1 Characteristics of Polymers .............................. 1-1
1.1 What Is a Polymer? ....................................... 1-1
1.2 Molecular Weight of Polymers ............................. 1-3
1.2.1 Number-Average Molecular Weight (Mn) .............. 1-3
1.2.2 Weight-Average Molecular Weight (Mw) .............. 1-3
1.2.3 Viscosity-Average Molecular Weight (Mv) ........... 1-4
1.2.4 Polydispersity Index .............................. 1-4
1.3 Polymerization Processes ................................. 1-6
1.3.1 Addition or Chain Polymerization .................. 1-6
1.3.2 Coordination Addition Polymerization ............. 1-11
1.3.3 Step Polymerization .............................. 1-14
1.3.4 Supramolecular Polymerization .................... 1-18
1.3.5 Copolymerization ................................. 1-22
1.4 Configurations of Polymer Molecules ..................... 1-24
1.5 Conformations of a Polymer Molecule ..................... 1-25
1.6 Polymer Crystallinity ................................... 1-26
1.6.1 Determinants of Polymer Crystallinity ............ 1-27
1.7 The Amorphous State ..................................... 1-28
1.8 Structural Shape of Polymer Molecules ................... 1-29
1.9 Thermal Transitions in Polymers ......................... 1-31
1.9.1 Tg and Tm ........................................ 1-31
1.9.2 Regions of Viscoelastic Behavior ................. 1-34
1.9.3 Factors Affecting Tg ............................. 1-36
1.9.3.1 Chain Flexibility ....................... 1-36
1.9.3.2 Steric Effects .......................... 1-37
1.9.3.3 Configurational Effects ................. 1-37
1.9.3.4 Effect of Cross-Linking ................. 1-38
1.9.4 Factors Affecting Tm ............................. 1-38
1.9.4.1 Symmetry ................................ 1-38
1.9.4.2 Intermolecular Bonding .................. 1-39
1.9.4.3 Tacticity ............................... 1-40
1.9.4.4 Branching, Chain Flexibility, and
Molecular Weight ........................ 1-40
1.9.5 Relation between Tm and Tg ....................... 1-40
1.10 Designing a Polymer Structure for Improved Properties ... 1-40
1.11 Cross-Linking of Polymer Chains ......................... 1-42
1.11.1 Reactions of Functional Groups ................... 1-42
1.11.2 Vulcanization .................................... 1-45
1.11.3 Radiation Cross-Linking .......................... 1-49
1.11.4 Photochemical Cross-Linking ...................... 1-51
1.11.5 Ionic Cross-Linking .............................. 1-52
1.11.1 Solubility Behavior of Polymers .................. 1-53
1.12.1 Solubility Parameter ............................. 1-53
1.13 Effects of Corrosives on Polymers ....................... 1-60
1.14 Thermal Stability and Flame Retardation ................. 1-63
1.14.1 Thermal Degradation .............................. 1-67
1.14.2 Ablation ......................................... 1-69
1.14.3 Flame Retardation ................................ 1-70
1.15 Deterioration of Polymers ............................... 1-70
1.15.1 Chemical Deterioration ........................... 1-71
1.15.2 Degradation by Radiation ......................... 1-74
1.15.3 Microbiological Deterioration .................... 1-74
1.16 Stabilization of Polymers ............................... 1-75
1.16.1 Antioxidants and Related Compounds ............... 1-76
1.16.2 Chemical Structures of Antioxidants .............. 1-78
1.16.3 Stabilization of Selected Polymers ............... 1-80
1.16.3.1 Polypropylene ........................... 1-82
1.16.3.2 Polyethylene ............................ 1-82
1.16.3.3 Polystyrene ............................. 1-83
1.16.3.4 Acrylonitrile-Butadiene-Styrene
Copolymers .............................. 1-83
1.16.3.5 Polycarbonate ........................... 1-83
1.16.3.6 Nylons .................................. 1-83
1.16.3.7 Thermoplastic Elastomers ................ 1-84
1.16.3.8 Polyacetal .............................. 1-85
1.16.3.9 Polyvinyl Chloride) ..................... 1-85
1.16.3.10 Rubber ................................. 1-86
1.17 Metal Deactivators ...................................... 1-86
1.18 Light Stabilizers ....................................... 1-88
1.18.1 Light Stabilizer Classes ........................ 1-89
1.18.1.1 UV Absorbers ............................ 1-90
1.18.1.2 Quenchers ............................... 1-91
1.18.1.3 Hydroperoxide Decomposers ............... 1-92
1.18.1.4 Free-Radical Scavengers ................. 1-93
1.19 Light Stabilizers for Selected Plastics ................. 1-96
1.19.1 Polypropylene .................................... 1-96
1.19.2 Polyethylene ..................................... 1-96
1.19.3 Styrenic Polymers ................................ 1-97
1.19.4 Polyvinyl Chloride) .............................. 1-97
1.19.5 Polycarbonate .................................... 1-98
1.19.6 Polyacrylates .................................... 1-98
1.19.7 Polyacetal ....................................... 1-98
1.19.8 Polyurethanes .................................... 1-98
1.19.7 Polyacetal ....................................... 1-98
1.19.8 Polyurethanes .................................... 1-98
1.19.9 Polyamides ....................................... 1-99
1.20 Diffusion and Permeability .............................. 1-99
1.20.1 Diffusion ....................................... 1-100
1.20.2 Permeability .................................... 1-100
1.21 Polymer Compounding .................................... 1-101
1.21.1 Fillers ......................................... 1-103
1.22 Plasticizers ........................................... 1-104
1.22.1 Phthalic Acid Esters ............................ 1-108
1.22.2 Phosphoric Acid Esters .......................... 1-108
1.22.3 Fatty Acid Esters ............................... 1-108
1.22.4 Polymeric Plasticizers .......................... 1-109
1.22.5 Miscellaneous Plasticizers ...................... 1-110
1.23 Antistatic Agents ...................................... 1-111
1.23.1 External Antistatic Agents ...................... 1-111
1.23.2 Internal Antistatic Agents ...................... 1-112
1.23.3 Chemical Composition of Antistatic Agents ....... 1-112
1.23.3.1 Antistatic Agents Containing
Nitrogen ............................... 1-113
1.23.3.2 Antistatic Agents Containing
Phosphorus ............................. 1-114
1.23.3.3 Antistatic Agents Containing Sulfur .... 1-115
1.23.3.4 Betaine-Type Antistatic Agents ......... 1-115
1.23.3.5 Nonionic Antistatic Agents ............. 1-115
1.24 Flame Retardants ....................................... 1-115
1.24.1 Halogen Compounds ............................... 1-116
1.24.2 Phosphorus Compounds ............................ 1-117
1.24.3 Halogen-Antimony Synergetic Mixtures ............ 1-118
1.24.4 Intumescent Flame Retardants .................... 1-119
1.25 Smoke Suppressants ..................................... 1-119
1.26 Colorants .............................................. 1-119
1.27 Antimicrobials ......................................... 1-120
1.28 Toxicity of Plastics ................................... 1-121
1.28.1 Plastic Devices in Pharmacy and Medicine ........ 1-121
1.28.1.1 Packing ................................ 1-122
1.28.1.2 Tubings and Blood Bag Assemblies ....... 1-122
1.28.1.3 Implants ............................... 1-122
1.28.1.4 Adhesives .............................. 1-122
1.28.1.5 Dental Materials ....................... 1-122
1.28.1.6 Nanomedicines and Drug Delivery ........ 1-123
1.28.2 Biodegradable Plastics .......................... 1-124
1.28.3 Oxo-Biodegradable Plastics ...................... 1-124
1.28.4 Toxicity of Plastic Combustion Products ......... 1-125
1.28.5 Toxicity Testing ................................ 1-125
References ............................................. 1-125
2 Fabrication Processes .................................... 2-1
2.1 Types of Processes ....................................... 2-1
2.2 Tooling for Plastics Processing .......................... 2-1
2.2.1 Types of Mold ..................................... 2-2
2.2.2 Types of Dies ..................................... 2-2
2.2.3 Tool Design ....................................... 2-3
2.3 Compression Molding ...................................... 2-4
2.3.1 Open Flash ........................................ 2-5
2.3.2 Fully Positive .................................... 2-5
2.3.3 Semipositive ...................................... 2-5
2.3.4 Process Applicability ............................. 2-5
2.4 Transfer Molding ......................................... 2-6
2.4.1 Ejection of Molding ............................... 2-8
2.4.2 Heating System .................................... 2-8
2.4.3 Types of Presses .................................. 2-9
2.4.4 Preheating ........................................ 2-9
2.4.5 Preforming ....................................... 2-10
2.4.6 Flash Removal .................................... 2-10
2.5 Injection Molding of Thermoplastics ..................... 2-10
2.5.1 Types of Injection Units ......................... 2-11
2.5.2 Clamping Units ................................... 2-13
2.5.3 Molds ............................................ 2-13
2.5.3.1 Mold Designs ............................ 2-13
2.5.3.2 Number of Mold Cavities ................. 2-14
2.5.3.3 Runners ................................. 2-15
2.5.3.4 Gating .................................. 2-15
2.5.3.5 Venting ................................. 2-17
2.5.3.6 Parting Line ............................ 2-17
2.5.3.7 Cooling ................................. 2-17
2.5.3.8 Ejection ................................ 2-17
2.5.3.9 Standard Mold Bases ..................... 2-18
2.5.4 Structural Foam Injection Molding ................ 2-18
2.5.5 Co-Injection (Sandwich) Molding .................. 2-18
2.5.6 Gas-Assisted Injection Molding ................... 2-20
2.6 Injection Molding of Thermosetting Resins ............... 2-21
2.6.1 Screw-Injection Molding of Thermosetting Resins .. 2-21
2.7 Extrusion ............................................... 2-22
2.7.1 Extruder Capacity ................................ 2-23
2.7.2 Extruder Design and Operation .................... 2-24
2.7.2.1 Typical Screw Construction .............. 2-24
2.7.2.2 Screw Zones ............................. 2-24
2.7.2.3 Motor Drive ............................. 2-25
2.7.2.4 Heating ................................. 2-25
2.7.2.5 Screw Design ............................ 2-25
2.7.3 Multiple-Screw Extruders ......................... 2-28
2.7.4 Blown-Film Extrusion ............................. 2-28
2.7.5 Flat Film or Sheet Extrusion ..................... 2-29
2.7.6 Pipe or Tube Extrusion ........................... 2-32
2.7.7 Wire and Cable Coverings ......................... 2-33
2.7.8 Extrusion Coating ................................ 2-33
2.7.9 Profile Extrusion ................................ 2-34
2.8 Blow Molding ............................................ 2-34
2.8.1 Extrusion Blow Molding ........................... 2-35
2.8.2 Injection Blow Molding ........................... 2-35
2.8.3 Blow Molds ....................................... 2-37
2.9 Calendering ............................................. 2-37
2.10 Spinning of Fibers ...................................... 2-38
2.10.1 Melt Spinning .................................... 2-39
2.10.2 Dry Spinning ..................................... 2-40
2.10.3 Wet Spinning ..................................... 2-40
2.10.4 Cold Drawing of Fibers ........................... 2-42
2.11 Thermoforming ........................................... 2-42
2.11.1 Vacuum Forming ................................... 2-42
2.11.2 Pressure Forming ................................. 2-42
2.11.3 Mechanical Forming ............................... 2-43
2.12 Casting Processes ....................................... 2-44
2.12.1 Simple Casting ................................... 2-44
2.12.2 Plastisol Casting ................................ 2-45
2.12.2.1 Dip Casting ............................. 2-46
2.12.2.2 Slush Casting ........................... 2-46
2.12.2.3 Rotational Casting ...................... 2-47
2.13 Reinforcing Processes ................................... 2-47
2.13.1 Molding Methods ................................. 2-47
2.13.1.1 Hand Lay-Up or Contact Molding .......... 2-48
2.13.1.2 Spray-Up ................................ 2-49
2.13.1.3 Matched Metal Molding ................... 2-49
2.13.1.4 Vacuum-Bag Molding ...................... 2-50
2.13.1.5 Pressure-Bag Molding .................... 2-50
2.13.1.6 Continuous Pultrusion ................... 2-50
2.13.1.7 Filament Winding ........................ 2-50
2.13.1.8 Prepreg Molding ......................... 2-52
2.13.2 Fibrous Reinforcements .......................... 2-55
2.13.2.1 Glass Fibers ............................ 2-55
2.13.2.2 Graphite Carbon Fibers .................. 2-56
2.13.2.3 Fiber Manufacture ....................... 2-57
2.13.2.4 Properties and Applications ............. 2-59
2.13.2.5 Aramid Fibers ........................... 2-59
2.13.2.6 Applications ............................ 2-60
2.13.2.7 Extended-Chain Polyethylene Fibers ...... 2-60
2.14 Reaction Injection Molding .............................. 2-62
2.14.1 Machinery ........................................ 2-64
2.14.2 Polyurethanes .................................... 2-64
2.14.3 Nylons ........................................... 2-65
2.15 Structural Reaction Injection Molding ................... 2-65
2.15.1 Applications ..................................... 2-66
2.16 Resin Transfer Molding .................................. 2-66
2.17 Foaming Processes ....................................... 2-67
2.17.1 Rigid Foam Blowing Agents ........................ 2-69
2.17.2 Polystyrene Foams ................................ 2-69
2.17.2.1 Extruded Polystyrene Foam ............... 2-70
2.17.2.2 Expandable Polystyrene .................. 2-70
2.17.2.3 Structural Foams ........................ 2-71
2.17.3 Polyolefin Foams ................................. 2-72
2.17.4 Polyurethane Foams ............................... 2-76
2.17.4.1 Flexible Polyurethane Foams ............. 2-76
2.17.4.2 Rigid and Semirigid Foams ............... 2-79
2.17.5 Foamed Rubber .................................... 2-80
2.17.6 Epoxy Resins ..................................... 2-80
2.17.7 Urea-Formaldehyde Foams .......................... 2-81
2.17.8 Silicone Foams ................................... 2-82
2.17.9 Phenolic Foams ................................... 2-83
2.17.10 Poly(Vinyl Chloride) Foams ...................... 2-83
2.17.11 Special Foams ................................... 2-86
2.18 Rubber Compounding and Processing Technology ............ 2-88
2.18.1 Compounding Ingredients .......................... 2-88
2.18.1.1 Processing Aids ......................... 2-94
2.18.1.2 Fillers ................................. 2-95
2.18.2 Mastication and Mixing ........................... 2-96
2.18.2.1 Open Mill ............................... 2-96
2.18.2.2 Internal Batch Mixers ................... 2-97
2.18.3 Reclaimed Rubber ................................. 2-99
2.18.4 Some Major Rubber Products ...................... 2-100
2.18.4.1 Tires .................................. 2-100
2.18.4.2 Belting and Hoses ...................... 2-102
2.18.4.3 Cellular Rubber Products ............... 2-104
2.19 Miscellaneous Processing Techniques .................... 2-104
2.19.1 Coating Processes ............................... 2-104
2.19.1.1 Fluidized Bed Coating .................. 2-106
2.19.1.2 Spray Coating .......................... 2-106
2.19.1.3 Electrostatic Spraying ................. 2-106
2.19.2 Powder Molding of Thermoplastics ................ 2-107
2.19.2.1 Static (Sinter) Molding ................ 2-107
2.19.2.2 Rotational Molding ..................... 2-107
2.19.2.3 Centrifugal Casting .................... 2-108
2.19.3 Adhesive Bonding of Plastics .................... 2-108
2.19.3.1 Solvent Cementing ...................... 2-109
2.19.3.2 Adhesive Bonding ....................... 2-110
2.19.3.3 Joining of Specific Plastics ........... 2-110
2.19.4 Welding ......................................... 2-114
2.19.4.1 Hot-Gas Welding ........................ 2-114
2.19.4.2 Fusion Welding ......................... 2-114
2.19.4.3 Friction Welding ....................... 2-115
2.19.4.4 High-Frequency Welding ................. 2-115
2.19.4.5 Ultrasonic Welding ..................... 2-115
2.20 Decoration of Plastics ................................. 2-115
2.20.1 Painting ........................................ 2-116
2.20.2 Printing ........................................ 2-116
2.20.2.1 Gravure Printing ....................... 2-116
2.20.2.2 Flexography ............................ 2-117
2.20.2.3 Screen Process Printing ................ 2-117
2.20.2.4 Pad Printing ........................... 2-117
2.20.3 Hot Stamping .................................... 2-117
2.20.4 In-Mold Decorating .............................. 2-118
2.20.5 Embossing ....................................... 2-118
2.20.6 Electroplating .................................. 2-119
2.20.7 Vacuum Metallizing .............................. 2-119
References ............................................. 2-120
3 Plastics Properties and Testing .......................... 3-1
3.1 Introduction ............................................. 3-1
3.2 Mechanical Properties .................................... 3-1
3.2.1 Stress and Strain ................................. 3-2
3.2.2 Stress-Strain Behavior ............................ 3-4
3.2.3 Viscoelastic Behavior of Plastics ................. 3-7
3.2.3.1 Modulus and Compliance ................... 3-8
3.2.4 Stress-Strain-Time Behavior ....................... 3-8
3.2.4.1 The WLF Equations ........................ 3-9
3.2.5 Creep Behavior ................................... 3-11
3.2.6 Maxwell Model .................................... 3-12
3.2.6.1 Stress-Strain Relation .................. 3-13
3.2.6.2 Generalized Maxwell Model ............... 3-15
3.2.7 Kelvin or Voigt Model ............................ 3-17
3.2.7.1 Stress-Strain Relation .................. 3-18
3.2.8 Four-Element Model ............................... 3-19
3.2.9 Zener Model ...................................... 3-20
3.2.10 Superposition Principle .......................... 3-21
3.2.11 Isometric and Isochronous Curves ................. 3-22
3.2.12 Pseudoelastic Design Method ...................... 3-23
3.2.13 Effect of Temperature ............................ 3-26
3.2.14 Time-Temperature Superposition ................... 3-26
3.2.15 Dynamic Mechanical Properties .................... 3-28
3.2.15.1 Maxwell Element ......................... 3-29
3.2.15.2 Terminology of Dynamic Mechanical
Experiments ............................. 3-32
3.2.15.3 Dynamic Mechanical Behavior at Thermal
Transitions ............................. 3-34
3.2.16 Rheological Behavior ............................. 3-35
3.2.16.1 Classification of Fluid Behavior ........ 3-36
3.2.16.2 Effect of Shear Rate on Viscosity ....... 3-39
3.2.16.3 Effect of Molecular Weight on
Viscosity ............................... 3-39
3.2.16.4 Effect of Temperature on Polymer
Viscosity ............................... 3-40
3.2.16.5 Effect of Pressure on Viscosity ......... 3-41
3.2.16.6 Wrissenberg Effects ..................... 3-41
3.2.16.7 Irregular Flow or Melt Fracture ......... 3-42
3.2.17 Measurement of Viscosity ......................... 3-42
3.2.17.1 Rotational Viscometers .................. 3-43
3.2.17.2 Capillary Rheometers .................... 3-44
3.2.18 Plastics Fractures ............................... 3-46
3.2.19 Impact Behavior of Plastics ...................... 3-46
3.2.20 Fatigue of Plastics .............................. 3-50
3.2.21 Hardness ......................................... 3-52
3.2.22 Indentation Hardness ............................. 3-52
3.2.22.1 Brinell Hardness Number ................. 3-52
3.2.22.2 Vickers Hardness Number ................. 3-53
3.2.22.3 Knoop Hardness Number ................... 3-53
3.2.22.4 Rockwell Hardness Number ................ 3-53
3.2.22.5 Barcol Hardness ......................... 3-53
3.2.22.6 Durometer Hardness ...................... 3-54
3.2.23 Rebound Hardness ................................. 3-54
3.2.24 Scratch Hardness ................................. 3-55
3.2.25 Stress Corrosion Cracking of Polymers ............ 3-55
3.3 Reinforced Plastics ..................................... 3-57
3.3.1 Types of Reinforcement ........................... 3-58
3.3.2 Types of Matrix .................................. 3-58
3.3.3 Analysis of Reinforced Plastics .................. 3-58
3.3.3.1 Continuous Fibers ....................... 3-59
3.3.3.2 Discontinuous Fibers .................... 3-62
3.3.3.3 Fiber Length Less than Ic ............... 3-64
3.3.3.4 Fiber Length Equal to Ic ................ 3-65
3.3.3.5 Fiber Length Greater than Ic ............ 3-65
3.3.4 Deformation Behavior of Fiber-Reinforced
Plastic .......................................... 3-66
3.3.5 Fracture of Fiber-Reinforced Plastics ............ 3-66
3.3.5.1 Tension ................................. 3-67
3.3.5.2 Compression ............................. 3-67
3.3.5.3 Flexure or Shear ........................ 3-67
3.3.6 Fatigue Behavior of Reinforced Plastics .......... 3-68
3.3.7 Impact Behavior of Reinforced Plastics ........... 3-68
3.4 Electrical Properties .................................... 3-68
3.4.1 Dielectric Strength .............................. 3-69
3.4.2 Insulation Resistance ............................ 3-70
3.4.3 Arc Resistance ................................... 3-71
3.4.4 Dielectric Constant .............................. 3-72
3.4.4.1 Polarization and Dipole Moment .......... 3-74
3.4.4.2 Dielectric Constant versus Frequency .... 3-76
3.4.4.3 Dielectric Constant versus
Temperature ............................. 3-76
3.4.4.4 Dielectric Losses ....................... 3-77
3.4.4.5 Dielectric Losses of Polar Polymers ..... 3-78
3.5 Optical Properties ...................................... 3-78
3.5.1 Optical Clarity .................................. 3-79
3.5.2 Index of Refraction .............................. 3-80
3.5.3 Piped Lighting Effect ............................ 3-81
3.5.4 Stress-Optical Characteristics ................... 3-83
3.6 Thermal Properties ...................................... 3-83
3.6.1 Specific Heat .................................... 3-83
3.6.2 Thermal Expansion ................................ 3-84
3.6.3 Thermal Conductivity ............................. 3-86
3.6.4 Transition Temperatures and Temperature
Limitations ...................................... 3-88
3.6.5 Standard Properties of Plastics .................. 3-90
3.7 Identification of Common Plastics ....................... 3-91
3.7.1 Behaviors on Heating and Ignition ................ 3-91
3.7.2 Tests for Characteristic Elements ................ 3-92
3.7.3 Specific Tests ................................... 3-95
References ............................................. 3-102
4 Industrial Polymers ...................................... 4-1
4.1 Introduction ............................................. 4-1
4.2 Part I: Addition Polymers ................................ 4-2
4.2.1 Polyolefins ....................................... 4-3
4.2.1.1 Polyethylene ............................. 4-3
4.2.1.2 Polypropylene ............................ 4-9
4.2.1.3 Polyallomer ............................. 4-15
4.2.1.4 Polyvinyl Chloride) ..................... 4-16
4.2.1.5 Poly(Vinylidene Chloride) ............... 4-24
4.2.1.6 Polytetrafluoroethylene and Other
Fluoropolymers .......................... 4-25
4.2.1.7 Polyisobutylene ......................... 4-29
4.2.1.8 Polystyrene ............................. 4-30
4.2.1.9 Polybutadiene (Butadiene Rubber) ........ 4-31
4.2.1.10 Polyisoprene ............................ 4-31
4.2.1.11 Polychloroprene ......................... 4-32
4.2.2 Olefin Copolymers ................................ 4-32
4.2.2.1 Styrene-Butadiene Rubber ................ 4-32
4.2.2.2 Nitrile Rubber .......................... 4-33
4.2.2.3 Ethylene-Propylene-Elastomer ............ 4-33
4.2.2.4 Butyl Rubber ............................ 4-35
4.2.2.5 Thermoplastic Elastomers ................ 4-35
4.2.2.6 Fluoroelastomers ........................ 4-38
4.2.2.7 Styrene-Acrylonitrile Copolymer ......... 4-39
4.2.2.8 Acrylonitrile-Butadiene-Styrene
Terpolymer .............................. 4-39
4.2.2.9 Ethylene-Methacrylic Acid Copolymers
(Ionomers) .............................. 4-42
4.2.3 Acrylics ......................................... 4-43
4.2.3.1 Polyacrylonitrile ....................... 4-43
4.2.3.2 Polyacrylates ........................... 4-44
4.2.3.3 Polymethacrylates ....................... 4-45
4.2.3.4 Polyacrylamide .......................... 4-47
4.2.3.5 Poly(Acrylic Acid) and
Poly(Methacrylic Acid) .................. 4-48
4.2.3.6 Acrylic Adhesives ....................... 4-49
4.2.4 Vinyl Polymers ................................... 4-50
4.2.4.1 Poly(Vinyl Acetate) ..................... 4-50
4.2.4.2 Poly(Vinyl Alcohol) ..................... 4-52
4.2.4.3 Poly(Vinyl Acetals) ..................... 4-53
4.2.4.4 Poly(Vinyl Cinnamate) ................... 4-53
4.2.4.5 Poly(Vinyl Ethers) ...................... 4-54
4.2.4.6 Poly(Vinyl Pyrrolidone) ................. 4-54
4.2.4.7 Poly(Vinyl Carbazole) ................... 4-54
4.3 Part II: Condensation Polymers ..................... 4-55
4.3.1 Polyesters ...................................... 4-55
4.3.1.1 Poly(Ethylene Terephthalate) ............ 4-55
4.3.1.2 Poly(Butylene Terephthalate) ............ 4-57
4.3.1.3 Poly(Dihydroxymethylcyclohexyl
Terephthalate) .......................... 4-58
4.3.1.4 Unsaturated Polyesters .................. 4-59
4.3.1.5 Aromatic Polyesters ..................... 4-66
4.3.1.6 Wholly Aromatic Copolyester ............. 4-68
4.3.1.7 Polycarbonates .......................... 4-69
4.3.2 Polyamides ....................................... 4-71
4.3.2.1 Aliphatic Polyamides .................... 4-72
4.3.2.2 Aromatic Polyamides ..................... 4-80
4.3.2.3 Polyimides .............................. 4-82
4.3.3 Formaldehyde Resins .............................. 4-87
4.3.3.1 Phenol-Formaldehyde Resins .............. 4-88
4.3.3.2 Urea-Formaldehyde Resins ................ 4-92
4.3.3.3 Melamine-Formaldehyde Resins ............ 4-96
4.3.4 Polyurethanes .................................... 4-97
4.3.4.1 Polyurethane Rubbers and Spandex
Fibers .................................. 4-99
4.3.4.2 Flexible Polyurethane Foam ............. 4-103
4.3.4.3 Rigid and Semirigid Polyurethane Foams . 4-104
4.3.4.4 Polyurethane Coatings .................. 4-105
4.3.5 Ether Polymers .................................. 4-106
4.3.5.1 Polyacetal ............................. 4-107
4.3.5.2 Poly(Ethylene Oxide) ................... 4-109
4.3.5.3 Applications ........................... 4-110
4.3.5.4 Polypropylene Oxide) ................... 4-112
4.3.5.5 Epoxy Resins ........................... 4-114
4.3.5.6 Poly(Phenylene Oxide) .................. 4-126
4.3.6 Cellulosic Polymers ............................. 4-128
4.3.6.1 Regenerated Cellulose .................. 4-128
4.3.6.2 Cellulose Nitrate ...................... 4-129
4.3.6.3 Cellulose Acetate ...................... 4-130
4.3.6.4 Other Cellulose Esters ................. 4-131
4.3.6.5 Cellulose Ethers ....................... 4-131
4.3.7 Sulphide Polymers ............................... 4-132
4.3.7.1 Polysulfides ........................... 4-132
4.3.7.2 Poly(Phenylene Sulfide) ................ 4-133
4.3.8 Polysulfone ..................................... 4-134
4.3.8.1 Properties ............................. 4-135
4.3.9 Polether Ether Ketone ........................... 4-136
4.3.10 Polybenzimidazole ............................... 4-138
4.3.11 Silicones and Other Inorganic Polymers .......... 4-139
4.3.11.1 Silicones .............................. 4-139
4.3.11.2 Polyphosphazenes ....................... 4-145
4.3.11.3 Polythiazyl ............................ 4-146
4.3.12 Polyblends ...................................... 4-146
4.3.12.1 Prediction of Polyblend Properties ..... 4-150
4.3.12.2 Selection of Blend Components .......... 4-151
4.3.12.3 Compatibilization of Polymers .......... 4-152
4.3.12.4 Industrial Polyblends .................. 4-154
4.3.12.5 Nanoblends ............................. 4-156
4.3.13 Interpenetrating Polymer Networks ............... 4-157
4.3.13.1 Industrial IPNs ........................ 4-159
References ............................................. 4-159
5 Polymers in Special Uses ................................. 5-1
5.1 Introduction ............................................. 5-1
5.2 High-Temperature and Fire-Resistant Polymers ............. 5-1
5.2.1 Temperature-Resistant Polymers .................... 5-2
5.2.2 Fire-Resistant Polymers ........................... 5-4
5.3 Liquid Crystal Polymers .................................. 5-5
5.3.1 Thermotropic Main-Chain Liquid Crystal Polymers .. 5-11
5.3.2 Side-Chain Liquid Crystal Polymers ............... 5-13
5.3.3 Chiral Nematic Liquid Crystal Polymers ........... 5-14
5.3.4 Properties of Commercial LCPs .................... 5-17
5.3.5 Applications ..................................... 5-19
5.4 Electroactive Polymers .................................. 5-19
5.4.1 Filled Polymers .................................. 5-19
5.4.1.1 EMI Shielding ........................... 5-22
5.4.1.2 Conductive Coating ...................... 5-24
5.4.1.3 Signature Materials ..................... 5-25
5.4.2 Inherently Conductive Polymers ................... 5-26
5.4.2.1 Doping .................................. 5-28
5.4.2.2 Conducting Mechanisms ................... 5-33
5.4.2.3 Applications ............................ 5-35
5.4.3 Photoconductive Polymers ......................... 5-43
5.4.4 Polymers in Fiber Optics ......................... 5-44
5.4.5 Polymers in Nonlinear Optics ..................... 5-47
5.4.6 Langmuir-Blodgett Films .......................... 5-48
5.4.7 Piezo-and Pyroelectric Polymers .................. 5-49
5.4.7.1 Applications ............................ 5-51
5.4.8 Polymeric Electrolytes ........................... 5-53
5.5 Polymers in Photoresist Applications .................... 5-55
5.5.1 Negative Photoresists ............................ 5-58
5.5.2 Positive Photoresists ............................ 5-61
5.5.2.1 Near-UV Application ..................... 5-61
5.5.2.2 Mid-and Deep-UV Photoresists ............ 5-63
5.5.3 Electron Beam Resists ............................ 5-66
5.5.4 Plasma-Developable Photoresists .................. 5-67
5.6 Photoresist Applications for Printing ................... 5-68
5.6.1 Printing Plates .................................. 5-68
5.6.1.1 Relief or Raised-Image Plates ........... 5-68
5.6.1.2 Photolithography/Planographic Plates .... 5-70
5.6.1.3 Photogravure ............................ 5-70
5.6.2 Photoengraving ................................... 5-70
5.6.3 Printed Circuits ................................. 5-71
5.6.4 Collotype and Proofing Systems ................... 5-71
5.7 Optical Information Storage ............................. 5-71
5.8 Polymers in Adhesives ................................... 5-72
5.8.1 Solvent-Based Adhesives .......................... 5-73
5.8.2 Water-Based Adhesives ............................ 5-75
5.8.3 Hot Melt Adhesives ............................... 5-76
5.8.4 Radiation-Curable Adhesives ...................... 5-76
5.9 Degradable Polymers ..................................... 5-77
5.9.1 Packaging Application ............................ 5-79
5.9.2 Medical and Related Applications ................. 5-80
5.9.2.1 Synthetic Polymers ...................... 5-80
5.9.2.2 Controlled Release Agents ............... 5-81
5.9.2.3 Tissue Engineering ...................... 5-82
5.10 Ionic Polymers .......................................... 5-84
5.10.1 Physical Properties and Applications ............. 5-86
5.10.1.1 Ionic Cross-Linking ..................... 5-86
5.10.1.2 Ion-Exchange ............................ 5-86
5.10.1.3 Hydrophilicity .......................... 5-88
5.10.2 Ionomers ......................................... 5-91
5.10.2.1 Polyethylene Ionomers ................... 5-91
5.10.2.2 Elastomeric Ionomers .................... 5-93
5.10.2.3 Ionomers Based on
Polytetrafluoroethylene ................. 5-94
5.10.2.4 Ionomers Based on Polysulfones .......... 5-96
5.10.2.4 Ionomers Based on Polysulfones .......... 5-96
5.10.3 Polyelectrolytes ................................. 5-97
5.10.3.1 Ion-Exchangers ......................... 5-97
5.10.3.2 Applications .......................... 5-102
5.10.3.3 Polycarboxylates ....................... 5-105
5.10.3.4 Integral Polyelectrolytes .............. 5-105
5.11 Scavenger Resins ....................................... 5-106
5.12 Synthetic Polymer Membranes ............................ 5-107
5.12.1 Membrane Preparation ............................ 5-107
5.12.1.1 Wet-Extrusion Process .................. 5-107
5.12.1.2 Hollow-Fiber Membranes ................. 5-110
5.12.2 Membrane Modules ................................ 5-111
5.12.3 Applications .................................... 5-113
5.13 Hydrogels and Smart Polymers ........................... 5-115
5.13.1 Smart Polymers .................................. 5-117
5.14 Dendritic Polymers ..................................... 5-123
5.14.1 Applications .................................... 5-124
5.15 Shape Memory Polymers .................................. 5-126
5.16 Microencapsulation ..................................... 5-128
5.16.1 Processes for Microencapsulation ................ 5-129
5.16.1.1 Complex Coacervation ................... 5-129
5.16.1.2 Polymer-Polymer Incompatibility ........ 5-130
5.16.1.3 Interfacial and in Situ
Polymerization ......................... 5-130
5.16.1.4 Spray Drying ........................... 5-133
5.16.1.5 Fluidized-Bed Coating .................. 5-134
5.16.1.6 Co-Extrusion Capsule Formation ......... 5-135
5.16.1.7 Other Processes ........................ 5-136
5.16.2 Applications .................................... 5-137
5.17 Polymer Nanocomposites ................................. 5-138
5.17.1 Preparation of Polymer Nanocomposites ........... 5-139
5.17.2 Applications of Polymer Nanocomposites .......... 5-144
5.18 Wood-Polymer Composites ................................ 5-146
5.18.1 WPC Feedstocks .................................. 5-147
5.18.1.1 Wood ................................... 5-147
5.18.1.2 Plastics ............................... 5-148
5.18.1.3 Compounded Pellets ..................... 5-148
5.18.1.4 Additives .............................. 5-148
5.18.2 Manufacture of WPC Products ..................... 5-148
5.18.2.1 Compounding ............................ 5-149
5.18.2.2 Extrusion .............................. 5-149
5.18.3 Properties of WPC Products ...................... 5-151
5.18.4 Applications of WPC Products .................... 5-152
5.19 Polymerization-Filled Composites ....................... 5-154
References ............................................. 5-155
6 Recycling of Polymers .................................... 6-1
6.1 Introduction ............................................. 6-1
6.2 Outline of Recycling Methods ............................. 6-2
6.3 Recycling of Poly (Ethylene Terephthalate) ............... 6-8
6.3.1 Direct Reuse ...................................... 6-8
6.3.2 Reuse after Modification .......................... 6-9
6.3.2.1 Glycolysis .............................. 6-10
6.3.2.2 Methanolysis ............................ 6-12
6.3.2.3 Ammonolysis ............................. 6-12
6.3.2.4 Hydrolysis .............................. 6-12
6.3.2.5 Depolymerization in Supercritical
Fluids .................................. 6-13
6.3.2.6 Enzymatic Depolymerization .............. 6-13
6.3.3 Incineration ..................................... 6-14
6.4 Recycling of Polyurethanes .............................. 6-15
6.4.1 Thermopressing Process ........................... 6-15
6.4.2 Kneader Process .................................. 6-16
6.4.3 Hydrolysis ....................................... 6-17
6.4.3.1 Glycolysis .............................. 6-17
6.4.3.2 Ammonolysis ............................. 6-17
6.5 Recycling of Poly (Vinyl Chloride) ...................... 6-19
6.5.1 Characterization of Used PVC ..................... 6-19
6.5.2 In-Line PVC Scrap ................................ 6-20
6.5.3 PVC Floor Coverings .............................. 6-22
6.5.4 PVC Roofing Sheets ............................... 6-22
6.5.5 Post-Consumer PVC ................................ 6-22
6.6 Recycling of Cured Epoxies .............................. 6-23
6.7 Recycling of Mixed Plastics Waste ....................... 6-23
6.7.1 Direct Reuse ..................................... 6-24
6.7.2 Homogeneous Fractions ............................ 6-27
6.7.3 Liquefaction of Mixed Plastics ................... 6-27
6.8 Post-Consumer Polyethylene Films ........................ 6-28
6.9 Recycling of Ground Rubber Tires ........................ 6-29
6.10 Recycling of Car Batteries .............................. 6-31
6.11 Plastic Recycling Equipment and Machinery ............... 6-31
6.11.1 Plastocompactor .................................. 6-32
6.11.2 Debaling and Initial Size Reduction .............. 6-32
6.11.2.1 Shredder ................................ 6-33
6.11.2.2 Cutter or Guillotine .................... 6-33
6.11.2.3 Screw Shredder .......................... 6-33
6.11.2.4 Granulators ............................. 6-33
6.11.2.5 Fine Grinding ........................... 6-34
6.11.3 Cleaning and Selection .......................... 6-34
6.11.3.1 Dry Separation .......................... 6-35
6.11.3.2 Wet Separation .......................... 6-36
6.11.3.3 Other Methods ........................... 6-37
6.11.4 Resin Detectors: Type and Configuration .......... 6-37
6.11.5 Automatic Sortation .............................. 6-39
6.11.5.1 PVC/PETand Commingled Plastics
Sortation ............................... 6-39
6.11.6 Recycle Installations ............................ 6-41
References .............................................. 6-41
7 Trends in Polymer Applications ........................... 7-1
7.1 Introduction ............................................. 7-1
7.2 Polymers in Packaging .................................... 7-2
7.2.1 Retorting ......................................... 7-4
7.2.2 Asceptic Packaging ................................ 7-4
7.2.3 Hot-Filling ....................................... 7-5
7.2.4 Controlled-Atmosphere Packaging ................... 7-5
7.2.5 High-Barrier Films ................................ 7-5
7.2.6 Oxygen Scavenger-Based Packaging .................. 7-6
7.2.7 Plastic Bottles ................................... 7-6
7.2.8 Chemical Containers ............................... 7-7
7.2.9 Dual Ovenables .................................... 7-7
7.2.10 Closures .......................................... 7-8
7.2.11 Biodegradable Packaging ........................... 7-8
7.2.12 Pharmaceutics Packaging and Nanomedicines ......... 7-9
7.2.13 Wood-Plastic Composites .......................... 7-10
7.3 Polymers in Building and Construction
7.3.1 Roofing .......................................... 7-11
7.3.2 Flooring ......................................... 7-11
7.3.3 Windows .......................................... 7-12
7.3.4 Pipes ............................................ 7-13
7.3.5 Insulation ....................................... 7-13
7.3.6 Polymer-Concrete Composites ...................... 7-14
7.3.7 Wood-Plastic Composites .......................... 7-16
7.4 Polymers in Corrosion Prevention and Control ............ 7-16
7.4.1 Flue Gas Desulfurization ......................... 7-17
7.4.2 Chemical Resistant Masonry ....................... 7-17
7.4.3 Piping Systems ................................... 7-18
7.4.4 Boiler and Cooling Water Treatment ............... 7-18
7.4.5 Biodegradable Scale Inhibitor .................... 7-18
7.4.6 Reinforcing Steel in Concrete .................... 7-19
7.5 Plastics in Automotive Applications ..................... 7-20
7.5.1 Exterior Body Parts .............................. 7-20
7.5.2 Interior Components .............................. 7-21
7.5.3 Load-Bearing Parts ............................... 7-22
7.5.4 Under-the-Bonnet (Hood) .......................... 7-22
7.5.5 Future Trends .................................... 7-23
7.5.6 Polymer Nanocomposites ........................... 7-23
7.5.7 "Green" Composites ............................... 7-24
7.6 Polymers in Aerospace Applications ...................... 7-25
7.6.1 Carbon Fibers .................................... 7-25
7.6.2 Resins ........................................... 7-26
7.7 Polymers in Electrical and Electronic Applications ...... 7-27
7.7.1 Wire and Cable Insulation ........................ 7-28
7.7.2 Polymer Insulators ............................... 7-29
7.7.3 Printed Circuit Boards ........................... 7-29
7.7.4 Connectors ....................................... 7-29
7.7.5 Enclosures ....................................... 7-30
7.7.6 Optical Fibers ................................... 7-30
7.7.7 Information Storage Discs ........................ 7-31
7.7.8 Polymeric FET and LED ............................ 7-32
7.8 Polymers in Agriculture and Horticulture ................ 7-33
7.8.1 Plastic Film ..................................... 7-33
7.8.2 Plastic Crates ................................... 7-34
7.8.3 Building ......................................... 7-34
7.8.4 Pipes and Hoses .................................. 7-34
7.8.5 Greenhouses ...................................... 7-35
7.9 Polymers in Domestic Appliances and Business Machines ... 7-35
7.9.1 Large Appliances ................................. 7-36
7.9.2 Small Appliances ................................. 7-37
7.9.3 Business Equipment ............................... 7-37
7.9.4 Air Filters ...................................... 7-38
7.9.5 Solar Systems .................................... 7-38
7.10 Polymers in Medical and Biomedical Applications ......... 7-39
7.10.1 Medical Packaging ................................ 7-39
7.10.2 Nontoxic Sterilizable Items ...................... 7-40
7.10.3 Biodegradable Polymers ........................... 7-41
7.10.4 Conducting Polymer Nanotubes ..................... 7-41
7.10.5 Biomimetic Actuators ............................. 7-42
7.10.6 Dental Resin Composites .......................... 7-43
7.10.7 Appliances ....................................... 7-43
7.10.8 Disposables ...................................... 7-43
7.11 Polymers in Marine and Offshore Applications ............ 7-44
7.11.1 Cables ........................................... 7-44
7.11.2 Coatings ......................................... 7-44
7.11.3 Other Applications ............................... 7-45
7.12 Polymers in Sport ....................................... 7-45
7.12.1 Synthetic Surfaces ............................... 7-45
7.12.2 Footwear ......................................... 7-46
7.12.3 Equipment ........................................ 7-46
References .............................................. 7-47
Appendices
Al Trade Names for Some Industrial Polymers ............ Al-1
A2 Commonly Used Abbreviations for Industrial Polymers . A2-1
A3 Index of Trade Names, Manufacturers, and Suppliers
of Antioxidants ..................................... A3-1
A4 Index of Trade Names, Manufacturers, and Suppliers
of Metal Deactivators ............................... A4-1
A5 Index of Trade Names, Manufacturers, and Suppliers
of Light Stabilizers ................................ A5-1
A6 Index of Trade Names and Suppliers of Frame
Retardants .......................................... A6-1
A7 Index of Trade Names and Suppliers of Foaming
Agents .............................................. A7-1
A8 Harmonic Motion of a Maxwell Model .................. A8-1
A9 Formulations of Flame-Retarded Selection
Thermoplastics ...................................... A9-1
A10 Formulations of Selected Rubber Compounds .......... A10-1
A11 Formulations of Selected PVC Compounds ............. Al1-1
A12 Formulations of Polyurethane Foams ................. A12-1
A13 Commercial Polymer Blends and Alloys ............... A13-1
A14 Conversion of Units ................................ A14-1
A15 Typical Properties of Polymers Used for Molding
and Extrusion ...................................... A15-1
A16 Typical Properties of Cross-Linked Rubber
Compounds .......................................... A16-1
A17 Typical Properties of Representative Textile
Fibers ............................................. A17-1
Index ......................................................... 1-1
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