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| موضوع: كتاب Handbook of Thermoplastic Elastomers الإثنين 23 أكتوبر 2023, 6:47 am | |
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أخواني في الله أحضرت لكم كتاب Handbook of Thermoplastic Elastomers Jiri George Drobny Drobny Polymer Associates
و المحتوى كما يلي :
Contents Preface xvii 1 Introduction 1 1.1 Elasticity and Elastomers . 1 1.2 Thermoplastic Elastomers 2 1.2.1 Phase Structure . 2 1.2.2 Methods of Synthesis of Thermoplastic Elastomers 3 1.2.2.1 Methods of Synthesis of Block Copolymers . 3 1.2.2.2 Methods of Synthesis of Other Thermoplastic Elastomers . 4 1.2.3 Phase Separation 4 1.2.4 Classification of Thermoplastic Elastomers 5 1.2.4.1 Nomenclature of Block Copolymers . 5 1.2.5 Advantages and Disadvantages of Thermoplastic Elastomers . 6 1.2.6 Demand for Thermoplastic Elastomers and Its Growth 7 References . 7 2 A Brief History of Thermoplastic Elastomers . 9 References 10 3 Additives 13 3.1 Antioxidants . 13 3.2 Light Stabilizers 13 3.2.1 UV Absorbers 14 3.2.2 Quenchers 14 3.2.3 Free Radical Scavengers 14 3.2.4 Evaluation of UV Stability 14 3.3 Nucleating Agents . 14 3.4 Flame Retardants . 15 3.4.1 Flammability Tests . 16 3.5 Colorants . 17 3.5.1 Optical Properties of Colorants 17 3.5.2 Characteristics of Colorants 17 3.5.3 Inorganic Pigments 17 3.5.4 Organic Pigments . 18 3.5.5 Special Effect Pigments . 18 3.5.6 Colorant Forms . 18 3.6 Antistatic Agents 19 3.6.1 Types of Antistatic Agents . 19 3.6.2 Electrically Conductive Materials . 19 3.7 Slip Agents 19 3.8 Antiblocking Agents 20 3.9 Processing Aids 20 3.10 Fillers and Reinforcements 20 3.10.1 Fillers Commonly Used in Thermoplastic Polymers . 21 3.10.1.1 Cubic and Spheroidal Fillers . 21 3.10.1.2 Platy Fillers . 22 3.10.1.3 Fibrous Fillers . 22 3.10.1.4 Nanofillers 22 3.11 Plasticizers 23 3.11.1 Types of Plasticizers . 23 3.11.2 Methods of Incorporation 23 3.12 Other Additives . 23 3.13 Selection of Additives 24 vii3.14 Health, Hygiene, and Safety . 25 References 25 4 Processing Methods Applicable to Thermoplastic Elastomers . 29 4.1 Introduction . 29 4.1.1 Properties Influencing Processing 29 4.1.1.1 Flow Properties 29 4.1.1.2 Thermal Properties 31 4.1.1.3 Shrinkage and Warping 32 4.1.2 Pre-Processing . 33 4.1.2.1 Drying . 34 4.1.2.2 Coloring 34 4.2 Mixing and Blending . 35 4.2.1 Basic Concepts Pertaining to Mixing 36 4.2.1.1 Melting 36 4.2.1.2 Rheology and Flow Pertaining to Mixing . 36 4.2.1.3 Residence Time 38 4.2.1.4 Specific Mechanical Energy . 38 4.2.2 Polymer Blends . 39 4.2.3 Mixing Equipment . 40 4.2.3.1 Batch Mixers 40 4.2.3.2 Continuous Mixers 42 4.2.3.3 Other Mixing Machinery 43 4.2.4 Material Feeding and Feeders 47 4.2.5 Finishing Operations . 47 4.2.5.1 Filtration . 47 4.2.5.2 Size Reduction . 47 4.3 Extrusion . 51 4.3.1 Fundamentals of Extrusion Processes . 51 4.3.2 The Extruder . 52 4.3.3 Extrusion Methods . 54 4.3.3.1 Film and Sheet Extrusion . 55 4.3.3.2 Coextrusion . 60 4.3.3.3 Wire Coating 60 4.3.3.4 Extrusion of Pipe and Tubing 62 4.3.3.5 Extrusion of Profiles . 65 4.3.3.6 Extrusion Coating . 65 4.3.4 Process Control in Extrusion . 65 4.4 Injection Molding 66 4.4.1 General Considerations 66 4.4.2 Basic Technology . 67 4.4.3 The Process . 67 4.4.4 Injection Molding Machinery 67 4.4.4.1 Clamp Unit . 68 4.4.4.2 Injection Unit 69 4.4.4.3 Power Systems 72 4.4.4.4 Control Systems 72 4.4.5 The Injection Mold . 74 4.4.5.1 Injection Mold Components 74 4.4.5.2 Injection Mold Types 74 4.4.6 Injection Mold Feed Systems . 76 4.4.6.1 Cold Runners 77 4.4.6.2 Sprues 78 4.4.6.3 Gates . 78 4.4.6.4 Hot Runners 80 4.4.7 Injection Mold Features . 81 4.4.7.1 Materials . 81 4.4.7.2 Cooling 81 4.4.7.3 Venting 83 viii CONTENTS4.4.7.4 Ejection 84 4.4.8 Materials of Construction 84 4.4.9 Dimensional Stability of Parts . 84 4.5 Compression Molding 86 4.5.1 Types of Compression Molds . 87 4.5.2 The Compression Molding Press 89 4.5.3 Compression Molding of Thermoplastics . 89 4.6 Transfer Molding 90 4.6.1 Background . 90 4.6.2 Transfer-In Compression Molding 90 4.6.3 Plunger Molding 91 4.6.4 Screw Transfer Molding . 91 4.6.5 Types of Transfer Molds 91 4.6.6 Transfer Molding of TPEs . 93 4.6.6.1 Mold Design 93 4.6.6.2 Operation of the Mold 96 4.6.6.3 Transfer Molding Process Variables 96 4.7 Blow Molding 97 4.7.1 Blow Molding Processes 97 4.7.1.1 The Extruder 98 4.7.1.2 The Parison Head 98 4.7.2 Extrusion Blow Molding 99 4.7.3 Injection Blow Molding . 102 4.7.4 Stretch Blow Molding 102 4.7.5 Dip Blow Molding . 103 4.7.6 Multiblock Blow Molding 104 4.7.7 Coextrusion Blow Molding Techniques 104 4.7.8 Sequential Extrusion . 104 4.7.9 Molds for Blow Molding . 105 4.7.9.1 Basic Features . 105 4.7.9.2 Pinch-Off Zone 105 4.7.9.3 Blowing and Calibrating Devices . 106 4.7.9.4 Venting and Surface Finish . 106 4.7.9.5 Cooling . 107 4.7.10 Examples of Blow Molded Parts 108 4.8 Rotational Molding . 108 4.8.1 Background 108 4.8.2 Basic Process Technology 109 4.8.3 Rotational Molding Equipment . 110 4.8.3.1 Batch Systems 111 4.8.3.2 Carousel Machines . 111 4.8.3.3 Shuttle Machines 112 4.8.3.4 Clamshell Machines 112 4.8.4 Equipment and Process Design 112 4.8.4.1 Molds 112 4.8.4.2 Mold Surface Preparation 114 4.8.5 Operation of Rotomolding Processes 114 4.8.5.1 Oven Dwell Time 115 4.8.5.2 Cooling Cycle 117 4.8.5.3 Venting . 117 4.8.5.4 Part Stripping . 117 4.8.5.5 Rotation Rate and Ratio . 118 4.8.6 Rotolining Process 118 4.8.7 Melting of Polymer and Part Formation . 119 4.8.8 Troubleshooting 120 4.8.9 Conclusion . 120 4.9 Foaming of Thermoplastics . 121 4.9.1 Introduction . 121 4.9.2 Background 121 CONTENTS ix4.9.3 Foaming Technology 121 4.9.3.1 Mechanical Foaming . 122 4.9.3.2 Chemical Foaming . 122 4.9.3.3 Physical Foaming . 122 4.9.4 Foam Manufacturing Processes 123 4.10 Thermoforming 124 4.10.1 Process Basics 124 4.10.2 Process Factors . 125 4.10.2.1 Forming Force 126 4.10.2.2 Mold Type . 127 4.10.2.3 Sheet Prestretch 127 4.10.2.4 Material Input 128 4.10.2.5 Process Phase . 128 4.10.2.6 Heating . 128 4.11 Calendering 129 4.12 Secondary Manufacturing Processes 129 4.12.1 Film and Sheet Orientation 129 4.12.1.1 Machine Direction Orientation . 130 4.12.1.2 Transverse Direction Orientation . 131 4.12.1.3 Biaxial Orientation . 131 4.12.1.4 Heat Shrinkable Films and Tubing . 132 4.12.2 Welding . 133 4.12.2.1 Heated Tool Welding . 133 4.12.2.2 Hot Gas Welding 133 4.12.2.3 Ultrasonic Welding . 134 4.12.2.4 Spin Welding . 135 4.12.2.5 Infrared Welding 136 4.12.2.6 High Frequency Welding 136 4.12.2.7 Vibration Welding . 137 4.12.2.8 Induction Welding . 137 4.12.2.9 Microwave Welding 138 4.12.2.10Other Welding Methods . 139 4.12.3 Adhesive Bonding 141 4.12.3.1 Principles of Adhesive Bonding 141 4.12.3.2 Methods of Surface Treatment 142 4.12.3.3 Types of Polymeric Adhesives 145 4.12.3.4 Application of Adhesives 146 4.12.3.5 Formation of an Adhesive Bond . 146 4.12.3.6 Measurement of the Bond Strength . 146 4.12.4 Mechanical Fastening . 147 4.12.5 Decorating . 148 4.12.5.1 Applique´s . 148 4.12.5.2 Painting 148 4.12.5.3 In-Mold Decorating 148 4.12.5.4 Metallization . 148 4.12.5.5 Printing . 149 4.12.5.6 Other Decorating Processes 150 4.12.6 Cross-Linking . 150 4.13 General Processing Technology of TPEs . 150 4.13.1 Compounding of TPEs . 150 4.13.2 Injection Molding . 151 4.13.2.1 Overmolding . 152 4.14 Process Simulation . 153 4.15 Product Development and Testing 153 References . 154 5 Styrenic Block Copolymers 161 5.1 Introduction 161 5.2 Polystyrene–Polydiene Block Copolymers . 162 x CONTENTS5.2.1 Synthesis of Polystyrene–Polydiene Block Copolymers 162 5.2.2 Morphology of Polystyrene–Polydiene Block Copolymers 163 5.2.3 Critical Molecular Weight for Domain Formation . 164 5.2.4 Properties of Polystyrene–Polydiene Block Copolymers . 165 5.2.4.1 Structure–Property Relationships 165 5.2.4.2 Tensile Properties . 166 5.2.4.3 Viscous and Viscoelastic Properties 166 5.2.4.4 Solution Properties 167 5.2.4.5 Swelling 168 5.2.5 Formulating Styrenic TPEs 168 5.2.5.1 Formulating S–B–S Block Copolymers 168 5.2.5.2 Formulating S–EB–S Block Copolymers . 169 5.2.6 Compounding . 170 5.2.6.1 Melt Mixing 170 5.2.6.2 Dry Blending . 170 5.2.6.3 Solution Mixing . 170 5.2.7 Processing of Compounds from SBCs . 171 5.2.7.1 Extrusion . 171 5.2.7.2 Injection Molding 172 5.2.7.3 Blow Molding 173 5.2.7.4 Thermoforming . 173 5.2.7.5 Compression Molding 173 5.2.7.6 Bonding and Sealing . 173 5.3 SBCs Synthesized by Carbocationic Polymerization . 173 5.3.1 The Polymerization Process . 173 5.3.2 Properties of S–IB–S Block Copolymers 174 References . 175 6 Thermoplastic Elastomers Prepared by Dynamic Vulcanization . 179 6.1 Introduction 179 6.2 The Dynamic Vulcanization Process . 180 6.3 Properties of Blends Prepared by Dynamic Vulcanization 181 6.3.1 TPVs Based on Polyolefins . 181 6.3.1.1 TPVs from EPDM–Polyolefin Blends 181 6.3.1.2 TPVs from Diene Rubbers and Polyolefins . 181 6.3.1.3 TPVs from Butyl and Halobutyl Rubber and PP Resins 182 6.3.1.4 TPVs from Butadiene-Acrylonitrile Rubber and Polyamides 182 6.3.1.5 TPVs Based on Polyacrylate Rubber and Polyamides . 185 6.4 Processing and Fabrication of TPVs . 185 6.4.1 Rheology 185 6.4.2 Extrusion 185 6.4.3 Injection Molding . 186 6.4.4 Compression Molding . 186 6.4.5 Blow Molding . 187 6.4.6 Thermoforming 187 6.4.7 Calendering 187 6.4.8 Extrusion Foaming 187 6.4.9 Bonding of TPVs . 188 References . 189 7 Polyolefin-Based Thermoplastic Elastomers 191 7.1 Introduction 191 7.2 Thermoplastic Polyolefin Blends 191 7.2.1 Compounding of TPOs 193 7.3 Morphology 193 7.4 Properties of TPOs . 193 7.4.1 Mechanical Properties of TPOs 193 7.4.1.1 Stress–Strain Properties . 193 7.4.2 Service Temperatures . 194 7.4.3 Weathering . 195 CONTENTS xi7.4.4 Chemical Resistance 195 7.4.5 Adhesion 195 7.4.6 Electrical Properties . 195 7.5 Processing of TPOs 195 7.5.1 Injection Molding . 196 7.5.1.1 Equipment and Process Conditions . 196 7.5.1.2 Mold Design . 196 7.5.2 Extrusion 196 7.5.2.1 Equipment and Process Conditions . 196 7.5.3 Other Processing Methods 197 7.6 Painting of TPOs 198 References . 198 8 Thermoplastic Elastomers Based on Halogen-Containing Polyolefins 201 8.1 Introduction 201 8.2 Blends of PVC with Nitrile Rubber (NBR) . 201 8.2.1 Melt Compounding and Processing 202 8.2.2 Physical and Mechanical Properties . 202 8.2.3 Other Properties . 202 8.3 Blends of PVC with Other Elastomers . 203 8.3.1 Blends of PVC with Copolyester Elastomers . 203 8.3.2 Blends of PVC with Thermoplastic Polyurethane Elastomers 204 8.4 Melt-Processable Rubber . 204 8.4.1 Physical and Mechanical Properties . 205 8.4.2 Chemical Resistance 206 8.4.3 Weather and Flame Resistance 206 8.4.4 Electrical Properties . 207 8.4.5 Grades of MPR 207 8.4.6 Blends with Other Polymers . 208 8.4.7 Processing . 209 8.4.7.1 Injection Molding 209 8.4.7.2 Extrusion . 209 8.4.7.3 Extrusion Blow Molding . 210 8.4.7.4 Calendering . 211 8.4.7.5 Compression Molding 211 8.4.7.6 Bonding and Welding . 212 8.5 Thermoplastic Fluorocarbon Elastomer . 212 References . 213 9 Thermoplastic Polyurethane Elastomers . 215 9.1 Introduction 215 9.2 Synthesis of TPUs . 216 9.2.1 Raw Materials for TPUs 216 9.2.1.1 Raw Materials for Soft Segments 216 9.2.1.2 Raw Materials for Hard Segments . 216 9.2.1.3 Other Raw Materials . 217 9.3 Morphology 218 9.3.1 Morphology of Hard Segments . 218 9.4 Thermal Transitions 218 9.5 Properties . 219 9.5.1 Mechanical Properties . 219 9.5.1.1 Stress–Strain Properties . 221 9.5.1.2 Compression Set 221 9.5.1.3 Hardness . 221 9.5.1.4 Stiffness 221 9.5.1.5 Dynamic Properties 221 9.5.2 Thermal Properties . 222 9.5.3 Hydrolytic Stability 222 9.5.4 Chemical Resistance 223 9.5.5 Abrasion Resistance 223 xii CONTENTS9.5.6 Ultraviolet Stability 223 9.5.7 Electrical Properties . 223 9.6 Processing of TPUs 223 9.6.1 Rheology of TPUs 224 9.6.2 Drying 224 9.6.3 Injection Molding . 224 9.6.3.1 Operating Conditions . 227 9.6.3.2 Insert Molding 228 9.6.3.3 The Use of Regrind 228 9.6.4 Extrusion 228 9.6.4.1 Screw Design 228 9.6.4.2 Die Design 229 9.6.4.3 Extrusion Temperature Profiles 229 9.6.4.4 Extrusion Methods Used 229 9.6.4.5 PostExtrusion Conditioning . 229 9.6.5 Calendering 229 9.6.6 Blowmolding 229 9.6.7 Thermoforming 229 9.7 Blends of TPU with Other Polymers . 230 9.8 Bonding and Welding . 230 9.8.1 Heat Welding and Sealing 230 9.8.2 Solvent and Adhesive Bonding . 230 References . 230 10 Thermoplastic Elastomers Based on Polyamides . 235 10.1 Introduction 235 10.2 Synthesis 235 10.2.1 Synthesis of PEAs, PEEAs, and PCEAs 235 10.2.2 Synthesis of PE-b-As 236 10.2.3 Synthesis of Other Thermoplastic PolyamideElastomers . 236 10.3 Morphology 237 10.4 Structure–Property Relationships . 238 10.5 Physical and Mechanical Properties . 238 10.5.1 Tensile Properties 238 10.5.2 Properties at Elevated Temperatures 239 10.5.3 Tear Strength . 241 10.5.4 Abrasion Resistance 241 10.5.5 Compression Set . 242 10.5.6 Flex Properties 242 10.6 Chemical and Solvent Resistance 242 10.7 Electrical Properties 243 10.8 Other Properties . 243 10.8.1 Weatherability . 243 10.8.2 Adhesion 243 10.9 Compounding . 243 10.10 Processing . 244 10.10.1 Rheology 244 10.10.2 Drying 244 10.10.3 Injection Molding . 244 10.10.4 Extrusion 245 10.10.5 Other Processing Methods 245 10.11 Bonding and Welding . 245 10.11.1 Bonding . 245 10.11.2 Welding . 246 References . 246 11 Thermoplastic Polyether Ester Elastomers 249 11.1 Introduction 249 11.2 Synthesis 249 11.3 Morphology 249 CONTENTS xiii11.4 Properties of Commercial COPEs 250 11.4.1 Stress–Strain Properties . 250 11.4.2 Dynamic Properties . 250 11.4.3 Cut Growth Resistance 251 11.4.4 Impact Resistance 251 11.4.5 Responses to Changes of Temperature 252 11.4.6 Abrasion Resistance 252 11.4.7 Electrical Properties . 253 11.4.8 Chemical Resistance 253 11.4.9 Other Properties . 254 11.5 COPE Blends . 255 11.5.1 Blends of Different Grades of COPE . 255 11.5.2 Blends with Other Polymers . 255 11.6 Processing . 255 11.6.1 General . 255 11.6.2 Melt Rheology . 256 11.6.3 Injection Molding . 257 11.6.3.1 Screw Design 257 11.6.3.2 Clamping Force . 257 11.6.3.3 Molding Conditions 257 11.6.3.4 Molds 257 11.6.3.5 Shrinkage . 258 11.6.3.6 Overmolding (Insert Molding) . 259 11.6.4 Extrusion 259 11.6.4.1 Screw Design 259 11.6.4.2 Processing Conditions 259 11.6.5 Blow Molding . 261 11.6.5.1 Processing Conditions 261 11.6.6 Melt Casting 261 11.6.7 Rotational Molding 262 11.6.8 Welding and Bonding 262 11.6.8.1 Welding 262 11.6.8.2 Bonding and Adhesion 262 11.6.9 Finishing . 262 References . 263 12 Ionomeric Thermoplastic Elastomers 265 12.1 Introduction 265 12.2 Synthesis 265 12.3 Morphology 265 12.4 Properties and Processing 266 References . 267 13 Other Thermoplastic Elastomers 269 13.1 Elastomeric Star Block Copolymers . 269 13.1.1 General Methods for the Synthesis of Star Copolymers . 269 13.1.2 Physical Properties of Star Block Copolymers 270 13.2 TPEs Based on Interpenetrating Networks 270 13.2.1 Synthesis of Thermoplastic IPNs . 271 13.2.2 Properties and Processing of Thermoplastic IPNs . 271 13.3 TPE Based on Polyacrylates 272 13.3.1 Synthesis of Triblock Copolymers Based on Methyl Methacrylate and Butadiene 272 13.3.2 Properties of M–B–M Triblock Copolymers 272 13.3.3 Synthesis of Poly(MMA-t BA-MMA) Elastomers . 272 13.3.4 Synthesis of Poly(MMA-b-Alkylacrylate-b-MMA) . 272 13.3.5 Mechanical Properties of Fully Acrylic Triblock and Branched Block Copolymers 273 References . 273 xiv CONTENTS14 Thermoplastic Elastomers Based on Recycled Rubber and Plastics . 277 14.1 Introduction 277 14.2 EPDM Scrap . 277 14.3 Butadiene-acrylonitrile Rubber (NBR) Scrap . 277 14.4 Recycled Rubber 277 14.5 Waste Latex 278 14.6 Waste Plastics 278 References . 278 15 Applications of Thermoplastic Elastomers 281 15.1 Introduction 281 15.2 Applications for Styrenic TPEs . 281 15.2.1 SBCs as Replacement of Vulcanized Rubber 282 15.2.2 SBCs in Adhesives, Sealants, and Coatings . 283 15.2.2.1 Solution Behavior of SBCs . 286 15.2.2.2 Examples of Applications 287 15.2.3 Blends of SBC with Other Polymers . 288 15.2.3.1 Blends of SBCs and PS . 288 15.2.3.2 Blends of SBCs and Polyolefins . 288 15.2.3.3 Blends of SBCs with Thermosets 288 15.2.4 Modified Asphalt . 289 15.3 Applications of Thermoplastic Vulcanizates (TPVs) and ETPVs . 289 15.3.1 Introduction . 289 15.3.2 Comparison of TPVs and Thermoset Rubber Materials . 289 15.3.3 Commercial Applications of TPVs . 290 15.3.3.1 Automotive Applications . 290 15.3.3.2 Hose, Tubing, and Sheet 290 15.3.3.3 Mechanical Rubber Goods and Consumer Goods 291 15.3.3.4 Architectural and Construction 292 15.3.3.5 Electrical and Electronics 292 15.3.3.6 Medical and Food Contact . 293 15.4 Applications of Thermoplastic Polyolefin Elastomers (TPOs) 294 15.4.1 Automotive . 294 15.4.2 Wire and Cable 294 15.4.3 Mechanical Goods 294 15.4.4 Other Applications 295 15.5 Applications of Melt-Processable Rubber (MPR) 296 15.5.1 Industrial Hose 296 15.5.2 Automotive . 296 15.5.3 Wire and Cable 297 15.5.4 Elastomeric Sheeting 297 15.5.5 Molded Goods . 297 15.5.6 Fabric Coating . 297 15.5.7 Other Applications 298 15.6 Applications of PVC Blends . 298 15.6.1 PVC–Nitrile Rubber (NBR) Blends 298 15.6.2 PVC–Copolyester Elastomer (COPE) Blends . 299 15.6.3 PVC–TPU Blends 299 15.7 Application of TPUs 300 15.7.1 Introduction . 300 15.7.2 Commercial Applications . 300 15.7.2.1 Automotive 300 15.7.2.2 Hose and Tubing 300 15.7.2.3 Wire and Cable . 300 15.7.2.4 Wheels and Casters . 301 15.7.2.5 Film and Sheet . 302 15.7.2.6 Adhesives, Sealants, and Coatings . 302 15.7.2.7 Mechanical Goods, Consumer, and Sporting Goods . 302 15.7.2.8 Medical Applications . 303 CONTENTS xv15.7.2.9 Blends with Other Polymers 304 15.8 Application of Thermoplastic Polyether Ester Elastomers 304 15.8.1 General Properties and Processing 304 15.8.2 Commercial Applications . 304 15.8.2.1 Automotive Applications . 304 15.8.2.2 Electrical/Electronic Applications . 304 15.8.2.3 Extruded and Molded Mechanical Goods . 305 15.8.2.4 Other Applications . 305 15.9 Applications of Polyamide TPEs 306 15.9.1 Introduction . 306 15.9.2 Commercial Applications . 307 15.9.2.1 Automotive 307 15.9.2.2 Sporting Goods . 307 15.9.2.3 Wire and Cable . 308 15.9.2.4 Technical Goods 308 15.9.2.5 Medical Applications . 309 15.9.2.6 Other Applications . 309 15.10 Applications of Ionomeric TPEs 310 15.10.1 Introduction . 310 15.10.2 Commercial Applications . 311 15.10.2.1Adhesives . 311 15.10.2.2Other Applications . 311 15.11 Applications of Other TPEs . 311 15.11.1 Applications of Star Block Copolymers . 311 15.11.2 Applications of Thermoplastic Interpenetration Networks (IPNs) . 312 15.11.3 Applications of Special Blends and Proprietary Compounds 313 References . 313 16 Recycling of Thermoplastic Elastomers 317 16.1 Introduction 317 16.2 Recycling Methods for Thermoplastic Elastomers (TPEs) 317 References . 318 17 Recent Developments and Trends 319 17.1 Current State . 319 17.2 Drivers for the Growth of TPEs 319 17.3 Trends in Technical Development 319 17.3.1 Trends in Development and Uses of Individual TPEs 319 17.4 Other New Developments 321 References . 321 Appendix 1: Books, Conferences, Major Review Articles . 323 Appendix 2: Major Suppliers of Thermoplastic Elastomers and Compounds 325 Appendix 3: ISO Nomenclature for Thermoplastic Elastomers . 329 Appendix 4: Processing Data Sheets for Commercial Thermoplastic Elastomers and Compounds 333 Appendix 5: Technical Data Sheets for Commercial Thermoplastic Elastomers and Compounds 345 Appendix 6: Recent TPE Patents . 379 Glossary 381 Index 391 Index 3D blow molding, 105 abrasion resistance, 381 of commercial COPEs, 252–253 of polyamides, 241–242 of TPUs, 223 acrylonitrile, 184 additives, 13–25 antiblocking agents, 20 antimicrobials, 23 antioxidants, 13 antistatic agents, 19, see also separate entry colorants, 17–19 fillers, 20–23, see also separate entry flame retardants, 15–17 health, hygiene and safety, 25 light stabilizers, 13–14 nucleating agents, 14–15 plasticizers, 23, see also separate entry processing aids, 20 reinforcements, 20–23 selection of, 24–25 slip agents, 19–20 adhesion/adhesive bonding, 141–147, 381, see also polymeric adhesives adherend, 381 adhesive bond formation, 146 adhesive bond strength, 381 application of, 146 bond strength measurement, 146–147 in copolyesters processing, 262 corona discharge treatment, 143 corona treatment, 143 failure, 381 flame treatment, 143 plasma treatment, 143 principles of, 141–142 surface treatment level, evaluation, 144–145 surface treatment methods, 142–145 aging, 13 agitators, 40 Alcryn, 2, 10 general purpose grades, 362–363, 366–367 injection molding grades, 364–365 alumina trihydrate (ATH), 15 amorphous phase, 381 amorphous polymer, 381 anaerobic adhesives, 145 anionic polymerization, 3 annealing, 381 anthraquinones, 18 antiblocking agents, 20 antimicrobials, 23 antimony trioxide, 16 antioxidants, 13 antistatic agents, 19 electrically conductive materials, 19 external antistats, 19 internal antistats, 19 ionic, 19 nonionic, 19 types of, 19 antithixotropic fluids, 37 apparent viscosity, 29 applications of TPEs, 281–315 of (TPVs) and ETPVs, 289–294 of interpenetrating networks (IPNs), thermoplastic, 312–313 of ionomeric TPEs, 310–311 of melt-processible rubber (MPR), 296–298, see also under melt-processible rubber (MPR) of polyamide TPEs, 306–310, see also under polyamide TPEs of PVC blends, 298–299 of star block copolymers, 311–313 styrenic TPEs, 281–289, see also under styrenic TPEs of thermoplastic polyether ester elastomers, 304–306, see also under thermoplastic polyether ester elastomers of thermoplastic polyolefin elastomers (TPOs), 294–296, see also under thermoplastic polyolefin elastomers of TPUs, 300–304, see also under thermoplastic polyurethane elastomers aramid fibers, 22 arc spraying, 148 arm-first synthesis method, 269–270 ASTM D471, 381 ASTM International, 381 auxiliary-ram molds, 93 azo pigments, 18 balanced runner, 77 Banbury mixer, 41–42 bar, 381 barium sulfate, 21 barrier screw, 54 batch mixers, 40–42 bed, 136 belt process, 218 biaxial orientation, 131–132, 381 one-step biaxial orientation, 131 two-step biaxial orientation process, 131 Bingham plastic, 37 391blending, in TPEs processing, 35–51 block copolymers linear block, 3 nomenclature of, 5–6 star block copolymer, 3 synthesis methods, 3 blow molding, 30, 97–108 3D blow molding, 105 blow molding processes, 97–99 blowing and calibrating devices, 106 coextrusion blow molding techniques, 104 continuous extrusion blow molding process, 100 cooling, 107 in copolyesters processing, 261 dip blow molding, 103–104 extrusion blow molding, 99–102 extrusion stretch blow molding, 103 injection blow molding, 102 injection stretch blow molding processes, 103 intermittent accumulator extrusion, 101 molds for, 105–107 multiblock blow molding, 104 of polyolefin-based TPEs, 198 of TPVs, 187 parison head, 98–99 in polystyrene–polydiene block copolymers, 173 reciprocating screw intermittent extrusion, 101 sequential extrusion, 104–105 single-stage extrusion, 100 single-stage injection, 103 stretch blow molding, 102–103 in TPUs processing, 229 venting and surface finish, 106–107 blown film extrusion, 57–59, 260 blown process, 132 blow-up ratio (BUR), 58 bonding and welding in MPR, 211–212 of polyamides, 245–246 bonding in copolyesters processing, 262 of TPUs, 230 of TPVs, 188–189 bubble process, 132 butadiene-acrylonitrile rubber (NBR) scrap, 277 calcined limestone (CaO), 21 calcium carbonate, 21 calender/calendering, 129, 381 of MPR, 211 of polyolefin-based TPEs, 197 in TPUs processing, 229 of TPVs, 187 carbocationic polymerization, SBCs synthesized by, 173–175 polymerization process, 173–174 S–IB–S block copolymers, properties of, 174–175 carbon black, 382 carbon fibers, 22 carbonifics, 15 carousel machines, 111–112 Carreau model, 30 cast film process, 55–57, 260, 382 cationic polymerization, 4 centrifugal pelletizers, 49 char forming systems, 15 chemical blowing agents (CBAs), 123 chemical resistance, of TPUs, 223 chill roll process, 56–57 choker bar, 59 clamshell machines, 112 clay, 22 coalescence, 382 coat hanger die, 59 coefficient of thermal expansion, 382 coextrusion, 60, 104, 261 cohesive energy density, 141 cohesive failure, 381–382 cohesive strength, 141 co-injection molding, 152 cold flow, 382 color concentrates, 18 colorants, 17–19 characteristics of, 17 color concentrates, 18 colorant forms, 18–19 dry colorants, 18 dyes, 17 inorganic pigments, 17–18 liquid colorants, 18 optical properties of, 17 pigments, 17, see also separate entry coloring, in TPEs processing, 34–35 color concentrate or masterbatch, 35 color-compounded polymers, 35 in-process coloring, 34 pre-process coloring, 34 commercial COPEs abrasion resistance, 252–253 chemical resistance, 253–254 cut growth resistance, 251 dynamic properties, 250–251 electrical properties, 253 flame resistance, 254 impact resistance, 251 melting characteristics of, 254 properties of, 250–255 resistance to fluids, 254 resistance to ionizing radiation, 254 resistance to permeation, 254 responses to changes of temperature, 252 stress–strain properties, 250 392 HANDBOOK OF THERMOPLASTIC ELASTOMERSthermal properties, 254 weathering resistance, 254 compounding, 35 of polystyrene–polydiene block copolymers, 170–171 dry blending, 170 melt mixing, 170 solution mixing, 170–171 of TPEs, 150–151 compression molding, 30, 86–90 components, 86 compression molding press, 89 direct positive mold design, 87 flash mold design, 87 fully automatic, 87 hand molds, 87 landed positive mold design, 88 of MPR, 211 in polystyrene–polydiene block copolymers, 173 semiautomatic, 87 semi-positive horizontal flash mold design, 88 semi-positive vertical flash mold design, 88 stages of, 86 standard designs for closure of cavities in, 87 of TPVs, 186–187 types of, 87–89 compression set properties of TPUs, 221 Compuplast, 153 concentricity, 61 conduction, 382 contact adhesives, 145, 382 contact angle, 141, 382 control systems, in injection molding, 72 controlled/living radical polymerization (CLRP), 4 convection, 382 cooling cycle, in rotational molding, 117 COPEs, see copolyesters copolyesters (COPEs), 203–204, 249–263 commercial COPEs, 250–255, see also separate entry COPE blends, 255 metallization of, 262 morphology, 249–250 printing on, 263 processing, 255–263, see also separate entry synthesis, 249 copolyetherester thermoplastic elastomers, 9 copolymerization, 382 corefirst synthesis method, 269–270 corona treatment, 143, 382 coupling method of polystyrene–polydiene block copolymers synthesis, 162–163 covalent bond, 382 cover extrusion, 260 creep, 382 critical shear rate, 382 critical surface tension, 141 cross model, 30 cross-linking, 150, 382 crystallinity, 66, 383 crystalline hydrocarbon polymers, 169 crystalline melting point, 383 crystalline multiblock copolymers, 5 crystallization temperature, 383 cyanoacrylates, 146 decompression foaming, 123 decorating, 148–150 applique´ s, 148 cross-linking, 150 in-mold decorating, 148 metallization, 148–149, see also separate entry painting, 148 printing, 149–150, see also separate entry deflection temperature under load, 383 deformation under load, 383 degradation, 13, 383 density, 383 Desmopan Desmopan445, 368 Desmopan453, 369 diblock copolymer, 5 dicing, 50–51 die(s), 62, 67 die land, 383 die lips, 59 die-face pelletizers, 49 spider-type tube die, 63 tube and pressure die, 63 dielectric breakdown strength or voltage, 383 dielectric constant, 383 dielectric dissipation factor, 383 differential scanning calorimetry, 383 diisocyanate polyaddition reaction, 9 dip blow molding, 103–104 dipole polarization, 136 dispersive mixing, 36 distributive mixing, 36 DowTM ENR TPO typical properties, 352 drag flow, 38 Dray mixer, 46 dry blending, 170 dry colorants, 18 dry-cut eccentric pelletizers, 49 drying, 34 in polyamides processing, 244 Dulmage section, 46 DuPont, 9 DuPontTM ETPV typical properties, 354 durometer, 383 dyes, 17 dynamic vulcanization, TPEs prepared by, 179–189, see also thermoplastic vulcanizates (TPVs) properties of blends prepared by, 181–185 INDEX 393Ecdel, 9 eddy currents, 138 ejection, 172 in injection molding, 84 ElastamaxTM styrenic block copolymers typical properties, 345 elasticity/elastomers, 1–2, 36, 383 elastomer adhesives, 145 elastomeric star block copolymers, 269–270, see also star copolymers electrical properties, of TPUs, 223 electrically conductive materials, 19 electroless plating, 149 electrolytic plating, 149 electron beam radiation, 383 Ellis model, 30 elongation at break, 383 elongational flow, 36 EngageTM 8100 series typical properties, 353 entanglements, molecular, 1 enthalpy, 31 epoxy resins, 145 Estane ester-based products typical properties, 369–370 Estane ether-based products typical properties, 370–371 etching, 144 ethylene propylene diene monomer (EPDM), 151, 277 ethylene-propylene copolymers (EPM), 9 ethylene-vinylacetate copolymer (EVA), 277 exfoliation, 22 expandable foaming, 123 extended mandrel technique, 64 extrusion, 30, 51–66, 171–173 blown film extrusion, 172 coextrusion, 60 control variables, 66 conventional cross-head design, 62 in copolyesters processing, 259–261 extended mandrel technique, 64 extruder, 52–54 extrusion blow molding, 99–102 extrusion coating, 65 extrusion foaming, of TPVs, 187–188 extrusion methods, 54–65 extrusion screw, features, 53 film and sheet extrusion, 55–60, see also separate entry fundamentals of, 51–52 of MPR, 210–211 of pipe and tubing, 62–65 in polyamides processing, 245 of polyolefin-based TPEs, 196–197 process control in, 65–66 processing, of MPR, 209–210 of profiles, 65 of S–B–S block copolymers, 171–172 of S–EB–S block copolymers, 171–172 self-centered die cross-head design, 62 single-screw extruder, 52 in TPUs processing, 228–229 die design, 229 extrusion methods used, 229 extrusion temperature profiles, 29 postextrusion conditioning, 229 of TPVs, 185–186 vacuum trough method, 63 wire coating, 60–62 fabric coating, 260 Farrel continuous mixer (FCM), 42–43 fatigue, 384 fatigue life, 384 fatigue strength, 384 feedback, 74 feeders, 47 feedscrew nomenclature, 45 fibrous fillers, 22 aramid fibers, 22 carbon fibers, 22 glass fibers (chopped strand), 22 fibrous reinforcements, 33 filament, 384 fillers and reinforcements, 20–23, 184 barium sulfate, 21 carbon black, 21 clay, 22 cubic and spheroidal fillers, 21 fibrous fillers, 22, see also separate entry glass and ceramic beads, 21 Kaolin, 22 mica, 22 nanofillers, 22–23 platy fillers, 22 synthetic silica, 21 talc, 22 film and sheet extrusion, 55–60 blown film extrusion, 57–59 cast film extrusion, 55–57 chill roll cast film process, 55–56 sheet extrusion, 59–60 water quench cast film process, 56 filtration, 47 finishing operations, in TPEs processing, 47–51 dicing, 50–51 filtration, 47 granulation, 51 pelletizing, 48–50, see also separate entry size reduction, 47–51 flame retardants, 15–17 char forming systems, 15 394 HANDBOOK OF THERMOPLASTIC ELASTOMERSflammability tests, 16–17 intumescent systems, 15 limiting oxygen index (LOI) test, 16–17 polyolefins, 15 flame spraying, 143, 148 flavanthrones, 18 flexural modulus of elasticity, 384 flocking, 150 flood feeding, 45 Flory–Rehner equation, 168 fluorescent pigments, 18 fluorescent whitening agents, 24 fluoropolymer-based processing, 20 foam extrusion, 261 foaming of TPEs, 121–124 accumulating extrusion, 124 cell growth, 121–122 cell initiation, 121 cell stabilization, 121 chemical foaming, 122 cooling extruder, 124 decompression foaming, 123 expandable foaming, 123 flash extrusion, 124 foam extrusion, 124 foam manufacturing processes, 123–124 foaming technology, 121–123 mechanical foaming, 122 physical foaming, 122–123 polymeric foams versus solid polymers, 121 primary extruder, 124 free radical scavengers, 14, 384 free surface energy, 388 friction ratio, 40 fully automatic compression mold, 87 gamma radiation, 384 gamma ray irradiation, 384 gates, 77, 78–80 positions, recommendations in, 79 sprue-gating, 80 types, 79, 172 general-purpose screw, 69 Geniomertypical properties, 375 GeolastTM TPV, typical properties, 355 glass and ceramic beads, 21 glass fibers (chopped strand), 22 graft copolymer, 5, 191, 384 grafting, 384 granulation, 51 graphite, 384 gravure coating, 384 Grilamid, 9 halogen-containing polyolefins, TPEs based on, 201–213, see also polyvinyl chloride blends of PVC with NBR, 201–203, see also under nitrile rubber melt-processible rubber, 204–212, see also separate entry thermoplastic fluorocarbon elastomer, 212–213 hand compression mold, 87 hard polymer/elastomer graft copolymers, 5 heat activated assembly adhesives, 145 heat deflection temperatures (HDTs), 15, 384 heat distortion temperature (HDT), 384 heated tool welding, 133 high density polyethylene (HDPE), 32 Hookean elastic, 36 hot gas welding, 133–134 hot melt adhesive, 145, 384 hot runners, 80–81, 172 direct hot runner gates, 81 HybrarTM triblock copolymer, properties, 347 hydrolytic stability, of TPUs, 222–223 hysteresis, 138, 384 Hytrel, 9, 373 immiscible polymers, 39 impact strength, 385 induction welding, 137–138 inert fillers, 169 infrared welding, 136 injection molding, 30, 66–86, 102, 151–153, 385 basic sequence of injection unit, 70 basic technology, 67 clamp unit, 68–69 co-injection molding, 152 cold runners, 77–78 components, 74 control systems, 72–74 cooling feature, 81–83 in copolyesters processing, 257–259 crystallinity, 66 dimensional stability of parts, 84–86 direct hydraulic clamp unit, 68 ejection feature, 84 features, 81–84 gates, 77, 78–80, see also separate entry general considerations, 66–67 heat, 66 hot runners, 80–81 injection mold feed systems, 76–81 injection molding machinery, 67–74 injection unit, 67, 69–72 insert molding, 153 materials feature, 81 materials of construction, 84 mold types, 74–76 of MPR, 209 operation, 75 overmolding, 152–153 INDEX 395injection molding (continued ) in polyamides processing, 244–245 of polyolefin-based TPEs, 196 in polystyrene–polydiene block copolymers, 172 power systems, 72 process factors, 73 process, 67 processing steps in, 68 runner, 77 single-stage ram or plunger, 69 single-stage screw, 69 sprues, 77–78 stack molds, 76 thermal conductivity, 66 three-plate molds, 75–76 toggle clamp unit, 68 in TPUs processing, 224–228 of TPVs, 186 two-plate molds, 75 two-shot molding, 152 two-stage ram, 69 two-stage screw/ram, 69 venting feature, 83–84 viscosity, 66 injection stretch blow molding processes, 103 inorganic pigments, 17–18 insert molding, 153 in TPUs processing, 228 intercalation, 22 interfacial tension, 39 intermittent extrusion, 101 internal mixers, 41–42 interpenetrating polymer network (IPN), TPEs based on, 270–272 applications, 312–313 properties and processing of, 271–272 synthesis, 271 intumescent systems, 15 ionizing radiation, 385, 387 ionomeric TPEs, 385 applications, 310–311 IRM 902, 385 IRM 903, 385 ISO nomenclature for TPEs, 329–331 isoindolines, 18 isomers, 5 jacketing (or sheathing), 61 kaolin, 22 Kopel KP polyester elastomers typical properties, 373 Kraton, 9 Kraton D (IR) polymer grades, properties, 347 Kraton D (SBS) radial polymer grades typical properties, 347 Kraton D (SIS) polymer grades, 348 Kraton D oiled polymer grades, 347 Kraton G polymer grades typical properties, 349–350 land area, 59 land length, 79 lap joint, 385 lap shear test, 146 laser, 385 laser treatment, 144 laser welding, 140–141 latent heat of fusion, 31 let-down ratio, 35 lettering, 150 lewis base, 385 light stabilizers, 13–14 free radical scavengers, 14 quenchers, 14 UV absorbers, 14 limiting oxygen index (LOI), 16, 385 linear welding, 137 linking, 1 physical, 1 liquid colorants, 18 Lomod, 9 lubricants, 20 machine direction orientation (MDO), 130–131 machinery for mixing, 43–47 feedscrew nomenclature, 45 single-screw extruders, 43–46 twin-screw extruders, 46–47, see also separate entry Maddock mixer, 46 magnesium hydroxide, 15 major suppliers of TPEs, 325–327 manual hot gas welding, 134 masterbatch, 35 matched die forming, 385 M–B–M triblock copolymers, 272 mechanical fastening, 147–148 melt bonding techniques, 212 melt casting, in copolyesters processing, 261–262 melt flow index (MFI), 29 melt flow rate (MFR), 29 melt fracture occurs, 382 melt mixing, 170 melt processible polymer, 385 melting, 36 melt-processible rubber (MPR), 2, 29, 204–212 applications of, 296–298 automotive applications, 296–297 blends with other polymers, 208 bonding and welding processing, 211–212 bonding to other materials, 212 calendering, 211 chemical resistance, 206 396 HANDBOOK OF THERMOPLASTIC ELASTOMERScompression molding, 211 compression set and creep of, 207 elastomeric sheeting applications, 297 electrical properties, 207 extrusion blow molding processing, 210–211 extrusion processing, 209–210 extrusion/calendering grades, 207 fabric coating applications, 297–298 grades of MPR, 207–208 industrial hose applications, 296 injection molding grades, 208 injection molding processing, 209 melt bonding techniques, 212 molded goods applications, 297 physical and mechanical properties, 205–206 processing, 209–212 tensile properties, 206 ultrasonic welding, 212 weather and flame resistance, 206–207 wire and cable applications, 297 metallization, 148–149 electroless plating, 149 electrolytic plating, 149 flame and arc spraying, 148 sputtering, 149 vacuum metallization, 148 mica, 22 micron, 385 microwave welding, 138–139 miscellaneous block copolymers, 5 miscible polymers, 39 mixing, in TPEs processing Banbury mixer, 41 basic concepts, 36–39 batch mixers, 40–42 blending and, 35–51 continuous mixers, 42–43 continuous mixing, 40 dispersive mixing, 44 distributive mixing, 44 equipment, 40–47 Farrel continuous mixer (FCM), 42–43 finishing operations, 47–51, see also separate entry internal mixers, 41–42 material feeding and feeders, 47 melting, 36 mixing machinery, 43–47, see also under machinery mixing rolls, operation of, 41 polymer blends, 39–40 residence time, 38 rheology and flow pertaining to, 36–38 roll mills, 40–41 specific mechanical energy (SME), 38–39 modular co-rotating twin-screw extruders. modular, 46–47 moisture-cure adhesives, 145 molded part or molding, 67 Moldflow, 153 molding techniques and extrusion for TPEs, 30 blow molding, 30 compression molding, 30 injection molding, 30 rotational molding and rotolining, 30 transfer molding, 30 molecular weight between entanglements (Me), 1 monoazo pigments, 18 monofilaments, 260 multiblock blow molding, 104 multifunctional initiation method of polystyrene–polydiene block copolymers synthesis, 162 nanofillers, 22–23 nanometer, 385 NBR (butadiene-acrylonitrile rubber), 9 network, polymer, 1 Newtonian fluids, 29, 36, 385 nitrile rubber (NBR) blends of PVC with, 201–203 melt compounding and processing, 202 physical and mechanical properties, 202 nonazo pigments, 18 non-Newtonian fluids, 29 time-dependent fluids, 38 time-independent fluids, 38 nucleating agents, 14–15 inorganic additives, 15 organic compounds, 15 polymers, 15 offset printing, 386 olefin, 386 one-shot method, 218 orbital welding, 137 organic pigments, 18 orientation, 386 overmolding, 152–153 in copolyesters processing, 259 oxidation, 144 ozone, 386 painting of TPOs, 198 palletizing/pelletizers, 48–50 centrifugal pelletizers, 49 die-face pelletizers, 49 dry-cut eccentric pelletizers, 49 layout for, 51 rotary knife pelletizers, 50 strand pelletizers, 48 underwater pelletizers, 49 water ring pelletizer, 49 paracrystalline, 218 INDEX 397paraffins, 386 parison, 97–99, 386 part stripping, in rotational molding, 117–118 parting line, 105 pascal, 386 pearlescent pigments, 18 Pebax typical properties, 374 peel strength, 386 peel tests, 146–147 Pellethane TPU 2355 series typical properties, 371–372 Pelprene, 9 pendant methyl group, 386 permeability, 386 perylenes, 18 phosphorescent pigments, 18 photodegradation, 13 physical blowing agents (PBAs), 123 Physical linking, 1 pigments, 17 as nucleating agents, 17 azo pigments, 18 black pigments, 17 blue pigments, 18 brown pigments, 18 fluorescent pigments, 18 green pigment, 18 monoazo pigments, 18 nonazo pigments, 18 orange pigments, 18 organic pigments, 18 pearlescent pigments, 18 phosphorescent pigments, 18 red pigments, 18 special effect pigments, 18 white pigments, 17 yellow pigments, 18 pinch-off zones, 105–106 plasma treatment, 143 cold plasma, 143 plasticizers, 23 methods of incorporation, 23 types of, 23 plastics, TPEs based on, 277–279 plastisols, 23 platy fillers, 22 plug assist, 128 plunger molding, 91 Poisson’s ratio, 386 polar molecule, 386 Poly(MMA-tBA-MMA) elastomers, synthesis, 272 Poly(vinyl chloride) (PVC) blends applications of, 298–299 polyacrylates, TPEs based on, 272–273 synthesis, 272 Polyaddition, 4 polyamide TPEs, 9, 235–246, see also polyesteramides (PEAs); polyetheresteramides (PEEAs); polycarbonateesteramides (PCEAs); polyether-block-amides (PE-b-As) abrasion resistance, 241–242 adhesion, 243 applications, 306–310 automotive applications, 307 bonding and welding, 245–246 chemical and solvent resistance, 242–243 commercial applications, 307–310 compounding, 243–244 compression set, 242 drying, 244 electrical properties, 243 extrusion, 245 flex properties, 242 glass transition temperatures and melting points of, 236 medical applications, 309 morphology, 237–238 physical and mechanical properties, 238–242 processing, 244–245 properties at elevated temperatures, 239–241 rheology, 244 sporting goods applications, 307–308 structure property relationships, 238 synthesis, 235–237 tear strength, 241 technical goods applications, 308–309 tensile properties, 238–239 weatherability, 243 wire and cable applications, 308 polyazos, 18 polycarbonateesteramides (PCEAs), 235 dry heat aging of, 241 synthesis, 235–236 tensile properties, 239 polyesteramides (PEAs), 235 dry heat aging of, 241 synthesis, 235–236 tensile properties, 239 polyether sulfone (PES), 32 polyether-block-amides (PE-b-As), 235 physical and mechanical properties, 237 synthesis, 236 polyetheresteramides (PEEAs), 235 dry heat aging of, 241 synthesis, 235–236 tensile properties, 239 polyethylene (PE), 386 polymer blends, 39–40 polymeric adhesives anaerobic adhesives, 145 contact adhesives, 145 cyanoacrylates, 146 398 HANDBOOK OF THERMOPLASTIC ELASTOMERSelastomer, 145 epoxy resins, 145 heat activated assembly adhesives, 145 hot-melt adhesives, 145 moisture-cure adhesives, 145 polyurethane- and isocyanate-based adhesives, 146 silicones, 146 thermoplastic elastomers, 145 two-part adhesives consist, 145 types of, 145–146 polymerization process, 3–4, 173–174 anionic, 3 cationic, 4 with core-shell morphologies, 5 with Ziegler-Natta catalysts, 4 polyolefin-based TPEs, 15, 191–198, 386 adhesion, 195 chemical resistance, 195 compounding of, 192–193 electrical properties, 195 mechanical properties, 193–194 morphology, 193 painting of, 198 processing of, 195–198, see also under processing properties of, 193–195 service temperatures, 194 stress–strain properties, 193–194 weathering, 194–195 polypropylene (PP), 31, 169, 386 polypropylene oxide (PPO), 32 polystyrene–polydiene block copolymers, 162–173 blow molding, 173 bonding, 173 compounding, 170–171, see also separate entry compression molding, 173 coupling method of synthesis, 162 critical molecular weight for domain formation, 164–165 effect of elastomer type, 165 effect of hard segment type, 165–166 effect of polystyrene content, 165 effects of molecular weight, 165 injection molding, 172 morphology of, 163–164 multifunctional initiation method of synthesis, 162 processing of compounds from SBCs, 171–172, see also under extrusion properties of, 165–168 sealing, 173 sequential method of synthesis, 162 solution properties, 167–168 structure property relationships, 165–166 styrenic TPEs, formulating, 168–170, see also separate entry swelling, 168 synthesis of, 162–163 tensile properties, 166 thermoforming, 173 viscous and viscoelastic properties, 166–167 polytetrafluoroethylene (PTFE) , 386 polyurethane-and isocyanate-based adhesives, 146 polyvinyl chloride (PVC) blends, 201, 387 PVC–COPE blends, applications, 299 PVC–NBR blends, applications, 298–299 PVC–TPU blends, applications, 299 with copolyester elastomers, 203–204 with NBR, 201–203, see also under nitrile rubber with thermoplastic polyurethane elastomers, 204 polyvinylidene fluoride (PVDF), 387 positive displacement, 38 Power Law Model, 30 power systems, in injection molding, 72 preform, 102 prepolymer method, 218 pre-processing methods for TPEs, 33–35 press, 67 pressure sensitive adhesive, 387 primers, 144, 387 printing, 149–150 decorating processes, 150 diffusion process, 149 fill and wipe processes, 150 laser printing, 150 pad transfer, 149 screen printing, 149 processing, see also individual entries of copolyesters, 255–263 adhesion, 262 blow molding, 261 bonding, 262 extrusion, 259–261 finishing, 262–263 injection molding, 257–259 melt casting, 261–262 melt rheology, 256–257 overmolding (insert molding), 259 rotational molding, 262 welding, 262 of melt-processible rubber (MPR), 209–212 of polyolefin-based TPEs, 195–198 blow molding, 198 calendering, 197 extrusion, 196–197 general injection molding parameters for, 197 injection molding, 196 thermoforming, 197 process control in extrusion, 65–66 processing aids, 20 of TPUs, 223–230 blowmolding, 229 calendering, 229 drying, 224 INDEX 399processing (continued ) extrusion, 228–229 injection molding, 224–228 insert molding, 228 operating conditions, for injection molding, 227–228 regrind use in, 228 rheology, 224 thermoforming 229–230 processing data sheets for commercial TPEs and compounds, 333–343 of copolyester thermoplastic elastomers, 342 of melt processible rubber, 340 of polyamide thermoplastic elastomers, 342–343 polyolefin-based TPE (TPO), 336–337 styrenic block copolymers, 333–336 of thermoplastic polyurethanes, 340–341 of thermoplastic vulcanizates, 337–339 processing methods of TPEs, 29–160 blow molding, 97–108, see also separate entry calendering, 129 coloring, 34–35, see also separate entry compounding of TPEs, 150–151 compression molding, 86–90, see also separate entry drying, 34 extrusion, 51–66, see also separate entry flow properties influencing, 29–31 foaming, 121–124, see also foaming general processing technology, 150–153 injection molding, 66–86, see also separate entry melt-processing methods, 29 mixing and blending, 35–51, see also mixing molding techniques and extrusion, 30 pre-processing, 33–35 process heat requirements, 31 process simulation, 153 product development and testing, 153–154 properties influencing, 29–33 rotational molding, 108–121, see also separate entry secondary manufacturing processes, 129–150, see also separate entry shrinkage, 32–33 thermal properties influencing, 31–32 thermoforming, 124–129, see also separate entry transfer molding, 90–97, see also separate entry warping, 32–33 quenchers, 14 quinacridones, 18 radiation dose, 387 random block copolymers that, 191 reaction extruder process, 218 reactor thermoplastic polyolefins (RTPO), 192 recent developments and trends, of TPEs, 319–322 current state, 319 in development and uses of individual TPEs, 319–321 drivers for the growth of TPEs, 319 organosilane technology, 321 in technical development, 319–321 TPV developments, 320 TPVs based on natural rubber (NRTPVs), 320 reciprocating screw injection unit, 69–70 reciprocating screw intermittent extrusion, 101 recycled rubber, TPEs based on, 277–279 butadiene-acrylonitrile rubber (NBR) scrap, 277 recycling of TPEs, 317–318 energy recovery, 317 to generic plastic, 317 to mixed plastic, 317 recycling methods, 317–318 regeneration of raw materials, 317 Reference Fuel A, 387 Reference Fuel B, 387 Reference Fuel C, 387 Reference Fuel D, 387 regrind, use in TPUs processing, 228 reinforcements, 20–23 residence time concept, 71 residence time, 38 resistant welding, 139 restrictor bar, 59 rheology, 387 in copolyesters processing, 256–257 and flow pertaining to mixing, 36–38 in polyamides processing, 244 of TPUs, 224 of TPVs, 185 rheometers, 30 rheopectic fluids, 37 roll mills, 40–41 rotary knife pelletizers, 50 rotational molding, 108–121 and rotolining, 30 background, 108–109 basic process technology, 109–110 batch systems, 111 benefits, 111 build-up time, 115 carousel machines, 111–112 clamshell machines, 112 cooling cycle, 117 in copolyesters processing, 262 design consideration for, 113 equipment and process design, 112–114 equipment for, 110–112 fusion time, 115 limitations, 111 melting of polymer and part formation, 119–120 mold surface preparation, 114 operation of, 114–118 oven dwell time, 115–117 400 HANDBOOK OF THERMOPLASTIC ELASTOMERSpart stripping, 117–118 rotation rate and ratio, 118 rotolining process, 118–119 shuttle machines, 112 spin-casting or centrifugal casting, 110 troubleshooting, 120 variables influencing oven dwell time, 116 venting, 117 rotors, 40 runner, 77 Santoprene, 9 SantopreneTM TPV, typical properties, 356–358 Sarlink 3139 D typical properties, 359 S–B–S block copolymers, 168–169 screws, 43–46, 172, see also feedscrew nomenclature; single-screw extruders barrier or melt extraction screw, 54 geometrical attributes of, 46 intermeshing screw, 47 left-handed screw, 46 mixing performance of, 54 modifications, 46 right-handed screw, 46 screw transfer molding, 91 tangential screw, 47 vented screw, 54 S–EB–S block copolymers, 169–170 secondary manufacturing processes, 129–150 adhesive bonding, 141–147, see also separate entry biaxial orientation, 131–132 bubble process, 132 decorating, 148–150, see also separate entry film and sheet orientation, 129–133 heat shrinkable films and tubing, 132–133 machine direction orientation (MDO), 130–131 mechanical fastening, 147–148 transverse direction orientation (TDO), 131 welding, 133–141, see also separate entry semiautomatic compression mold, 87 Semi-Crystalline Polymer, 387 sequential extrusion, 104–105 sequential method of polystyrene–polydiene block copolymers synthesis, 162 shear displacement of a plane of solid body parallel, 387 shear forces, 36 shear tests, 146 sheet extrusion, 59–60 shelf life, 387 shore hardness, 387 shrinkage, 32–33, 172 shuttle machines, 112 S–iB–S Styrene–isobutylene–styrene block copolymer, 388 with polystyrene, 388 silicone oils, 169 silicones, 146 single press method, 211 single-phase melt-processable rubber (MPR), 10 single-screw extruders, 43–46, 52 components of, 44 S–I–S Styrene–isoprene–styrene block copolymer, 388 slip agents, 19–20 slush molding process, 108 softening point, 388 solubility, 388 parameter, 388 solution mixing, 170–171 solution properties, of polystyrene–polydiene block copolymers, 167–168 special effect pigments, 18 specific mechanical energy (SME), 38–39 spherulites, 14, 388 spin welding, 135–136 spiral flow method, 31 sprues, 77–78, 172 sputtering, 149 stalk height, 58 star block (radial) copolymers, 269–270, 388 applications of, 311–313 arm-first synthesis method, 269 corefirst synthesis method, 269 physical properties, 270 synthesis of, 269–270 stereoblock copolymers, 191 strain, 388 strand pelletizers, 48 stress relaxation, 388 stretch blow molding, 102–103 stripper plates, 172 styrene-diene block copolymers, 9 styrenic block copolymer (SBC), 5, 151, 161–177 polystyrene–polydiene block copolymers, 162–173, see also separate entry styrene–butadiene–styrene block copolymer, 162 synthesized by carbocationic polymerization, 173–175, see also under carbocationic polymerization thermoplastic elastomers based on, 163 styrenic TPEs applications of, 281–289 as replacement of vulcanized rubber, 282–283 blends of SBCs and polyolefins, 288 blends of SBCs and PS, 288 blends of SBCs with thermosets, 288–289 effect of the addition of resins and oils, 286–287 in adhesives, sealants, and coatings, 283–288 in pressure sensitive adhesives, 287 solution behavior of SBCs, 286 solvents for SBCs, 286 formulating, 168–170 compounding styrenic thermoplastic elastomers, 169 INDEX 401styrenic TPEs (continued ) S–B–S block copolymers, 168–169 S–EB–S block copolymers, 169–170 surface energy, 141 surface grafting, 144 surface tension, 40, 141, 388 swelling, of polystyrene–polydiene block copolymers, 168 synergistic effect, 16 taber abrasion resistance, 388 talc, 22 tan delta or dissipation factor, 383 tear strength, of polyamides, 241 technical data sheets for commercial TPEs and compounds, 345–378 COPA data sheets, 374–375 COPE data sheets, 373 MPR data sheets, 362–368 SBC data sheets, 345–352 silicone TPE data sheets, 375–378 TPO data sheets, 352–353 TPU data sheets, 368–372 TPV data sheets, 354–362 tensile properties of polystyrene–polydiene block copolymers, 166 tensile strength, 388 tensile stress, 388 tenter frame, 131 Texin TPU 200 series typical properties, 372 texturing, 150 thermal conductivity, 66 thermal properties, of TPUs, 222 thermal transitions, in TPUs, 218–219 thermal treatment, 144 thermoforming, 124–129 forming force, 126–127 heating, 128 matched mold (die) forming, 126 material input, 128 melt phase forming, 128 mold type, 127 of polyolefin-based TPEs, 197 in polystyrene–polydiene block copolymers, 173 pressure forming, 126 principal options available in, 125 process basics, 124–125 process factors, 125–129 process phase, 128 sheet prestretch, 127–128 solid phase forming, 128 in TPUs processing, 229–230 of TPVs, 187 vacuum forming, 126 Thermolast typical properties, 360 thermoplastic elastomers (TPEs), 2–7 advantages and disadvantages of, 6–7 applications of, 281–315, see also under applications classification, 5–6 demand for, 7 flexural modulus, regions, 2 glass transition and crystalline melt temperatures of, 3 history of, 9–11 macrophase separation, 5 microphase separation, 5 phase separation, 4–5 phase structure, 2–3 processing methods applicable to, 29–160, see also under processing methods property ranges, 6 stiffness of, 2 synthesis methods, 3 thermoplastic fluorocarbon elastomer, 212–213 properties of, 212 structure of, 212 thermoplastic olefins (TPOs), 320 thermoplastic polyether ester elastomers, 249–263, see also copolyesters (COPEs) applications, 304–306 automotive applications, 304 commercial applications, 304 electrical/electronic applications, 304–305 extruded and molded mechanical goods applications, 305 thermoplastic polyolefin blends (TPOs), 9, 191–198, see also polyolefin-based TPEs, 191–198 applications of, 294–296 automotive applications, 294 mechanical goods applications, 294 wire and cable applications, 294 thermoplastic polyurethane elastomers (TPUs), 9, 191, 201, 204, 215–230 abrasion resistance, 223 adhesives applications, 302 antidegradants for TPUs synthesis, 217 applications, 300–304 automotive applications, 300 blends with other polymers, 230 bonding, 230 chemical resistance, 223 coatings applications, 302 commercial applications, 300 compression set, 221 dynamic properties, 221–222 electrical properties, 223–224 film and sheet applications, 302 hard segment, 215–216 hardness, 221 hose and tubing applications, 300 hydrolytic stability, 222–223 ineral fillers for TPUs synthesis, 217 402 HANDBOOK OF THERMOPLASTIC ELASTOMERSlubricants for TPUs synthesis, 217 mechanical goods, consumer, and sporting goods applications, 302–303 mechanical properties, 219–222 medical applications, 303–304 mold release agents for TPUs synthesis, 217 morphology of hard segments, 218 morphology, 218 plasticizers for TPUs synthesis, 217 processing of TPUs, 223–230, see also separate entry properties, 219–223 raw materials for hard segments, 216–217 raw materials for soft segments, 216 raw materials for TPUs synthesis, 216–218 reinforcing fillers for TPUs synthesis, 217 sealants applications, 302 soft segment, 215–216 solvent and adhesive bonding, 230 stiffness, 221 stress–strain properties, 221 synthesis, 216–218 thermal properties, 222 thermal transitions, 218–219 ultraviolet stability, 223 UV absorbers for TPUs synthesis, 217 welding, 230 wheels and casters applications, 301 wire and cable applications, 300–301 thermoplastic vulcanizates (TPVs), 9 applications, 289–294 architectural and construction application, 292 automotive applications, 290 based on polyacrylate rubber and polyamides, 185 based on polyolefins, 181–185 blow molding, 187 bonding of, 188–189 calendering, 187 commercial applications, 290 compression molding, 186–187 electrical and electronics application, 292–293 extrusion foaming, 187–188 extrusion, 185–186 from butadiene-acrylonitrile rubber and polyamides, 182–185 from butyl and halobutyl rubber and PP resins, 182 from diene rubbers and polyolefins, 181–182 from EPDM–polyolefin blends, 181 hose, 290–291 hot air aging of NR/PP-based TPVs, 183 in mechanical rubber goods and consumer goods application, 291–292 injection molding, 186 mechanical properties of NR/PP-based TPVs, 183 medical and food contact application, 293–294 morphology, 181 processing and fabrication of, 185–189 rheology, 185 sheet application, 290–291 thermoforming, 187 tubing application, 290–291 thermoset rubber, 212 Thixotropic fluids, 37, 388 three-plate molds, 75–76 time-independent non-Newtonian fluids, 36–37 tool, 67 TPSiVTM series typical properties, 376–378 transfer molding, 30, 90–97 auxiliary-ram mold, 96 auxiliary-ram molds, 93 background, 90 cycle transfer molding, 92 integral transfer mold, 95 manual loose-plate transfer mold, 94 mold design, 93–96 operation of, 96 plunger molding, 91 plunger-type transfer mold, 92–93 process variables, 96–97 screw transfer molding, 91 screw transfer process, 94 semiautomatic floating plate mold, 95 transfer-in compression molding, 90–91 types of, 91–93 transverse direction orientation (TDO), 131 triblock copolymers, 272 tubing, 260 tubular process, 132 twin-screw extruders, 46–47 modular co-rotating twin-screw extruders, 46–47 modular counter-rotating twin-screw extruders, 47 two-part adhesives, 145 two-plate molds, 75 two-press method, 211 two-shot molding, 152 ultrasonic welding, 134–135, 212 ultraviolet (UV) UV absorbers, 14 UV stability, 13 evaluation, 14 of TPUs, 223 underwater pelletizers, 49 vacuum trough method, 63 van der Waals forces, 389 Vector styrenic block copolymers typical properties, 351 venting, 172 in injection molding, 83–84 in rotational molding, 117 vibration welding, 137 INDEX 403viscosity, 66, 389 viscous and viscoelastic properties of polystyrene–polydiene block copolymers, 166–167 warping, 32–33 waste latex, TPEs based on, 278 waste plastics, TPEs based on, 278 water quench cast film process, 56–57 water-quench blown-film process, 58–59 water ring pelletizer, 49 weathering, 194–195 Weber number, 40 welding, 133–141 in copolyesters processing, 262 extrusion welding, 139 heated tool welding, 133 high frequency welding, 136 hot gas welding, 133–134 induction welding, 137–138 infrared welding, 136 laser welding, 140 linear welding, 137 manual hot gas welding, 134 microwave welding, 138–139 of TPUs, 230 orbital welding, 137 resistant welding, 139 spin welding, 135–136 ultrasonic welding, 134–135 vibration welding, 137 wetting, 141, 389 wheel machines, 101 Williams Landel Flory (WLF) equation, 167 wire coating, 60–62 yield deformation, 389 yield stress, 37 young’s modulus, 389 Zeotherm typical properties, 361 Ziegler-Natta catalysts, 4 zinc borate, 1
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