NANOCOMPOSITES RUBBER PREPARATION, PROPERTIES, AND APPLICATIONS. Editors. Sabu Thomas. Ranimol Stephen INFORMATIONSBIBLIOTHEK UN1VERSITATSBIBLIOTHE.
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1 RUBBER NANOCOMPOSITES PREPARATION, PROPERTIES, AND APPLICATIONS Editors Sabu Thomas Mahatma Gandhi University, India Ranimol Stephen Cochin University of Science and Technology, India TECHNISCHE INFORMATIONSBIBLIOTHEK John Wiley & Sons (Asia) Pte Ltd UN1VERSITATSBIBLIOTHE.K HANNOVER
2 Contents List of Contributors Preface Editor Biographies xv xix xxi 1 Nanocomposites: State of the Art, New Challenges and Opportunities 1 Ranimol Stephen and Sabu Thomas 1.1 Introduction Various Nanofillers Layered Silicates Nanotubes Spherical Particles Polyhedral Oligomeric Silsesquioxanes Bionanofillers Rubber Nanocomposites Future Outlook, Challenges and Opportunities 11 References 12 2 Manufacturing Techniques of Rubber Nanocomposites 21 Jun Ma, Li-Qun Zhang and Li Geng 2.1 Introduction Conventional Manufacturing Techniques Rubber Nanocomposites Reinforcing Agent Melt Compounding Manufacturing Factors Control Filler Surface Modification Solution Blending Manufacturing Factors Control Preparing Exfoliated/Intercalated Nanocomposites Latex Compounding Manufacturing Factors Control The Effect of Rubber Type 57
3 Contents 2.5 Summary 61 Acknowledgments 61 References 61 3 Reinforcement of Silicone Rubbers by Sol-Gel In Situ Generated Filler Particles 63 Liliane Bokobza and Amadou Lamine Diop 3.1 Introduction Synthetic Aspects General Considerations Adopted Protocols Properties of the Hybrid Materials State of Dispersion Stress-Strain Curves Low Strain Dynamic Properties Mullins Effect Characterization of the Polymer-Filler Interface Thermal Properties Conclusions 82 References 82 4 Interface Modification and Characterization 87 Jun Ma, Li-Qun Zhang and Jiabin Dai 4.1 Introduction Particle Size Surface Activity Rubber Nanocomposites Without Interface Modification Hardness and 300% Tensile Modulus Tensile Strength Tensile Strain Tear Strength Rebound Resilience Processing Properties Advantages Disadvantages Interface Modification by Nonreactive Routes Interface Modification by Reactive Routes Characterization of Interface Modification Direct Methods for Interface Characterization Indirect Methods for Interface Characterization Conclusion 110 List of Abbreviations 110 Acknowledgments 111 References 111
4 Contents vii 5 Natural Rubber Green Nanocomposites 113 Alain Ditfresne 5.1 Introduction Preparation of Polysaccharide Nanocrystals Processing of Polysaccharide Nanocrystal-Reinforced Rubber Nanocomposites Morphological Investigation Swelling Behavior Toluene Swelling Behavior Water Swelling Behavior Influence of the Chemical Modification of the Filler Dynamic Mechanical Analysis Tensile Tests Successive Tensile Tests Barrier Properties Conclusions 143 References Carbon Nanotube Reinforced Rubber Composites 147 R. Verdejo, M.A. Lopez-Manchado, L, Valentini and J.M. Kenny 6.1 Introduction Functionalized Carbon Nanotubes Elastorneric Nanocomposites Natural Rubber Styrene-Butadiene Rubber Polyurethane Rubber Silicone Rubber Outlook 161 References Rubber/Clay Nanocomposites: Preparation, Properties and Applications 169 K. G. Gatos and J. Karger-Kocsis 7.1 Introduction Clays and Their Organophilic Modification Preparation of Rubber/Clay Nanocomposites Solution Intercalation Latex Route Melt Compounding Properties of Rubber/Clay Nanocomposites Crosslinking Mechanical Performance Barrier Properties Fire Resistance Others 187
5 viii Contents 7.5 Applications Outlook 189 Acknowledgments 190 References Cellulosic Fibril-Rubber Nanocomposites 197 Maya Jacob John and Sabu Thomas 8.1 Introduction Cellulose Cellulosic Nanoreinforcements Cellulosic Microfibrils Studies on Cellulosic/Latex Nanocomposites Conclusions 207 References Nanofillers In Rubber-Rubber Blends 209 Rosamma Alex 9.1 Introduction Types of Nanofillers Spherical Fillers Tubular Fillers Layered Clays Role of Nanofillers in Reinforcement Particle Size Rubber-Filler Interaction Filler-Filler Interactions Shape and Structure of Filler Filler Reinforcement with Reference to Concentration and Cure Methods to Enhance Polymer-Filler Interaction and Reinforcement Micromechanical Interlocking Physical and Chemical Interactions Modification of Nanofillers Role of Nanofiller as Compatibilizer Structure Compatibility Concept of NR-Based Latex Blends Forms of NR Suitable for Blend Nanocomposites Important Synthetic Latices used in Blend Nanocomposites Solubility Parameter and Mixing of Latices Particle Size and Molecular Weight Nonrubber Solids and Total Solids Content Preparation of Nanocomposites Solution Blending Latex Stage Compounding Melt Intercalation Rubber Blend Nanocomposites Based on Skim NR Latex and Fresh NR Latex: Preparation, Characterization and Mechanical Properties 229
6 and Contents ix 9.10 Advantages of Nanocomposites and Application of Rubber Nanocomposites 231 References Thermoplastic Polyurethane Nanocomposites 239 S.K. Smart, G.A. Edwards and D.J. Martin 10.1 Introduction Market Styrene Block Copolymers Thermoplastic Olefins Thermoplastic Vulcanizates Copolyester Elastomers Thermoplastic Polyurethanes TPU Chemistry, Morphology and Properties TPU Nanocomposites Layered Silicate/TPU Nanocomposites Carbon Nanotube/TPU Nanocomposites Future Perspectives 250 References Microscope Evaluation of the Morphology of Rubber Nanocomposites 255 Hiroaki Miyagawa 11.1 Introduction Optical Microscopy Scanning Electron Microscopy Micrographs with Secondary Electron Energy Dispersive X-Ray Spectroscopy (EDX) Electron Probe Microanalysis X-Ray Ultramicroscopy Transmission Electron Microscopy Sample Preparation for TEM Observations Bright-Field TEM Micrographs Scanning Transmission Electron Microscopy and EDX Electron Spectroscopy Imaging in Transmission Electron Microscopy D Transmission Electron Microtomography Scanning Probe Microscopy Atomic Force Microscopy Other AFM-Related Techniques Summary 285 References Mechanical Properties of Rubber Nanocomposites:... How, Why Then? 291 L. Chazeau, C. Gauthier and J.M. Chenal 12.1 Introduction Typical Mechanical Behavior of Rubber Nanocomposites 292
7 X Contents The Fillers and Their Main Characteristics Filler Reinforcement (Modulus Increase) Mechanical Behavior at Small Strain: the Payne Effect Mechanical Behavior at Larger Strains Aging, Fatigue and Ultimate Properties Conclusion How to Explain Reinforcement in Rubber Nanocomposite? Filler Morphology and Filler-Filler Interactions Filler-Matrix Interactions Indirect Influence of Fillers on Matrix Crosslinking Influence of Fillers on Rubber Crystallization Conclusion Modeling Attempts Polymer Network Contribution: Modeling Rubber Behavior Filler Contribution: How to Describe the Composite Effect? Account for the Filler-Filler and Filler-Matrix Interactions Conclusion General Conclusions 323 References Nonlinear Viscoelastic Behavior of Rubbery Bionanocomposites 331 Alireza S. Sarvestani and Esmaiel Jabbari 13.1 Introduction Rubbery Bionanocomposites Biofiber-Natural Rubber Composites Hydrogel Nanocomposites Nonlinear Viscoelasticity of Hydrogel Nanocomposites Filler-Gel Interfacial Structure Dynamics of the Adsorbed Layer Macroscopic Properties Model Predictions Conclusions 345 Acknowledgments 345 References Rheological Behavior of Rubber Nanocomposites 353 Philippe Cassagnau and Claire Barres 14.1 Introduction Linear Viscoelasticity General Trends Percolation Threshold Equilibrium Shear Modulus Payne Effect The Limit of Linearity Thixotropy and Recovery Flow Properties of Rubber Nanocomposites Shear Viscosity Rubber Nanocomposites Based on Nanoclays Extensional Viscosity 378
8 Spin Contents xi Yield Stress Wall Slip Extrudate Swell Conclusions 384 References Electron Spin Resonance in Studying Nanocomposite Rubber Materials 391 S. Valid 15.1 An Approach to the Study of Polymer Systems ESR Introduction Theoretical Background 393 Probe Study of Nanocomposite Rubber Materials Summary 403 References Studies on Solid-State NMR and Surface Energetics of Silicas for Improving Filler-Elastomer Interactions in Nanocomposites 407 Soo-Jin Park and Byung-Joo Kim 16.1 Introduction Surface Modification of Silicas Thermal Treatment Silane Coupling Method Direct Fluorination Solid-State NMR Analyses of Silicas Thermally Treated Silicas Silane-Treated Silicas Fluorinated Silicas Surface Energetics of Silicas Other Surface Analyses of Modified Silicas Thermally Treated Silicas Fluorinated Silicas Mechanical Interfacial Properties of the Compounds Thermally Treated Silicas Silane-Treated Silicas Fluorinated Silicas Conclusions 422 References Wide-Angle X-ray Diffraction and Small-Angle X-ray Scattering Studies of Rubber Nanocomposites 425 Valerio Cousin 17.1 Introduction WAXD: An Overview SAXS: An Overview Lamellar Fillers Nonlamellar Fillers Carbon Black 445
9 xii Contents Carbon Nanotubes Silica Polyhedral Oligomeric Silsesquioxane Rubber as a Filler or Compatibilizer in Nanocomposites Characterization of the Matrix in Polymer-Based Nanocomposites Strain-Induced Crystallization Thermoplastic Elastomers 472 References Barrier Properties of Rubber Nanocomposites 499 Changwoon Nah and M. Abdul Kader 18.1 Introduction Theoretical Consideration Fundamental Permeation Theories Diffusion through Polymer Membrane Filled with Particulate and Layered Fillers Experimental Studies Applications Conclusions 522 Acknowledgments 523 References Rubber/Graphite Nanocomposites 527 Guohua Chen and Weifeng Zhao 19.1 Introduction and Background Graphite and its Nanostructure Basic Issues on Graphite Graphite Intercalation Compounds Expanded Graphite Graphite Nanosheets Graphene and Graphite Oxide Rubber/Graphite Nanocomposites Preparation, Processing and Characterization Properties and Applications Future Outlook 546 Acknowledgments 546 References Aging and Degradation Behavior of Rubber Nanocomposites 551 Suneel Kumar Srivastava and Himadri Acharya 20.1 Introduction Types of Fillers Used in Rubber Nanocomposites Clay Minerals Layered Double Hydroxide Carbon Nanotubes and Other Inorganic Nanofillers Aging of Rubber Nanocomposites Natural Rubber 555
10 Contents xiii Ethylene Propylene Diene Terpolyrner Styrene Butadiene Rubber Nitrile Butadiene Rubber Hydrogenated Nitrile Butadiene Rubber Silicone Rubber Degradation of Rubber Nanocomposites Natural Rubber Ethylene Vinyl Acetate Ethylene Propylene Diene Terpolyrner Acrylonitrile Butadiene Rubber Hydrogenated Nitrile Butadiene Rubber Styrene Butadiene Rubber Silicone Rubber Butyl Rubber Summary 588 References Positron Annihilation Lifetime Spectroscopy (PALS) and Nanoindentation (NI) 595 Dariusz M. Bielinski and Ludomir Slusarski 21.1 Introduction Positron Annihilation Lifetime Spectroscopy Introduction Application of PALS to Study Rubber Morphology Final Remarks Nanoindentation Introduction Application of Nanoindentation to Study Rubber Morphology Application of Nanotribology to Study Rubber Morphology Final Remarks 626 References Thermoelasticity and Stress Relaxation Behavior of Synthetic Rubber/ Organoclay Nanocomposites 631 KM. Sukhyy, E.G. Privalko, V.P. Privalko andm.v. Burmistr 22.1 Introduction Experimental Materials Methods Polychloroprene/Organoclay Nanocomposites Structural Characterization of Unstretched Samples Thermoelastic Behavior Stress Relaxation Conclusions Styrene-co-Butadiene Rubber/Organoclay Nanocomposites Structural Characterization of Unstretched Samples Thermoelastic Behavior Stress Relaxation Conclusions 648 References 648
11 Contents 23 Theoretical Modeling and Simulation of Rubber Nanocomposites 651 Jan Kalfus and Josef Jancar 23.1 Introduction Brief Theory of Conformation Statistics and Chain Dynamics Basic Aspects of Rubber Elasticity Mechanisms of Nanocomposite Reinforcement Chains at Rubber-Filler Interfaces Structural Aspects Dynamical Aspects Structural Peculiarities of Rubbery Nanocomposites Concluding Remarks 672 Acknowledgments 672 References Application of Rubber Nanocomposites 675 Miroslawa El Fray and Lloyd A. Goettler 24.1 Introduction Rubbery Matrices Nanofillers Rubber Nanocomposites in Tire Engineering Applications Tread Innerliner Other Rubber Nanocomposite Membranes Applications of Rubber Nanocomposites in Sporting Goods Advanced Nanocomposites for Airspace Applications Nanorubbers in Medicine and Healthcare Conclusions 693 References 693 Index 697
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