Contents

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 (M, ) .......................................... 1-3 1.2.2 Weight-Average Molecular Weight (M, ) ........................................... 1-3

.......................................... 1.2.3 Viscosity-Average Molecular Weight (M, ) 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 T, ........................................................................ 1-31 1.9.2 Regions of Viscoelastic Behavior .................................................. 1-34 1.9.3 Factors Affecting T, ............................................................... 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 T,, .............................................................. 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 T,, and Tg ...................................................... 1-40 1.10 Designing a Polymer Structure for lmproved Properties ................................... 1-40 1.1 1 Cross-Linking of Polymer Chains ......................................................... 1-42

1.11 . 1 Reactions of Functional Groups ................................................... 1-42 1.1 1.2 Vulcanization ..................................................................... 1-45 1.1 1.3 Radiation Cross-Linking .......................................................... 1-49

..................................................... 1.11.4 Photochemical Cross-Linking 1-51 1.1 1.5 Ionic Cross-Linking ............................................................... 1-52

AdministratorText BoxRef. 668.4 CHA 4th ed.

Solubility Behavior of Polymers ........................................................... 1-53 1.12.1 Solubility Parameter .............................................................. 1-53 Effects of Corrosives on Polymers ......................................................... 1-60 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 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 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 Poly(Viny1 Chloride) .................................................. 1-85 1.16.3.10 Rubber ................................................................ 1-86

Metal Deactivators ........................................................................ 1-86 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

Light Stabilizers for Selected Plastics ...................................................... 1-96 1.19.1 Polypropylene .................................................................... 1-96 I . 19.2 Polyethylene ...................................................................... 1-96 1.19.3 Styrenic Polymers ................................................................. 1-97 1.19.4 Poly(Viny1 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 1.19.9 Polyamides ....................................................................... 1-99 Diffusion and Permeability ................................................................ 1-99 1.20.1 Diffusion ........................................................................ 1-100 1.20.2 Permeability ..................................................................... 1- 100 Polymer Compounding .................................................................. 1- 101 1.21.1 Fillers ............................................................................ 1-103 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 ........................................................ 1-1 10

Ref;

2 Fat 2.1 2.2

Antistatic Agents ......................................................................... 1-1 11 1.23.1 External Antistatic Agents ........................................................ 1- 11 1

1.23.2 Internal Antistatic Agents ........................................................ 1- 112 1.23.3 Chemical Composition of Antistatic Agents ...................................... 1 - 1 12

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 .................................... 1-1 15 1.23.3.4 Betaine-Type Antistatic Agents ......................................... 1 - 1 15 1.23.3.5 Nonionic Antistatic Agents ............................................. 1-1 15

1.24 Flame Retardants ........................................................................ 1 - 115 1.24.1 Halogen Compounds ............................................................ 1 - 1 16 1.24.2 Phosphorus Compounds ......................................................... 1- 117 1.24.3 Halogen-Antimony Synergetic Mixtures .......................................... 1-1 18 1.24.4 Intumescent Flame Retardants ................................................... 1- 119

1.25 Smoke Suppressants ..................................................................... 1-1 19 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 0x0-Biodegradable Plastics ...................................................... 1 - 124 1.28.4 Toxicity of Plastic Combustion Products ......................................... 1-125 1.28.5 Toxicity Testing .................................................................. 1 - 125

References ..................................................................................... 1 - 125

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 Injection Molding of Thermosetting Resins ................................................ 2-21 2.6.1 Screw-Injection Molding of Thermosetting Resins ................................. 2-21 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 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 Calendering ............................................................................... 2-37 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 Thermoforming ........................................................................... 2-42 2.1 1.1 Vacuum Forming ................................................................. 2-42 2.1 1.2 Pressure Forming ................................................................. 2-42 2.1 1.3 Mechanical Forming .............................................................. 2-43 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

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 2.1 3.1.6 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(Viny1 Chloride) Foams ..................................................... 2-83 2.17.1 1 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- 1 10 2.19.3.3 Toining of Specific Plastics ............................................. 2- 1 10

2.19.4 Welding ......................................................................... 2-1 14 2.19.4.1 Hot-Gas Welding ...................................................... 2- 1 14 2.19.4.2 Fusion Welding ........................................................ 2-1 14 2.19.4.3 Friction Welding ....................................................... 2- 1 15 2.19.4.4 High-Frequency Welding ............................................... 2-1 15 2.19.4.5 Ultrasonic Welding .................................................... 2- 115

2.20 Decoration of Plastics .................................................................... 2-1 15 2.20.1 Painting ......................................................................... 2-1 16 2.20.2 Printing ......................................................................... 2-1 16

2.20.2.1 Gravure Printing ....................................................... 2-1 16 2.20.2.2 Flexography ....................................................... 2- 11 7 2.20.2.3 Screen Process Printing ................................................ 2- 11 7 2.20.2.4 Pad Printing ........................................................... 2-1 17

2.20.3 Hot Stamping.. .................................................................. 2-1 17 2.20.4 In-Mold Decorating. ............................................................. 2-1 18 2.20.5 Embossing ....................................................................... 2-1 18 2.20.6 Electroplating .................................................................... 2- 119 2.20.7 Vacuum Metallizing .............................................................. 2- 119

References ..................................................................................... 2- 120

3 Plastics Properties a n d 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- 1 1 ................................................................... 3.26 Maxwell Model 3-12

.................................................... 3.2.6.1 Stressstrain 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 ................................................ 3.2.1 1 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 Weissenberg Effects 3-41

3.2.17 Measure

3.2.18 Plastics Fr 3.2.19 lmpact Be 3.2.20 Fatigue of Pl

.... 3.2.21 Hardness 3.2.22 Indentation H

B I I

!

3.2.23 Rebound H 3.2.24 Scratch Har 3.2.25 Stress Corrosi

3.3 Reinforced Plastics . . 3.3.1 TypesofRein 3.3.2 Types of Mat 3.3.3 Analys~s of R

3.3.3.1 COI 3.3.3.2 Dis 3.3.3.3 Fib 3.3.3.4 Flb 3.3.3.5 Fib

3.3.4 Deformation 3.3.5 Fracture of F

3.3.5.1 Tei 3.3.5.2 Cc 3.3.5.3 Fle

3.3.6 Fatigue Beha1 3.3.7 Impact Behav

3.4 Electrical Properties . 3.4.1 Dielectric Str 3.4.2 lnsulatlon Re 3.4.3 Arc Resistant 3.4.4 Dielectric Co

3.4.4.1 PO 3.4.4.2 Di 3.4.4.3 Di 3.4.4.4 Di 3.4.4.5 Di

3.5 Optical Properties.. 3.5.1 Optical Clar 3.5.2 Index of Rel 3.5.3 Piped L~ght 3.5.4 Stress-Optil

3.6 Thermal Properties 3.6.1 Specific He 3.6.2 Thermal Ex 3.6.3 Thermal C( 3.6.4 Transition ' 3.6.5 Standard P

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 Brine11 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 I, ................................................ 3-64 3.3.3.4 Fiber Length Equal to I, ................................................ 3-65 3.3.3.5 Fiber Length Greater than I, ............................................ 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 Poly(Viny1 Chloride) ..................................................... 4-16 4.2.1.5 Poly(Viny1idene 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 4.2.1.1 1 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 t 1 4.2.2.8 Acrylonitrile-Butadiene-Styrene Terpolymer ............................... 4-39 b

5 4.2.2.9 Ethylene-Methacrylic Acid Copolymers (Ionomers) ....................... 4-42 ?

4.2.3 Acrylics ............................................................................ 4-43 4.2.3.1 Polyacrylonitrile ........................................................... 4-43 1 4.2.3.2 Polyacrylates .............................................................. 4-44 ' 4.2.3.3 Polymethacrylates ......................................................... 4-45 4.2.3.4 Polyacrylamide ............................................................ 4-47 i 4.2.3.5 Poly(Acry1ic Acid) and Poly(Methacry1ic Acid) ............................ 4-48

.......................................................... 4.2.3.6 Acrylic Adhesives 4-49 4.2.4 Vinyl Polymers ..................................................................... 4-50

4.2.4.1 Poly(Viny1 Acetate) ........................................................ 4-50 4.2.4.2 Poly(Viny1 Alcohol) ....................................................... 4-52 4.2.4.3 Poly(Viny1 Acetals) ........................................................ 4-53 4.2.4.4 Poly(Viny1 Cinnamate) .................................................... 4-53 4.2.4.5 Poly(Viny1 Ethers) ......................................................... 4-54

................................................... 4.2.4.6 Poly(Viny1 Pyrrolidone) 4-54 4.2.4.7 Poly(Viny1 Carbazole) ..................................................... 4-54

4.3 Part 11: Condensation Polymers ........................................................... 4-55 .......................................................................... 4.3.1 Polyesters 4-55

4.3.1.1 Poly(Ethy1ene Terephthalate) .............................................. 4-55 4.3.1.2 Poly(Buty1ene 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

4.3.3 Formaldehyd

4.3.4 Polyurethanes

References ...............

5 Polymers in Special Use 5.1 Introduction ....... 5.2 High-Temperature a

5.2.1 Temperature 5.2.2 Fire-Resistal

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 ............................................................ 4-1 10 4.3.5.4 Poly(Propy1ene Oxide) .................................................. 4- 112 4.3.5.5 Epoxy Resins ........................................................... 4-1 14 4.3.5.6 Poly(Pheny1ene 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- 13 1

4.3.7 Sulphide Polymers ................................................................ 4- 132 4.3.7.1 Polysulfides .......................................................... 4-132 4.3.7.2 Poly(Pheny1ene 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 In'organic Polymers ........................................... 4-139

4.3.1 1.1 Silicones ................................................................ 4-139 4.3.1 1.2 Polyphosphazenes ....................................................... 4-145 4.3.1 1.3 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 I 5.3.5 Applications ...................................................................... 5-19

5.4 Electroactive Polymers .................................................................... 5-19 5.4.1 Filled Polymers ................................................................... 5-19 1

............................................................ 5-LL 5.4.1.2 Conductive Coating ...................................................... 5-24 5.4.1.3 Signature Materials ....................................................... 5-25

5.4.2 lnherently 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

5.5.2 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

5.6.4 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 P 6 5.8.4 Radiation-Curable Adhesives ...................................................... 5-76 r l .6 5.16.3 LSW ...................................................................... 5.9 Degradable Polymers 5-77 5.18.4 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 Aeents ................................................ 5-81 C-*i 5.9.2.3 Tissue Engineering .......................................................

5.10.1 Phys~cal Properties and Applications .............................................. 5-86 p.r 6.1 mum- 5.10.1.1 Ionic Cross-Linking 5-86 : p '7: 6.2 Outli-- ..................................................... 5.10.1.2 Ion-Exchange ........................................................... 5-86 $ . e 4 6 . 3 wc 5.10.1.3 Hydrophilicity .......................................................... 5-88 &'2 6.3.1 "

5.10.2 Ionorners ......................................................................... 5-91 I

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

5.10.3 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

5.1 1 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- 1 11 5.12.3 Applications ..................................................................... 5- 1 13

5.13 Hydrogels and Smart Polyn~ers .......................................................... 5- 115 5.13.1 Smart Polymers .................................................................. 5-1 17

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 Coace~a t ion ................................................. 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

6.4.3.1 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 Recvclina of Car Batteries ................................................................. 6-31 . " 6.1 1 Plastic Recycling Equipment and Machinery ............................................... 6-31 . . . .

6.1 1.1 Plastocompactor .................................................................. 6-32 6.1 1.2 Debaling and Initial Size Reduction ............................................... 6-32

6.11.2.1 Shredder ................................................................ 6-33 .... 76.1 Carbon 6.1 1.2.2 Cutter or Guillotine ..................................................... 6-33 6.1 1.2.3 Screw Shredder ......................................................... 6-33 6.1 1.2.4 Granulators ............................................................. 6-33 6.11.2.5 Fine Grinding ........................................................... 6-34

6.11.3 Cleaning and Selection ............................................................ 6-34 6.1 1.3.1 Dry Separation ......................................................... 6-35 6.1 1.3.2 Wet Separation ......................................................... 6-36 6.1 1.3.3 Other Methods ......................................................... 6-37

6.1 1.4 Resin Detectors: Type and Configuration .......................................... 6-37 6.1 1.5 Automatic Sortation .............................................................. 6-39

6.1 1.5.1 PVCIPET and Commingled Plastics Sortation ........................... 6-39 6.1 1.6 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

7.9.2 Small