Technology of Fluoropolymers

Mr. Jiri George Drobny Jiri George Drobny is the President of Drobny Polymer Associates, an international consulting firm specializing in fluoropolymer science and technology, radiation processing and elastomer technology. His career spans over 50 years in the polymer processing industry in Europe, the US and Canada, mainly in R&D with senior and executive responsibilities. Mr. Drobny is also active as an educator, author, and as technical and scientific translator. He is member of the Society of Plastic Engineers, American Chemical Society, Rubber Division of ACS and RadTech International. He resides in New Hampshire. Dr Sina Ebnesajjad Sina Ebnesajjad is the founder of FluoroConsultants Group (FCG) and has been the President of the company since 2006. He retired as a Sr Technology Associate in 2005 from the DuPont Co. after 23 years. FCG serves companies in a variety of areas including consulting, custom manufacturing and sourcing fluoropolymers. He is author, co-author and editor of over a dozen technical books including seven on fluoropolymers and three on the surface treatment of materials and adhesives technology.

PART I OVERVIEW OF FLUOROPOLYMERS

1 Introduction

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 5.1.1.1 Mechanical Properties 5.1.1.2 Optical Properties 5.1.2 Fluoroelastomers 5.2 Properties of Individual Commercial Fluoroplastics 5.2.1 Polytetrafluoroethylene 5.2.1.1 Molecular Weight 5.2.1.2 Molecular Conformation 5.2.1.3 Crystallinity and Melting Behavior 5.2.1.4 Mechanical Properties 5.2.1.5 Surface Properties 5.2.1.6 Absorption and Permeation 5.2.1.7 Electrical Properties 5.2.2 Modified Polytetrafluoroethylene 5.2.3 Copolymers of Tetrafluoroethylene and Hexafluoropropylene (FEP) 5.2.3.1 Mechanical Properties 5.2.3.2 Electrical Properties 5.2.3.3 Chemical Properties 5.2.3.4 Optical Properties 5.2.3.5 Other Properties 5.2.4 Copolymers of Tetrafluoroethylene and Perfluoroalkyl Ethers (PFA and MFA) 5.2.4.1 Physical and Mechanical Properties 5.2.4.2 Electrical Properties 5.2.4.3 Optical properties 5.2.4.4 Chemical Properties 5.2.5 Copolymers of Ethylene and Tetrafluoroethylene (ETFE) 5.2.5.1 Structure and Related Properties 5.2.5.2 Mechanical, Chemical and Other Properties 5.2.6 Polyvinylidene Fluoride (PVDF) 5.2.6.1 Mechanical Properties 5.2.6.2 Electrical Properties 5.2.6.3 Chemical Properties 5.2.7 Polychlorotrifluoroethylene (PCTFE) 5.2.7.1 Thermal Properties 5.2.7.2 Mechanical, Chemical and Other Properties 5.2.8. Copolymer of Ethylene and Chlorotrifluoroethylene (ECTFE) 5.2.8.1 Properties of ECTFE 5.2.9 Terpolymer of Tetrafluoroethylene, Hexafluoropropylene and Vinylidene Fluoride (THV Fluoroplastic) 5.2.9.1 Properties of THV Fluoroplastic 5.2.10 Terpolymer of Tetrafluoroethylene, Ethylene and Hexafluoropropylene (EFEP) 5.2.11 Polyvinyl Fluoride (PVF) 5.2.11.1 Properties of the PVF Polymer 5.2.11.2 Polyvinyl Fluoride Films and Their Properties 5.2.11.2.1 Chemical Properties 5.2.11.2.2 Optical Properties 5.2.11.2.3 Weathering Performance 5.2.11.2.4 Electrical Properties 5.2.11.2.5 Thermal Stability References

6 Processing of Polytetrafluoroethylene Resins 6.1 Processing of Granular Resins 6.1.1 Compression Molding 6.1.1.1 Preforming 6.1.1.2 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 6.2.2.1 Preparation of the Extrusion Mix 6.2.2.2 Preforming 6.2.2.3 Extrusion 6.2.3 Fabrication of Films, Tapes and Sealing Cords 6.2.3.1 Manufacture of Unsintered Tape 6.2.4 Fabrication of Tubing and Hoses 6.2.5 Fabrication of Thin Walled Pipes and Liners 6.2.5.1 Liner Extrusion 6.2.5.2 Drying and Sintering the Liner 6.2.6 Fabrication of Wire and Cable Insulation 6.2.6.1 Wire Extrusion System 6.2.6.2 Wire Extrusion Process 6.2.6.3 Drying and Sintering of Wire Insulation 6.2.7 Fabrication of Expanded PTFE 6.2.7.1 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 9.1.2.1 Emulsion Polymerization 9.1.2.1.1 Continuous Emulsion Polymerization 9.1.2.1.2 Semi-batch Emulsion Polymerization 9.1.2.2 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 9.3.1.1 Mixing of Fluorocarbon Elastomers 9.3.1.2 Processing of Fluorocarbon Elastomers 9.3.1.2.1 Calandering 9.3.1.2.2 Extrusion 9.3.1.2.3 Solution and Latex Coating 9.3.2 Curing of Fluorocarbon Elastomers 9.3.2.1 Cross-linking Chemistry 9.3.2.1.1 Cross-linking by Ionic Mechanism 9.3.2.1.2 Cross-linking by Radical Mechanism (Peroxid Cure) 9.3.2.1.3 Cross-linking by Ionizing Radiation 9.3.2.2 Molding Processes 9.3.2.2.1 Compression Molding 9.3.2.2.2 Transfer Molding 9.3.2.2.3 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 9.6.1.1 Typical Automotive Applications 9.6.1.2 Typical Aerospace and Military Applications 9.6.1.3 Typical Chemical and Petrochemical Applications 9.6.1.4 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 11.1.4.1 Fluid and Chemical Resistance 11.1.4.2 Heat Resistance 11.1.4.3 Low Temperature Behavior 11.1.4.4 Electrical Properties 11.1.4.5 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 11.2.2.1 Properties 11.2.2.2 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 13.2.2.1 Equipment 13.2.2.2 Formulations 13.2.2.3 Coating Process 13.2.2.4 Lamination 13.2.2.5 Applications of PTFE Coated Fabrics 13.2.3 Cast Films 13.2.3.1 Process and Equipment 13.2.3.2 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 15.3.1.1 Solvent-Based Coatings 15.3.1.2 Water-Based Coatings 15.3.1.3 Powder Coatings 15.3.1.4 Treatments of Textile, Leather, and Other Substrates 15.3.1.5 Medical and Dental Applications 15.3.1.6 Cladding of Optical Fibers 15.3.1.7 Elastomers 15.3.1.8 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