The third edition has been updated and expanded, providing industrial chemists, technologists, environmental scientists and engineers with the most accurate, compact, and practical source on fluoropolymers. Highlighting existing and new industrial, military, medical and consumer goods applications, this edition adds more detailed information on equipment and processing conditions. It explores breakthroughs in understanding property-structure relationships, new polymerization techniques and the chemistry underlying polymers, such as melt-processable fluoroplastics. It also expands upon critical environmental aspects of fluoropolymers, including heat and radiation degradation, health effects, and recycling.
- Revised, updated and expanded to continue to provide the most accurate, compact and practical source on fluoropolymers.
- Explores breakthroughs in understanding property-structure relationships, new polymerization techniques and the chemistry underlying polymers.
- Fluoropolymers are high up on the specialty polymers group and due to their unique properties, are naturally part of the solution to industrial sustainability challenges.
- Describes the technology of fluoropolymers, including thermoplastic and elastomeric products.
- Expands upon critical environmental aspects of fluoropolymers and recycling of these special polymers
PART I OVERVIEW OF FLUOROPOLYMERS
2 Societal Benefits and Evolution of Fluoropolymers 2.1 Basic Fluoropolymer Properties 2.2 Examples of Fluoropolymer Properties 2.3 Automotive Applications 2.4 Aerospace Wire and Cable 2.5 Aircraft Fuel Hose 2.6 Heart Rhythm Management-ICD 2.7 Pediatric Heart Repair 2.8 Thread Sealant 2.9 Chemical Processing Industry-Lined Pipes, Fittings, and Vessels 2.10 Semiconductor Chip Fabrication 2.11 Biomedical Applications 2.12 PTFE Micropowders 2.13 Applications of Fluoropolymers in Transportation 2.14 Properties of Thermoplastic Fluoropolymers 2.15 Delving Deeper into Properties 2.16 Forces Affecting the Fluoropolymer Industries References
PART II THERMOPLASTIC FLUOROPOLYMERS
3 Synthesis and Properties of Monomers of Thermoplastic Fluoropolymers 3.1 Preparation of Tetrafluoroethylene 3.2 Properties of Tetrafluoroethylene 3.3 Preparation of Hexafluoropropylene 3.4 Properties of Hexafluoropropylene 3.5 Synthesis of Perfluoroalkylvinylethers (PAVEs) 3.6 Properties of Perfluoroalkylvinylethers 3.7 Synthesis of Chlorotrifluoroethylene (CTFE) 3.8 Properties of Chlorotrifluoroethylene 3.9 Synthesis of Vinylidene Fluoride (VDF) 3.10 Properties of Vinylidene Fluoride 3.11 Synthesis of Vinyl Fluoride (VF) 3.12 Properties of Vinyl Fluoride (VF) References
4 Polymerization of Commercial Thermoplastic Fluoropolymers 4.1 Polymerization of Tetrafluoroethylene 4.1.1 Granular Resins 4.1.2 Fine Powder Resins 4.1.3 Aqueous Dispersions 4.1.4 Filled Compounds 4.1.5 Modified PTFE 4.2 Fluorinated Ethylene Propylene (FEP) 4.2.1 Industrial Process for the Production of FEP 4.3 Perfluoroalkoxy (PFA) Resin 4.3.1 Industrial Process for the Production of Perfluoroalkoxy Resin 4.4 Polychlorotrifluoroethylene (PCTFE) 4.4.1 Industrial Process for the Production of PCTFE 4.5 Polyvinylidene Fluoride (PVDF) 4.5.1 Industrial Process for the Production of PVDF 4.6 Polyvinyl Fluoride 4.6.1 Industrial Process for the Production of Polyvinyl Fluoride 4.7 Ethylene Chlorotrifluoroethylene (ECTFE) Copolymer 4.7.1 Industrial Process for the Production of ECTFE 4.8 Ethylene Tetrafluoroethylene (ETFE) Copolymer 4.8.1 Industrial Process for the Production of ETFE 4.9 Terpolymers of TFE, HFP and VDF (THV Fluoroplastic) 4.10 Terpolymers and Quarterpolymers of HFP, TFE and Ethylene References
5 Properties of Commercial Fluoropolymers 5.1 Properties as Related to the Structure of Fluoropolymers 5.1.1 Fluoroplastics 18.104.22.168 Mechanical Properties 22.214.171.124 Optical Properties 5.1.2 Fluoroelastomers 5.2 Properties of Individual Commercial Fluoroplastics 5.2.1 Polytetrafluoroethylene 126.96.36.199 Molecular Weight 188.8.131.52 Molecular Conformation 184.108.40.206 Crystallinity and Melting Behavior 220.127.116.11 Mechanical Properties 18.104.22.168 Surface Properties 22.214.171.124 Absorption and Permeation 126.96.36.199 Electrical Properties 5.2.2 Modified Polytetrafluoroethylene 5.2.3 Copolymers of Tetrafluoroethylene and Hexafluoropropylene (FEP) 188.8.131.52 Mechanical Properties 184.108.40.206 Electrical Properties 220.127.116.11 Chemical Properties 18.104.22.168 Optical Properties 22.214.171.124 Other Properties 5.2.4 Copolymers of Tetrafluoroethylene and Perfluoroalkyl Ethers (PFA and MFA) 126.96.36.199 Physical and Mechanical Properties 188.8.131.52 Electrical Properties 184.108.40.206 Optical properties 220.127.116.11 Chemical Properties 5.2.5 Copolymers of Ethylene and Tetrafluoroethylene (ETFE) 18.104.22.168 Structure and Related Properties 22.214.171.124 Mechanical, Chemical and Other Properties 5.2.6 Polyvinylidene Fluoride (PVDF) 126.96.36.199 Mechanical Properties 188.8.131.52 Electrical Properties 184.108.40.206 Chemical Properties 5.2.7 Polychlorotrifluoroethylene (PCTFE) 220.127.116.11 Thermal Properties 18.104.22.168 Mechanical, Chemical and Other Properties 5.2.8. Copolymer of Ethylene and Chlorotrifluoroethylene (ECTFE) 22.214.171.124 Properties of ECTFE 5.2.9 Terpolymer of Tetrafluoroethylene, Hexafluoropropylene and Vinylidene Fluoride (THV Fluoroplastic) 126.96.36.199 Properties of THV Fluoroplastic 5.2.10 Terpolymer of Tetrafluoroethylene, Ethylene and Hexafluoropropylene (EFEP) 5.2.11 Polyvinyl Fluoride (PVF) 188.8.131.52 Properties of the PVF Polymer 184.108.40.206 Polyvinyl Fluoride Films and Their Properties 220.127.116.11.1 Chemical Properties 18.104.22.168.2 Optical Properties 22.214.171.124.3 Weathering Performance 126.96.36.199.4 Electrical Properties 188.8.131.52.5 Thermal Stability References
6 Processing of Polytetrafluoroethylene Resins 6.1 Processing of Granular Resins 6.1.1 Compression Molding 184.108.40.206 Preforming 220.127.116.11 Sintering 6.1.2 Other Molding Methods 6.1.3 Ram Extrusion 6.2 Processing of Fine Powders 6.2.1 Introduction 6.2.2 Fabrication Methods for Products from Fine Powders 18.104.22.168 Preparation of the Extrusion Mix 22.214.171.124 Preforming 126.96.36.199 Extrusion 6.2.3 Fabrication of Films, Tapes and Sealing Cords 188.8.131.52 Manufacture of Unsintered Tape 6.2.4 Fabrication of Tubing and Hoses 6.2.5 Fabrication of Thin Walled Pipes and Liners 184.108.40.206 Liner Extrusion 220.127.116.11 Drying and Sintering the Liner 6.2.6 Fabrication of Wire and Cable Insulation 18.104.22.168 Wire Extrusion System 22.214.171.124 Wire Extrusion Process 126.96.36.199 Drying and Sintering of Wire Insulation 6.2.7 Fabrication of Expanded PTFE 188.8.131.52 The Expansion Process 7 Processing of Melt-Processible Fluoroplastics 7.1 Melt-Processible Perfluoroplastics 7.1.1 Copolymers of Polytetrafluoroethylene and Hexafluoropropylene (FEP) 7.1.2 Copolymers of Tetrafluoroethylene and Perfluoroalkyl ethers (PFA and MFA) 7.2 Processing of Other Melt-Processible Fluoroplastics 7.2.1 Copolymers of Ethylene and Tetrafluoroethylene (ETFE) 7.2.2 Polyvinylidene Fluoride (PVDF) 7.2.3 Polychlorotrifluoroethylene (PCTFE) 7.2.4 Copolymer of Ethylene and Chlorotrifluoroethylene (ECTFE) 7.2.5 Terpolymers of Tetrafluoroethylene, Hexafluoropropylene and Vinylidene Fluoride (THV Fluoroplastics) 7.2.6 Terpolymer of Ethylene, Tetrafluoroethylene and Hexafluoropropylene (EFEP)
8 Applications of Commercial Thermoplastic Fluoropolymers 8.1 Applications of PTFE and Modified PTFE 8.2 Applications of FEP 8.3 Applications of PFA and MFA 8.4 Applications of ETFE 8.5 Applications of PVDF 8.6 Applications of PCTFE 8.7 Applications of ECTFE 8.8 Applications of THV Fluoroplastics 8.9 Applications of EFEP 8.10 Applications of PVF 8.10.1 Aircraft Interiors 8.10.2 Architectural Applications 8.10.3 Graphics 8.10.4 Solar Applications References
PART III FLUOROELASTOMERS
9 Fluorocarbon Elastomers 9.1 Manufacturing Process for Fluorocarbon Elastomers 9.1.1 Industrial Synthesis of Monomers for Fluorocarbon Elastomers 9.1.2 Polymerization and Finishing of Fluorocarbon Elastomers 184.108.40.206 Emulsion Polymerization 220.127.116.11.1 Continuous Emulsion Polymerization 18.104.22.168.2 Semi-batch Emulsion Polymerization 22.214.171.124 Suspension Polymerization 9.2 Properties of Fluorocarbon Elastomers 9.2.1 Properties Related to the Polymer Structure 9.2.2 Properties of Currently Available Commercial Fluorocarbon lastomers 9.3 Fabrication Methods for Fluorocarbon Elastomers 9.3.1 Mixing and Processing 126.96.36.199 Mixing of Fluorocarbon Elastomers 188.8.131.52 Processing of Fluorocarbon Elastomers 184.108.40.206.1 Calandering 220.127.116.11.2 Extrusion 18.104.22.168.3 Solution and Latex Coating 9.3.2 Curing of Fluorocarbon Elastomers 22.214.171.124 Cross-linking Chemistry 126.96.36.199.1 Cross-linking by Ionic Mechanism 188.8.131.52.2 Cross-linking by Radical Mechanism (Peroxid Cure) 184.108.40.206.3 Cross-linking by Ionizing Radiation 220.127.116.11 Molding Processes 18.104.22.168.1 Compression Molding 22.214.171.124.2 Transfer Molding 126.96.36.199.3 Injection Molding 9.3.3 Post-curing Process 9.4 Physical and Mechanical Properties of Cured Fluorocarbon Elastomers 9.4.1 Heat Resistance 9.4.2 Compression Set Resistance 9.4.3 Low-temperature Flexibility 9.4.4 Resistance to Automotive Fuels 9.4.5 Resistance to Solvents and Chemicals 9.4.6 Steam Resistance 9.5 Formulation of Compounds of Fluorocarbon Elastomers 9.5.1 Fillers 9.5.2 Acid Acceptor Systems 9.5.3 Curatives 9.5.4 Plasticizers and Processing Aids 9.6 Applications of Fluorocarbon Elastomers 9.6.1 Applications of FKMs 188.8.131.52 Typical Automotive Applications 184.108.40.206 Typical Aerospace and Military Applications 220.127.116.11 Typical Chemical and Petrochemical Applications 18.104.22.168 Other Industrial Applications 9.6.2 Applications of FFKM 9.6.3 Applications of FEPM 9.6.4 Applications of FKMs in Coatings and Sealants 9.6.5 Applications of FKMs as Polymer Processing Additive 9.7 Examples of Fluorocarbon Elastomer Formulations 9.8 Fluoroelastomer Safety, Disposal, and Sustainability 9.8.1 Safety in Production 9.8.2 Safety in Applications 9.8.3 Disposal 9.8.4 Sustainability References
10 Fluorinated Thermoplastic Elastomers 10.1 Introduction 10.2 Types of Fluorinated Thermoplastic Elastomers 10.3 Methods to Produce Fluorinated Thermoplastic Elastomers 10.4 Commercial Fluorinated Thermoplastic Elastomers and Their Properties 10.5 Applications of Fluorinated Thermoplastic Elastomers 10.5.1 Chemical and Semiconductor Industries 10.5.2 Electrical Applications and Wire and Cable 10.5.3 Other Applications References
11 Fluoro-Inorganic Elastomers 11.1 Fluorosilicone Elastomers 11.1.1 Introduction 11.1.2 Polymerization Process for Fluorosilicone Elastomers 11.1.3 Processing of Fluorosilicone Elastomers and Compounds 11.1.4 Properties of Fluorosilicone Elastomer Compounds 22.214.171.124 Fluid and Chemical Resistance 126.96.36.199 Heat Resistance 188.8.131.52 Low Temperature Behavior 184.108.40.206 Electrical Properties 220.127.116.11 Surface Properties 11.1.5 Applications of Fluorosilicone Compounds 11.1.6 Fluorosilicone Liquid Systems 11.1.7 Toxicity and Safety 11.2 Polyphosphazene Elastomers 11.2.1 Introduction 11.2.2 Fluorinated Polyphosphazene Elastomers 18.104.22.168 Properties 22.214.171.124 Applications References
PART IV TECHNOLOGY OF FLUOROPOLYMER AQUEOUS SYSTEMS
12 Characteristics and Properties of Fluoropolymer Aqueous Systems 12.1 PTFE Dispersions 12.2 Other Perfluoropolymer Dispersions 12.2.1 FEP Dispersions 12.2.2 PFA and MFA Dispersions 12.2.3 Dispersions of Modified PTFE 12.2.4 Dispersions of PTFE Micropowders 12.3 Other Fluoroplastic Dispersions 12.3.1 Dispersions of PVDF 12.3.2 Dispersions of THV Fluoroplastic 12.4 Fluorocarbon Elastomers in Latex Form References
13 Processing and Applications of Fluoropolymer Aqueous Systems 13.1 Introduction 13.2 Processing and Applications of PTFE Dispersions 13.2.1 Impregnation 13.2.2 Fabric Coating 126.96.36.199 Equipment 188.8.131.52 Formulations 184.108.40.206 Coating Process 220.127.116.11 Lamination 18.104.22.168 Applications of PTFE Coated Fabrics 13.2.3 Cast Films 22.214.171.124 Process and Equipment 126.96.36.199 Applications of PTFE Cast Films 13.2.4 Processing and Applications of Dispersions of Modified PTFE 13.2.5 Processing and Applications of Dispersions of PTFE Micropowders 13.2.6 Other Processing and Applications of PTFE Aqueous Dispersions 13.3 Processing and Applications of Other Fluoropolymer Aqueous Systems 13.3.1 Aqueous Dispersions of FEP and PFA/MFA 13.3.2 Aqueous Dispersions of PVDF 13.3.3 Aqueous Dispersions of THV Fluoroplastic 13.3.4 Fluorocarbon Elastomers in Latex Form 13.4 Health and Safety 13.5 Disposal of Aqueous Fluoropolymer Dispersions References
PART V OTHER FLUOROPOLYMERS
14 Specialty Fluorinated Polymers 14.1 Amorphous Fluoropolymers 14.2 Fluorinated Acrylates 14.3 Fluorinated Polyurethanes 14.4 Fluorinated Thermoplastic Elastomers 14.5 Copolymers of Chlorotrifluoroethylene and Vinyl Ether 14.6 Perfluorinated Ionomers References 15 Applications of Specialty Fluorinated Polymers 15.1 Applications of Amorphous Perfluoropolymers 15.2 Applications of Amorphous Perfluoropolymers 15.3 Applications of Fluorinated Polyurethanes 15.3.1 Surface Coatings 188.8.131.52 Solvent-Based Coatings 184.108.40.206 Water-Based Coatings 220.127.116.11 Powder Coatings 18.104.22.168 Treatments of Textile, Leather, and Other Substrates 22.214.171.124 Medical and Dental Applications 126.96.36.199 Cladding of Optical Fibers 188.8.131.52 Elastomers 184.108.40.206 Other Applications 15.4 Applications of Fluorinated Thermoplastic Elastomers 15.5 Applications of Copolymers of CTFE and Vinyl Ether 15.6 Applications of Perfluorinated Ionomers References
PART VI EFFECTS OF TEMPERATURE AND OTHER VARIABLES ON FLUOROPOLYMERS
16 Effect of Temperature on Fluoropolymers 16.1 Introduction 16.2 Thermal Stability of PTFE 16.3 Thermal Stability of Copolymers of Tetrafluoroethylene 16.3.1 Thermal Stability of Fluorinated Ethylene Propylene (FEP) 16.3.2 Thermal stability of PFA 16.3.3 Thermal Stability of ETFE 16.3.4Thermal Stability of ECTFE 16.3.5 Thermal Stability of PCTFE 16.3.6 Thermal Stability of PVDF
17 Effects of Environment on Fluoropolymers 17.1 Introduction 17.2 Tetrafluoroethylene 17.3 Perfluorinated Copolymers of Tetrafluoroethylene 17.3.1 PFA and MFA 17.3.2 FEP 17.4 Ethylene Tetrafluoroethylene Copolymer 17.5 Polyvinylidene Fluoride 17.6 Polychlorotrifluoroethylene 17.7 Ethylene Chlorotrifluoroethylene Copolymer 17.8 Polyvinyl Fluoride References 18 Effects of Radiation on Fluoropolymers 18.1 Introduction 18.2 Effects of Ionizing Radiation on Fluoropolymers 18.2.1 Effects of Ionizing Radiation on Perfluoroplastics 18.2.2 Effects of Ionizing Radiation on Other Fluoroplastics 18.3 Effects of Ionizing Radiation on Fluorocarbon Elastomers 18.3.1 Effects of Ionizing Radiation on FKM Type of Fluorocarbon Elastomers 18.3.2 Effects of Ionizing Radiation on Perfluoroelastomers 18.3.3 Effects of Ionizing Radiation on TFE/P Elastomers 18.4 Effects of Ionizing Radiation on Fluorosilicone Elastomers 18.5 Effects of UV Radiation on Fluoropolymers References
PART VII SAFETY AND SUSTAINABILITY
19 Safety Aspects of Fluoropolymers 19.1 Introduction 19.2 Fluoropolymers, the Essential Plastics 19.3 Polymerization Aids 19.3.1 Replacement of Polymerization Aids 19.4 Tetrafluoroethylene 19.5 Toxicology of Fluoropolymers 19.6 Emissions during Processing 19.7 Polymer Fume Fever (PFF) 19.8 Fluoropolymer Dispersions 19.9 Hygiene and Personal Protective Equipment References
20 Disposal and Recycling 20.1 Introduction 20.2 Fluorine Ore-Fluorspar 20.3 Melt Processible Fluoropolymers 20.4 Polytetrafluoroethylene 20.5 PTFE Scrap Sources for Recycling 20.6 Routes to Reuse of Polytetrafluoroethylene 20.6.1 Virgin PTFE 20.6.2 Physical Processing - Recycling 20.6.3 Physical Processing - Reprocessing 20.7 Disposal of Fluoropolymers 20.8 Chemical Recycling ("Upcycling") References