Table Of ContentTechnology of Fluoropolymers
This third edition has been updated and expanded, providing industrial chemists, technologists, envi-
ronmental scientists, and engineers with an accurate, compact, and practical source of information on
fluoropolymers. Highlighting existing and new industrial, military, medical, and consumer goods appli-
cations, 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 on the important
properties of fluoropolymers, including heat and radiation degradation, health effects, and recycling.
Features:
• Revised, updated, and expanded to continue to provide an accurate, compact, and practical
source of information on fluoropolymers
• Explores the property-structure relationships, polymerization techniques, and the chemistry
underlying polymers
• Fluoropolymers rank high on the specialty polymers group and, due to their unique properties,
are naturally part of the solution to the industrial sustainability challenges of the twenty-first
century
• Describes the technology of fluoropolymers, including thermoplastic and elastomeric products
• Expands upon the important characteristics of fluoropolymers and their recycling.
Technology of
Fluoropolymers
A Concise Handbook
Third Edition
Jiri G. Drobny
Drobny Polymer Associates
Sina Ebnesajjad
FluoroConsultants Group
First edition published 2023
by CRC Press
6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742
and by CRC Press
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© 2023 Jiri G. Drobny and Sina Ebnesajjad
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ISBN: 978-1-032-01360-2 (hbk)
ISBN: 978-1-032-06886-2 (pbk)
ISBN: 978-1-003-20427-5 (ebk)
DOI: 10.1201/9781003204275
Typeset in Times
by SPi Technologies India Pvt Ltd (Straive)
Contents
List of Abbreviations ................................................................................................................................xv
Preface to the First Edition .....................................................................................................................xix
Preface to the Second Edition .................................................................................................................xxi
Preface to the Third Edition ..................................................................................................................xxiii
About the Authors ..................................................................................................................................xxv
Part I Overview of Fluoropolymers
1 Introduction ......................................................................................................................................3
Sina Ebnesajjad
References ..........................................................................................................................................8
2 Societal Benefits of Fluoropolymers ...............................................................................................9
Sina Ebnesajjad
2.1 Basic Fluoropolymer Properties .............................................................................................9
2.2 Examples of Fluoropolymer Properties ..................................................................................9
2.3 Automotive Applications ......................................................................................................10
2.4 Aerospace Wire and Cable ....................................................................................................10
2.5 Aircraft Fuel Hoses ...............................................................................................................12
2.6 Heart Rhythm Management: The Implantable Cardioverter Defibrillator ............................13
2.7 Pediatric Heart Repair ...........................................................................................................14
2.8 Thread Sealant ......................................................................................................................15
2.9 Chemical Processing Industry-lined Pipes, Fittings, and Vessels .........................................16
2.10 Semiconductor Chip Fabrication ..........................................................................................18
2.11 Biomedical Applications .......................................................................................................19
2.12 PTFE Micropowders .............................................................................................................19
2.13 Applications of Fluoroelastomers in Transportation .............................................................19
2.14 Properties of Thermoplastic Fluoropolymers .......................................................................20
2.15 Delving Deeper into Properties .............................................................................................20
2.16 Forces Affecting the Fluoropolymer Industries ....................................................................22
References ........................................................................................................................................22
Part II Thermoplastic Fluoropolymers
3 Synthesis and Properties of Monomers of Thermoplastic Fluoropolymers ..............................27
Sina Ebnesajjad
3.1 Preparation of Tetrafluoroethylene .......................................................................................27
3.2 Properties of Tetrafluoroethylene .........................................................................................29
3.3 Preparation of Hexafluoropropylene ....................................................................................30
3.4 Properties of Hexafluoropropylene ......................................................................................30
3.5 Synthesis of Perfluoroalkylvinylethers ................................................................................31
3.6 Properties of Perfluoroalkylvinylethers ...............................................................................32
v
vi Contents
3.7 Synthesis of Chlorotrifluoroethylene (CTFE) .......................................................................32
3.8 Properties of Chlorotrifluoroethylene ...................................................................................33
3.9 Synthesis of Vinylidene Fluoride ..........................................................................................33
3.10 Properties of Vinylidene Fluoride .........................................................................................35
3.11 Synthesis of Vinyl Fluoride ...................................................................................................35
3.12 Properties of Vinyl Fluoride ..................................................................................................35
References ........................................................................................................................................36
4 Polymerization of Commercial Thermoplastic Fluoropolymers ................................................39
Sina Ebnesajjad
4.1 Polymerization of Tetrafluoroethylene ..................................................................................39
4.1.1 Granular Resins .......................................................................................................40
4.1.2 Fine Powder Resins .................................................................................................43
4.1.3 Aqueous Dispersions ...............................................................................................44
4.1.4 Filled Compounds ...................................................................................................44
4.1.5 Modified PTFE ........................................................................................................44
4.2 Fluorinated Ethylene Propylene ............................................................................................45
4.2.1 Industrial Process for the Production of FEP ..........................................................45
4.3 Perfluoroalkoxy Resin...........................................................................................................45
4.3.1 Industrial Process for the Production of Perfluoroalkoxy Resins ...........................45
4.4 Polychlorotrifluoroethylene ..................................................................................................46
4.4.1 Industrial Process for the Production of Polychlorotrifluoroethylene.....................46
4.5 Polyvinylidene Fluoride ........................................................................................................46
4.5.1 Industrial Process for the Production of Polyvinylidene Fluoride ..........................46
4.6 Polyvinyl Fluoride.................................................................................................................47
4.6.1 Industrial Process for the Production of Polyvinyl Fluoride ...................................47
4.7 Ethylene Chlorotrifluoroethylene Copolymer .......................................................................47
4.7.1 Industrial Process for the Production of Ethylene Chlorotrifluoroethylene ............47
4.8 Ethylene Tetrafluoroethylene Copolymer .............................................................................47
4.8.1 Industrial Process for the Production of Ethylene Tetrafluoroethylene ..................47
4.9 Terpolymers of Tetrafluoroethylene, Hexafluoropropylene, and Vinylidene
Fluoride (THV Fluoroplastic) ...............................................................................................48
4.10 Terpolymers and Quarterpolymers of Hexafluoropropylene, Tetrafluoroethylene,
and Ethylene ..........................................................................................................................48
References ........................................................................................................................................48
5 Properties of Commercial Thermoplastic Fluoropolymers ........................................................51
Jiri G. Drobny
5.1 Properties as Related to the Structure of Fluoropolymers ....................................................51
5.1.1 Fluoroplastics ..........................................................................................................51
5.1.1.1 Mechanical Properties ............................................................................53
5.1.1.2 Optical Properties ...................................................................................53
5.1.2 Fluoroelastomers .....................................................................................................54
5.2 Properties of Individual Commercial Fluoroplastics ............................................................55
5.2.1 Polytetrafluoroethylene ...........................................................................................55
5.2.1.1 Molecular Weight....................................................................................55
5.2.1.2 Molecular Conformation ........................................................................55
5.2.1.3 Crystallinity and Melting Behavior ........................................................56
5.2.1.4 Mechanical Properties ............................................................................57
5.2.1.5 Surface Properties ...................................................................................57
5.2.1.6 Absorption and Permeation ....................................................................57
Contents vii
5.2.1.7 Electrical Properties ................................................................................58
5.2.2 Modified Polytetrafluoroethylene............................................................................58
5.2.3 Copolymers of Tetrafluoroethylene and Hexafluoropropylene (FEP) ....................59
5.2.3.1 Mechanical Properties ............................................................................59
5.2.3.2 Electrical Properties ................................................................................60
5.2.3.3 Chemical Properties ................................................................................60
5.2.3.4 Optical Properties ...................................................................................61
5.2.3.5 Other Properties ......................................................................................61
5.2.4 Copolymers of Tetrafluoroethylene and Perfluoroalkyl
Ethers (PFA and MFA) ............................................................................................61
5.2.4.1 Physical and Mechanical Properties .......................................................61
5.2.4.2 Electrical Properties ................................................................................62
5.2.4.3 Optical Properties ...................................................................................62
5.2.4.4 Chemical Properties ................................................................................62
5.2.5 Copolymers of Ethylene and Tetrafluoroethylene (ETFE) .....................................62
5.2.5.1 Structure and Related Properties ............................................................63
5.2.5.2 Mechanical, Chemical, and Other Properties .........................................63
5.2.6 Polyvinylidene Fluoride (PVDF) ............................................................................64
5.2.6.1 Mechanical Properties ............................................................................64
5.2.6.2 Electrical Properties ................................................................................64
5.2.6.3 Chemical Properties ................................................................................66
5.2.7 Polychlorotrifluoroethylene (PCTFE) .....................................................................66
5.2.7.1 Thermal Properties..................................................................................66
5.2.7.2 Mechanical, Chemical, and Other Properties .........................................66
5.2.8 Copolymer of Ethylene and Chlorotrifluoroethylene (ECTFE) ..............................67
5.2.8.1 Properties of ECTFE...............................................................................67
5.2.9 Terpolymer of Tetrafluoroethylene, Hexafluoropropylene, and Vinylidene
Fluoride (THV Fluoroplastic) .................................................................................68
5.2.9.1 Properties ................................................................................................68
5.2.10 Terpolymer of Ethylene, Tetrafluoroethylene,
and Hexafluoropropylene (EFEP) ...........................................................................69
5.2.11 Polyvinyl Fluoride (PVF) ........................................................................................70
5.2.11.1 Properties of the PVF Polymer ...............................................................70
5.2.11.2 Polyvinyl Fluoride Films and Their Properties.......................................71
References ........................................................................................................................................74
6 Processing of Polytetrafluoroethylene Resins ..............................................................................77
Jiri G. Drobny
6.1 Processing of Granular Resins ..............................................................................................77
6.1.1 Compression Molding .............................................................................................80
6.1.1.1 Preforming ..............................................................................................81
6.1.1.2 Sintering ..................................................................................................83
6.1.2 Other Molding Methods ..........................................................................................86
6.1.3 Ram Extrusion .........................................................................................................88
6.2 Processing of Fine Powders ..................................................................................................88
6.2.1 Introduction .............................................................................................................88
6.2.2 Fabrication Methods for Products from Fine Powders ...........................................95
6.2.2.1 Preparation of the Extrusion Mix ...........................................................95
6.2.2.2 Preforming ..............................................................................................96
6.2.2.3 Extrusion .................................................................................................96
6.2.3 Fabrication of Films, Tapes, and Sealing Cords ......................................................98
6.2.3.1 Manufacture of Unsintered Tape ............................................................98
viii Contents
6.2.4 Fabrication of Tubing and Hoses ..........................................................................100
6.2.4.1 Tube Extrusion ......................................................................................101
6.2.4.2 Drying and Sintering of Tubes ..............................................................101
6.2.5 Fabrication of Thick-Walled Pipes and Liners ......................................................101
6.2.5.1 Liner Extrusion .....................................................................................101
6.2.5.2 Drying and Sintering the Liner .............................................................102
6.2.6 Fabrication of Wire and Cable Insulation .............................................................102
6.2.6.1 Wire Extruder System ...........................................................................102
6.2.6.2 Wire Extrusion Process .........................................................................102
6.2.6.3 Drying and Sintering of Wire Insulation ..............................................103
6.2.7 Expanded PTFE ....................................................................................................104
6.2.7.1 The Expansion Process .........................................................................104
References ......................................................................................................................................107
7 Processing of Melt-Processible Fluoroplastics ...........................................................................109
Jiri G. Drobny
7.1 Melt-Processible Perfluoroplastics ......................................................................................110
7.1.1 Copolymers of Tetrafluoroethylene and Hexafluoropropylene:
Fluorinated Ethylene Propylene ............................................................................110
7.1.2 Copolymers of Tetrafluoroethylene and Perfluoroalkyl
Ethers (PFA and MFA) ..........................................................................................110
7.2 Processing of Other Melt-Processible Fluoroplastics .........................................................111
7.2.1 Copolymers of Ethylene and Tetrafluoroethylene (ETFE) ...................................111
7.2.2 Polyvinylidene Fluoride (PVDF) ..........................................................................111
7.2.3 Polychlorotrifluoroethylene (PCTFE) ...................................................................112
7.2.4 Copolymers of Ethylene and Chlorotrifluoroethylene (ECTFE) ..........................112
7.2.5 Terpolymers of Tetrafluoroethylene, Hexafluoropropylene, and Vinylidene
Fluoride (THV Fluoroplastics) ..............................................................................112
7.2.6 Terpolymer of Ethylene, Tetrafluoroethylene, and
Hexafluoropropylene: (EFEP) ...............................................................................112
References ......................................................................................................................................113
8 Applications of Commercial Thermoplastic Fluoropolymers ..................................................115
Jiri G. Drobny
8.1 Applications of PTFE and Modified PTFE .........................................................................115
8.2 Applications of FEP ............................................................................................................117
8.3 Applications of PFA and MFA ............................................................................................118
8.4 Applications of ETFE .........................................................................................................118
8.5 Applications of PVDF .........................................................................................................120
8.6 Applications of PCTFE .......................................................................................................121
8.7 Applications of ECTFE .......................................................................................................122
8.8 Applications of THV Fluoroplastics ...................................................................................125
8.9 Applications of EFEP .........................................................................................................126
8.10 Applications of PVF ...........................................................................................................126
8.10.1 Aircraft Interiors ...................................................................................................126
8.10.2 Architectural Applications ....................................................................................127
8.10.3 Graphic Applications .............................................................................................128
8.10.4 Solar Applications .................................................................................................128
References ......................................................................................................................................129
Contents ix
Part III Fluoroelastomers
9 Fluorocarbon Elastomers ............................................................................................................133
Jiri G. Drobny
9.1 Manufacturing Process for Fluorocarbon Elastomers .........................................................135
9.1.1 Industrial Synthesis of Monomers for Fluorocarbon Elastomers .........................135
9.1.2 Polymerization and Finishing of Fluorocarbon Elastomers ..................................136
9.1.2.1. Emulsion Polymerization .....................................................................137
9.1.2.2. Suspension Polymerization ...................................................................139
9.2 Properties of Fluorocarbon Elastomers ...............................................................................141
9.2.1 Properties Related to the Polymer Structure .........................................................141
9.2.2 Other Properties ....................................................................................................144
9.2.3 Properties of Currently Available Commercial Fluorocarbon Elastomers ............144
9.2.3.1 FKM Type 1: Copolymers of HFP and VDF ........................................144
9.2.3.2 FKM Type 2: Terpolymers of TFE, VDF, and HFP ..............................145
9.2.3.3 FKM Type 3: Terpolymers of TFE, PMVE, and VDF..........................145
9.2.3.4 FKM Type 4: Terpolymers of TFE, P, and VDF ...................................145
9.2.3.5 FKM Type 5: Pentapolymers of TFE, HFP, VDF,
Ethylene, and PMVE ............................................................................146
9.2.3.6. FFKM Perfluoroelastomers ..................................................................146
9.2.3.7. FEPM ....................................................................................................147
9.3 Fabrication Methods for Fluorocarbon Elastomers ............................................................150
9.3.1 Mixing and Processing of Compounds from Fluorocarbon Elastomers ...............150
9.3.1.1 Mixing of Compounds of Fluorocarbon Elastomers ............................150
9.3.1.2 Processing of Fluorocarbon Elastomers ...............................................150
9.3.2 Curing of Fluorocarbon Elastomers ......................................................................154
9.3.2.1 Cross-Linking Chemistry .....................................................................155
9.3.2.2 Molding Processes ................................................................................157
9.3.3 Post-Curing Process ..............................................................................................161
9.4 Physical and Mechanical Properties of Cured Fluorocarbon Elastomers ...........................161
9.4.1 Heat Resistance .....................................................................................................162
9.4.2 Compression Set Resistance .................................................................................162
9.4.3 Low-Temperature Flexibility ................................................................................162
9.4.4 Resistance to Automotive Fuels ............................................................................163
9.4.5 Resistance to Solvents and Chemicals ..................................................................164
9.4.6 Steam Resistance ...................................................................................................164
9.5. Formulation of Compounds of Fluorocarbon Elastomers ...................................................164
9.5.1 Fillers ....................................................................................................................164
9.5.2 Acid Acceptor Systems .........................................................................................164
9.5.3 Curatives................................................................................................................165
9.5.4 Plasticizers and Processing Aids ...........................................................................166
9.6 Applications of Fluorocarbon Elastomers ..........................................................................167
9.6.1 Applications of FKMs ...........................................................................................167
9.6.1.1 Typical Automotive Applications .........................................................168
9.6.1.2 Typical Aerospace and Military Applications .......................................168
9.6.1.3 Typical Chemical and Petrochemical Applications ..............................170
9.6.1.4 Other Industrial Applications ................................................................170
9.6.2 Applications of FFKMs ........................................................................................171
9.6.3 Applications of FEPM ..........................................................................................172
x Contents
9.6.4 Applications of FKMs in Coatings and Sealants ..................................................173
9.6.5 Applications of FKMs as Polymeric Processing Additives ..................................173
9.7 Examples of Fluorocarbon Elastomer Formulations ..........................................................174
9.7.1 Typical Formulations of Fluoroelastomer Compounds .........................................175
9.7.2 Rotary Seal for Airborne Applications ..................................................................175
9.7.3 Compounds for Compression Molded Seals .........................................................175
9.7.4 Basic O-Ring Compounds ....................................................................................176
9.7.5 Compound for Closed Cell Sponge ......................................................................177
9.7.6 Example of Compounds Based on FEPM (TFE/P) Elastomers ............................177
9.7.7 Example of Steam Resistant Formulations ...........................................................178
9.7.8 Basic Extrusion Compounds .................................................................................178
9.7.9 Example of FKM Compounds for Aerospace AMS 3216 and AMS 7276H ........179
9.7.10 No Post-Cure Fluoroelastomer Articles ................................................................180
9.7.11 Low Temperature Service Seals ............................................................................180
9.7.12 FFKM Compound for Aerospace-AMS 7257E ....................................................181
9.8 Fluoroelastomer Safety, Disposal, and Sustainability .........................................................182
9.8.1 Safety in Production ..............................................................................................182
9.8.2 Safety in Applications ...........................................................................................183
9.8.3 Disposal .................................................................................................................183
9.8.4 Sustainability .........................................................................................................183
References ......................................................................................................................................184
10 Fluorinated Thermoplastic Elastomers ......................................................................................187
Jiri G. Drobny
10.1 Introduction .........................................................................................................................187
10.2 Types of Fluorinated Thermoplastic Elastomers .................................................................187
10.3 Methods to Produce Fluorinated Thermoplastic Elastomers ..............................................187
10.4 Commercial Fluorinated Thermoplastic Elastomers and Their Properties .........................189
10.5 Applications of Fluorinated Thermoplastic Elastomers ......................................................193
10.5.1 Chemical and Semiconductor Industries ...............................................................193
10.5.2 Electrical, and Wire and Cable ..............................................................................193
10.5.3 Other Applications ................................................................................................193
References ......................................................................................................................................193
11 Fluoro-Inorganic Elastomers ......................................................................................................195
Jiri G. Drobny
11.1 Fluorosilicone Elastomers ...................................................................................................195
11.1.1 Introduction ...........................................................................................................195
11.1.2 Polymerization Process for Fluorosilicone Elastomers ........................................196
11.1.3 Processing of Fluorosilicone Elastomers and Compounds ...................................196
11.1.4 Properties of Fluorosilicone Elastomer Compounds ............................................197
11.1.4.1 Fluid and Chemical Resistance .............................................................197
11.1.4.2 Heat Resistance .....................................................................................197
11.1.4.3 Low Temperature Behavior ..................................................................198
11.1.4.4 Electrical Properties ..............................................................................199
11.1.4.5 Surface Properties .................................................................................199
11.1.5 Applications of Fluorosilicone Compounds .........................................................199
11.1.6 Fluorosilicone Liquid Systems ..............................................................................200
11.1.7 Toxicity and Safety ...............................................................................................202
11.2 Polyphosphazene Elastomers ..............................................................................................202
11.2.1 Introduction ...........................................................................................................202
