) Block Copolymer–Clay Nanocomposites / 262</p> <p>8.3 General Remarks on Rheology of Rubber–Clay Nanocomposites / 263</p> <p>8.4 Overview of Rheological Theories of Polymer–Clay Nanocomposites / 269</p> <p>8.5 Conclusion and Outlook / 270</p> <p>References / 271</p> <p>9 VULCANIZATION CHARACTERISTICS AND CURING KINETIC OF RUBBER–ORGANOCLAY NANOCOMPOSITES 275</p> <p>9.1 Introduction / 275</p> <p>9.2 Vulcanization Reaction / 276</p> <p>9.3 Rubber Cross-Linking Systems / 278</p> <p>9.3.1 Sulfur Vulcanization / 278</p> <p>9.3.2 Peroxide Vulcanization / 282</p> <p>9.4 The Role of Organoclay on Vulcanization Reaction / 283</p> <p>9.4.1 Influence of Organoclay Structural Characteristics on Rubber Vulcanization / 288</p> <p>9.5 Vulcanization Kinetics of Rubber–Organoclay Nanocomposites / 290</p> <p>9.6 Conclusions / 297</p> <p>References / 298</p> <p>10 MECHANICAL AND FRACTURE MECHANICS PROPERTIES OF RUBBER COMPOSITIONS WITH REINFORCING COMPONENTS 305</p> <p>10.1 Introduction / 305</p> <p>10.2 Testing of Viscoelastic and Mechanical Properties of Reinforced Elastomeric Materials / 307</p> <p>10.2.1 Dynamic–Mechanical Analysis / 307</p> <p>10.2.2 Tensile Testing / 310</p> <p>10.2.3 Assessment of Toughness Behavior under Impact-Like Loading Conditions / 313</p> <p>10.2.4 Hardness Testing / 315</p> <p>10.2.5 Special Methods / 316</p> <p>10.3 Characterization of the Fracture Behavior of Elastomers / 319</p> <p>10.3.1 Fracture Mechanics Concepts / 319</p> <p>10.3.2 Experimental Methods / 321</p> <p>10.4 Mechanism of Reinforcement in Rubber–Clay Composites / 328</p> <p>10.5 Theories and Modeling of Reinforcement / 333</p> <p>Acknowledgment / 336</p> <p>References / 336</p> <p>11 PERMEABILITY OF RUBBER COMPOSITIONS CONTAINING CLAY 343</p> <p>11.1 Introduction / 343</p> <p>11.1.1 Butyl Rubbers as Nanocomposite Base Elastomers / 343</p> <p>11.1.2 Measurement of Tire Innerliner Compound Permeability / 345</p> <p>11.1.3 Further Improvement in Tire Permeability / 346</p> <p>11.2 Nanocomposites / 346</p> <p>11.3 Preparation of Elastomer Nanocomposites / 352</p> <p>11.4 Temperature and Compound Permeability / 352</p> <p>11.5 Vulcanization of Nanocomposite Compounds and Permeability / 356</p> <p>11.6 Thermodynamics and BIMSM Montmorillonite Nanocomposites / 358</p> <p>11.7 Nanocomposites and Tire Performance / 362</p> <p>11.8 Summary / 364</p> <p>References / 364</p> <p>SECTION III COMPOUNDS WITH RUBBER–CLAY NANOCOMPOSITES</p> <p>12 RUBBER–CLAY NANOCOMPOSITES BASED ON APOLAR DIENE RUBBER 369</p> <p>12.1 Introduction / 369</p> <p>12.2 Preparation Methods / 371</p> <p>12.2.1 Latex / 371</p> <p>12.2.2 Solution / 373</p> <p>12.2.3 Melt Blending / 374</p> <p>12.3 Cure Characteristics / 377</p> <p>12.4 Clay Dispersion / 379</p> <p>12.4.1 Detection / 380</p> <p>12.4.2 Characterization / 383</p> <p>12.5 Properties / 387</p> <p>12.5.1 Mechanical (Dynamic–Mechanical) / 387</p> <p>12.5.2 Friction/Wear/Abrasion / 392</p> <p>12.5.3 Barrier / 393</p> <p>12.5.4 Fire Resistance / 396</p> <p>12.5.5 Others / 397</p> <p>12.6 Applications and Future Trends / 398</p> <p>Acknowledgment / 399</p> <p>References / 399</p> <p>13 RUBBER–CLAY NANOCOMPOSITES BASED ON NITRILE</p> <p>RUBBER 409</p> <p>13.1 Introduction / 409</p> <p>13.2 Preparation Methods and Clay</p> <p>Dispersion / 410</p> <p>13.2.1 Solution / 410</p> <p>13.2.2 Latex / 411</p> <p>13.2.3 Melt Blending / 412</p> <p>13.3 Cure Characteristics / 414</p> <p>13.4 Properties / 416</p> <p>13.4.1 Mechanical (Dynamic–Mechanical) / 416</p> <p>13.4.2 Friction/Wear / 421</p> <p>13.4.3 Barrier / 423</p> <p>13.4.4 Fire Resistance / 424</p> <p>13.4.5 Others / 425</p> <p>13.5 Outlook / 425</p> <p>Acknowledgment / 426</p> <p>References / 426</p> <p>xii CONTENTS</p> <p>FOR SCREEN VIEWING IN DART ONLY</p> <p>14 RUBBER–CLAY NANOCOMPOSITES BASED ON BUTYL AND</p> <p>HALOBUTYL RUBBERS 431</p> <p>14.1 Introduction / 431</p> <p>14.1.1 Butyl Rubber: Key Properties</p> <p>and Applications / 431</p> <p>14.1.2 Butyl Rubber–Clay Nanocomposites / 433</p> <p>14.2 Types of Clays Useful in Butyl Rubber–Clay</p> <p>Nanocomposites / 435</p> <p>14.2.1 Montmorillonite Clays / 435</p> <p>14.2.2 Hydrotalcite Clays / 435</p> <p>14.2.3 High Aspect Ratio Talc Fillers / 436</p> <p>14.2.4 Other Clays / 437</p> <p>14.3 Compatibilizer Systems for Butyl Rubber–Clay</p> <p>Nanocomposites / 438</p> <p>14.3.1 Surfactants and Swelling Agents / 439</p> <p>14.3.2 Butyl Rubber Ionomers / 439</p> <p>14.3.3 Maleic Anhydride-Grafted Polymers / 443</p> <p>14.3.4 Low Molecular Weight Polymers and Resins / 444</p> <p>14.4 Methods of Preparation of Butyl Rubber–Clay Nanocomposites / 444</p> <p>14.4.1 Melt Method / 445</p> <p>14.4.2 Solution Method / 445</p> <p>14.4.3 Latex Method / 447</p> <p>14.4.4 In Situ Polymerization / 448</p> <p>14.5 Properties and Applications of Butyl Rubber–Clay Nanocomposites / 449</p> <p>14.5.1 Air Barrier Properties / 449</p> <p>14.5.2 Reinforcement Properties / 452</p> <p>14.5.3 Vulcanization Properties / 454</p> <p>14.5.4 Adhesion Properties / 456</p> <p>14.5.5 Other Properties / 457</p> <p>14.6 Conclusions / 457</p> <p>References / 458</p> <p>15 RUBBER–CLAY NANOCOMPOSITES BASED ON OLEFINIC RUBBERS (EPM, EPDM) 465</p> <p>15.1 Introduction / 465</p> <p>15.2 Types of Clay Minerals Useful in EPM–, EPDM–Clay Nanocomposites / 466</p> <p>15.3 Compatibilizer Systems for Olefinic Rubber–Clay Nanocomposites / 467</p> <p>15.4 Preparation of EPDM–Clay Nanocomposites by an In Situ Intercalation Method / 469</p> <p>15.5 Characteristics of EPDM–Clay Nanocomposites / 473</p> <p>15.5.1 Gas Barrier Properties of EPDM–Clay Nanocomposites / 473</p> <p>15.5.2 Rheological Properties of EPDM–Clay Nanocomposites / 474</p> <p>15.5.3 Stability of EPDM–Clay Nanocomposites / 475</p> <p>15.5.4 Swelling Properties of EPDM–Clay Nanocomposites / 475</p> <p>15.5.5 Mechanical Properties of EPDM–Clay Nanocomposites / 476</p> <p>15.6 Preparation and Characteristics of EPM–Clay Nanocomposites / 479</p> <p>15.6.1 Tensile Properties of EPM–CNs / 480</p> <p>15.6.2 Temperature Dependence of Dynamic Storage Moduli of EPM–CNs / 481</p> <p>15.6.3 Creep Properties of EPM–CNs / 482</p> <p>15.6.4 Swelling Properties of EPM–CNs / 483</p> <p>15.7 Conclusions / 486</p> <p>References / 486</p> <p>16 RUBBER–CLAY NANOCOMPOSITES BASED ON THERMOPLASTIC ELASTOMERS 489</p> <p>16.1 Introduction / 489</p> <p>16.2 Selection of Materials / 491</p> <p>16.2.1 Polymer Resin / 491</p> <p>16.2.2 Nanoparticles / 493</p> <p>16.3 Experimental / 493</p> <p>16.3.1 Processing of Thermoplastic Elastomer Nanocomposites / 493</p> <p>16.3.2 Morphological Characterization / 494</p> <p>16.3.3 Thermal Properties Characterization / 495</p> <p>16.3.4 Flammability Properties Characterization / 495</p> <p>16.3.5 Thermophysical Properties Characterization / 496</p> <p>16.4 Numerical / 497</p> <p>16.4.1 Modeling of Decomposition Kinetics / 497</p> <p>16.5 Discussion of Results / 501</p> <p>16.5.1 Nanoparticle Dispersion / 501</p> <p>16.5.2 Thermal Properties / 503</p> <p>16.5.3 Flammability Properties / 507</p> <p>16.5.4 Microstructures of Posttest Specimens / 511</p> <p>16.5.5 Thermophysical Properties / 512</p> <p>16.5.6 Kinetic Parameters / 513</p> <p>16.6 Summary and Conclusions / 516</p> <p>16.7 Nomenclature / 517</p> <p>Acknowledgments / 518</p> <p>References / 518</p> <p>SECTION IV APPLICATIONS OF RUBBER–CLAY NANOCOMPOSITES</p> <p>17 AUTOMOTIVE APPLICATIONS OF RUBBER–CLAY NANOCOMPOSITES 525</p> <p>17.1 Introduction / 525</p> <p>17.2 Automotive Application of Rubber / 526</p> <p>17.2.1 Automotive Hose / 527</p> <p>17.2.2 Automotive Seals / 528</p> <p>17.2.3 Automotive Belts / 529</p> <p>17.2.4 Automotive Tubing / 529</p> <p>17.2.5 Door Seal and Window Channels / 529</p> <p>17.2.6 Diaphragms and Rubber Boots / 529</p> <p>17.2.7 Tire, Tube and Flap / 529</p> <p>17.2.8 Other Miscellaneous Rubber Parts / 531</p> <p>17.3 Prime Requirement of Different Elastomeric Auto Components from Application Point of View / 531</p> <p>17.4 Elastomeric Nanocomposites and Rubber Industry / 531</p> <p>17.5 Superiority of Clay/Clay Mineral in Comparison to Other Nanofillers / 534</p> <p>17.6 Organo-Modified Clay/Clay Minerals / 534</p> <p>17.7 Scope of Application of Elastomeric Nanocomposites in Automotive Industry / 534</p> <p>17.7.1 Lighter Weight and Balanced Mechanical Property / 535</p> <p>17.7.2 Barrier Property or Air Retention Property / 538</p> <p>17.7.3 Aging and Ozone Resistance / 539</p> <p>17.7.4 Solvent Resistance / 541</p> <p>17.7.5 Better Processability / 542</p> <p>17.7.6 Elastomeric Polyurethane–Organoclay Nanocomposites / 544</p> <p>17.7.7 Use of Organoclay Nanocomposites in Tire / 545</p> <p>17.8 Disadvantages of Use of Organoclay Elastomeric Nanocomposites in Automotive Industry / 548</p> <p>17.9 Conclusion / 549</p> <p>Acknowledgment / 550</p> <p>References / 550</p> <p>18 NONAUTOMOTIVE APPLICATIONS OF RUBBER–CLAY NANOCOMPOSITES 557</p> <p>18.1 Water-Based Nanocomposites / 557</p> <p>18.1.1 Barrier Properties / 557</p> <p>18.1.2 Comparison with Thermally Processed Elastomers / 566</p> <p>18.2 Applications / 566</p> <p>18.2.1 Sports Balls and Other Pneumatic Applications / 566</p> <p>18.2.2 Breakthrough Time Applications / 571</p> <p>References / 573</p> <p>INDEX 575</p>

<b>Maurizio Galimberti</b> 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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