Fluoroplastics – Volume 1
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Sina Ebnesajjad
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Fluoroplastics – Volume 1
Non-Melt Processible – Fluoropolymers
The Definitive User’s Guide and Data Book
Second Edition
Sina Ebnesajjad
Table of contents
Dedication
Series
2nd edition Acknowledgments
1st edition Acknowledgments
2nd edition Preface
1st edition Preface
Part I

  1. Discovery and History of Fluoropolymers
    1.1. Coming of Age of Polymer Science
    1.2. Roy Plunkett’s Story
    1.3. Commercialization of PTFE
    1.4. Developmental History of Fluoropolymers
  2. Production and Market Statistics
    2.1. Growth of Fluoropolymers
    2.2. Regional Consumption of Fluoropolymers
    2.3. Consumption of Fluoropolymers and PTFE
    2.4. Trends
  3. From Fundamentals to Applications
    3.1. Introduction
    3.2. Uniqueness of Fluorine
    3.3. Fluorine Characteristics
    3.4. What are Fluoropolymers?
    3.5. Fundamental Properties of Fluoropolymers
    3.6. Developmental History of Fluoropolymers
    3.7. Examples of Uses of Fluoropolymers
  4. Fluoropolymers: Properties and Structure
    4.1. Introduction
    4.2. Impact of F and C–F Bond on the Properties of Polytetrafluoroethylene
    4.3. Distruping the Linear PTFE Chain: Perfluorinated Ethylene–Propylene Copolymer and Polychlorotrifluoroethylene
    4.4. Reaction Mechanism
    4.5. Effect of Solvents on Fluoropolymers
    4.6. Molecular Interaction of Fluoropolymers: Low Friction and Low Surface Energy
    4.7. Conformations and Transitions of PTFE
    4.8. Conformations and Transitions of PCTFE
  5. Operational Classification of Fluoropolymers
    5.1. Introduction
    5.2. TFE Homopolymers
    5.3. TFE Copolymers
    5.4. CTFE Polymers
    5.5. VDF Polymers
    5.6. VF Polymers
    5.7. Process Classification
  6. Preparation of Tetrafluoroethylene and Other Monomers
    6.1. Introduction
    6.2. TFE Preparation
    6.3. Purification of TFE
    6.4. Properties of TFE
    6.5. Synthesis of HFP
    6.6. Properties of HFP
    6.7. Synthesis of PAVE
    6.8. Properties of PAVE
    6.9. Synthesis of CTFE
    6.10. Properties of CTFE
  7. Polymerization Surfactants
    7.1. Introduction
    7.2. Perfluorooctane Sulfonate
    7.3. Issues with PFOS
    7.4. Problems with PFOA
    7.5. EPA Action
    7.6. Alternative Surfactants for Fluoropolymer Polymerization
    7.7. Summary
  8. Polymerization and Finishing of Tetrafluoroethylene
    8.1. Introduction
    8.2. Polymerization Mechanism
    8.3. TFE Polymers
    8.4. Evolution of Suspension Polymerization of TFE
    8.5. Preparation of PTFE by Emulsion Polymerization
    8.6. Preparation of Dispersion Grade PTFE
    8.7. Preparation of Fine Powder PTFE
    8.8. CTFE Polymers and Polymerization
    8.9. Characterization of PTFE
    8.10. Characterization of PCTFE
  9. Commercial Grades of Fluoropolymers
    9.1. Introduction
    9.2. Granular PTFE
    9.3. PTFE Dispersions
    9.4. Fine Powder PTFE
    9.5. Polychlorotrifluoroethylene Polymers
    Part II
  10. Fabrication and Processing of Granular Polytetrafluoroethylene
    10.1. Introduction
    10.2. Resin Selection
    10.3. Compression Molding
    10.4. Automatic Molding
    10.5. Isostatic Molding
    10.6. Ram Extrusion
  11. Fabrication and Processing of Fine Powder Polytetrafluoroethylene
    11.1. Introduction
    11.2. Resin Handling and Storage
    11.3. Paste Extrusion Fundamentals
    11.4. Extrusion Aid or Lubricant
    11.5. Wire Coating
    11.6. Extrusion of Tubing
    11.7. Unsintered Tape
    11.8. Expanded PTFE Manufacturing
    11.9. Fine Powder Resin Selection
  12. Fabrication and Processing of Polytetrafluoroethylene Dispersions
    12.1. Introduction
    12.2. Applications
    12.3. Storage and Handling
    12.4. Surfactants
    12.5. Principles of Coating Technology
    12.6. Dispersion Formulation and Characteristics
    12.7. Glass Cloth Coating
    12.8. Impregnation of Flax and Polyaramide
    12.9. Coating Metal and Hard Surfaces
    12.10. PTFE Yarn Manufacturing
    12.11. Film Casting
    12.12. Anti-drip Applications
    12.13. Filled Bearings
    12.14. Dedusting Powders
    12.15. Other Applications
  13. Processing of Polychlorotrifluoroethylene
    13.1. Introduction
    13.2. Processing Considerations
    13.3. Compression Molding
    13.4. Injection Molding
    13.5. Extrusion
    13.6. Machining and Joining
  14. Fluorinated Additives
    14.1. Introduction
    14.2. PTFE Additives
    14.3. Applications of PTFE Additives
    14.4. Feedstock for PTFE Additives
    14.5. Manufacturing PTFE Additives
    14.6. PTFE-Modified Waxes
  15. Surface Treatment of Polytetrafluoroethylene for Adhesion
    15.1. Introduction
    15.2. Sodium Etching of Fluoroplastics
    15.3. Plasma Treatment of Fluoropolymers and PTFE
    15.4. Atmospheric Pressure Plasma Treatment
  16. Filled Fluoropolymer Compounds
    16.1. Introduction
    16.2. Granular-Based Compounds
    16.3. Fine Powder-Based Compounds
    16.4. Co-coagulated Compounds
    16.5. Processing Compounds
    16.6. Typical Properties of Filled Fluoropolymers
    16.7. Nanocomposites of PTFE
    16.8. Commercial Products
    Part III
  17. Chemical Properties of Fluoropolymers—Polytetrafluoroethylene and Polychlorotrifluoroethylene
    17.1. Introduction
    17.2. Chemical Compatibility of PTFE
    17.3. Chemical Compatibility of Polychlorotrifluoroethylene
    17.4. Permeation Fundamentals
    17.5. Environmental Stress Cracking
    17.6. Solubility Parameters
  18. Properties of Tetrafluoroethylene Homopolymers
    18.1. Introduction
    18.2. Crystallinity
    18.3. Molecular Weight
    18.4. Influence of Processing
    18.5. Microstructure and Fracture of PTFE
    18.6. Mechanical Properties
    18.7. Fatigue Properties
    18.8. Electrical Properties
    18.9. Thermal Behavior
    18.10. Flammability Characteristics
    18.11. Irradiation Behavior
    18.12. Surface Properties
    18.13. Refractive Index
    18.14. Standard Measurement Methods
  19. Properties of Polychlorotrifluoroethylene
    19.1. Introduction
    19.2. Crystallinity
    19.3. Mechanical Properties
    19.4. Electrical Properties
    19.5. Thermal Properties
    19.6. Irradiation Behavior
    19.7. Properties of PCTFE Films
    19.8. Barrier Properties
    19.9. Spectroscopic Properties
    19.10. Chemical and Weathering Properties
  20. Fabrication Techniques for Polytetrafluoroethylene
    20.1. Introduction
    20.2. Machining
    20.3. Adhesive Bonding Methods
    20.4. Welding and Joining
    20.5. Thermoforming
    20.6. Other Processes
  21. Applications of Polytetrafluoroethylene and Fluoropolymers
    21.1. Chemical Processing
    21.2. Piping
    21.3. Vessels
    21.4. CPI Components
    21.5. Self-Supporting Components
    21.6. Trends in Using Fluoropolymers in Chemical Service
    21.7. Semiconductor Processing
    21.8. Electrical Applications
    21.9. Mechanical Applications
    21.10. Automotive and Aerospace
    21.11. Medical Devices
    21.12. Summary
  22. Safety, Health, Environmental, Disposal, Recycling, and Economics
    22.1. Introduction
    22.2. Toxicology of Fluoropolymers
    22.3. Thermal Properties of PTFE
    22.4. Emission during Processing
    22.5. Safety Measures
    22.6. Food Contact
    22.7. Fluoropolymer Scrap and Recycling
    22.8. Environmental Protection and Disposal Methods
    Appendix 1. Chemical Resistance of Polytetrafluoroethylene (PTFE)
    Appendix 2. Chemical Resistance of Polychlorotrifluoroethylene (PCTFE)
    Appendix 3. Permeability of Polytetrafluoroethylene (PTFE)
    Appendix 4. Permeability of Polychlorotrifluoroethylene (PCTFE)
    Appendix 5. Melt Creep Viscosity of Polytetrafluoroethylene
    Glossary
    Index
    .
    GLOSSARY 691Index
    A
    Adjustable ducting hood, 482, 483f
    Agglomeration processes
    continuous process, 114, 115te116t
    Dravo pelletizing pan, 114e117,
    118f
    dry process, 111e112
    Fitzpatrick Homoloid Mill, 114, 117f
    mechanism, 110f
    particle size distribution, 118, 118f
    pellets production steps, 117
    pipeline homomixer, 113
    properties, 112, 112t
    protective colloid, 112e113
    PTFE-graphite mixture, 117e118
    toxicity and flammability, 110e111
    wet process, 112
    Air milling
    advantage of, 106
    Micron-MasterBSF Mill, 105e106,
    105f
    working principle, 105e106, 106f
    Alumina (Al2O3), 339e340
    Ammonia (NH3), 315e318
    Ammonium perfluorooctanoate (APFO),
    84, 84f
    Ammonium persulfate (APS)
    degradation, 96, 97f
    Amorphous locking, 272e273
    Amorphous phase, 398
    Annealing, 197, 197f
    Applications
    automotive and aerospace, 475e477
    chemical processing, 461
    chemical service, using fluoropolymers
    in, 467e468
    CPI components, 464e466
    electrical applications, 470e471
    mechanical applications, 471e475
    medical devices, 477
    piping, 461e462, 461f, 463f
    self-supporting components,
    466e467
    semiconductor processing, 468e470
    vessels, 463
    APT. See Atmospheric pressure plasma
    treatment (APT)
    Atmospheric pressure plasma treatment
    (APT), 328e333, 329t
    Atomic force microscopy (AFM),
    33e34, 35t
    Automatic molding, 38
    demolding, 199
    pressure/dwell period and specific
    gravity, 200, 201f
    steps of, 199, 200f
    B
    Barrier properties, 448
    Billet molding, 178e179, 179t
    cooling
    annealing, 197, 197f
    crystallinity, 194, 197t
    sintering cycle, 194, 196f
    tetrafluoroethylene sintering
    conditions, 194, 195t
    preforming
    dielectric breakdown voltage, 186,
    188f
    double acting compression molding,
    189, 191f
    mechanical properties vs. preform
    pressure, 185e186, 187f
    molding pressure, 186, 189f, 191f
    mold shrinkage vs. preform pressure,
    186, 190f
    preform removal systems,
    189, 192f
    press closing rates, 185e186, 187t
    press force vs. dwell time, 185e186,
    187f
    P/T diagram, 186, 188f
    resting time for degassing, 189e190,
    193f
    sintered PTFE parts vs. preform
    temperature and pressure, 184,
    185fe186f
    telescopic mold, 189, 193f
    tensile strength, 186, 188f
    transition point and linear thermal
    expansion, 184, 184f
    sintering
    cycle, 192, 196f
    mechanism, 190, 194f
    peak temperature/time effect,
    193e194, 196f
    seven-hour sintering, 190e192,
    194f
    tetrafluoroethylene sintering
    conditions, 192, 195t
    Bioconcentration factor (BCF), 85
    Bronze, 338e339, 339f
    Bulk polymerization
    CTFE, 140
    Burnout hood, 482, 483f
    C
    Calcium fluoride, 339e340
    Carbon fiber, 337e338, 338f
    Carbon powder, 337, 338f
    Centerless grinding, 454, 454t
    Chemical processing, 461
    Chemical properties, 452
    Chlorodifluoromethane
    perfluorocarbon, 50, 51t
    pyrolysis reactor, 59
    and tetrafluoroethylene
    pressure and temperature effect, 49,
    49t
    steam effect, 50, 50t
    Chlorotrifluoroethylene (CTFE)
    PCTFE, 139
    polymerization
    acrylic monomers, 141, 141f, 142t
    copolymers, 141, 141t
    film made from polymer, 142t
    peroxides, 139
    types, 140
    VDF-TrFE copolymer, 143, 143t
    properties, 72e73, 73t
    synthesis
    HCL and TFE, 72, 72t
    TCTFE, 70e71
    VDF, 45
    Coagulated dispersion, 95
    Compression molding, 38, 303, 303f
    billet molding, 178e179, 179t
    692cooling, 194e197, 196fe197f, 197t
    preforming, 184e190, 184fe187f,
    187t, 188fe193f
    sintering, 190e194, 194f, 195t
    carbonization, 179
    densification and sintering mechanism,
    182e184, 183f
    equipment
    mold design, 180e181, 180f
    ovens, 181e182
    presses, 181, 181f
    hot compression molding, 198e199,
    199t
    sintering cycles, 195t, 198f
    Contact angle, 285
    Crack propagation, 408
    Crystallinity, 301e302, 302t, 441e442
    Crystal model, 399
    D
    Daikin Neoflon, 300, 300t, 303
    Davis electric vertical extruder, 251f
    Degradation, 427
    Die land, 249
    Dielectric constant, 443, 444f
    Dielectric strength, 405, 405t
    Differential scanning calorimetry (DSC),
    401e402
    Diglyme, 319e320
    Diglyme etchants, 320
    1,1-Dihydropentafluoropropyl
    trifluorovinyl ether
    (1,1 DHPPTE), 69
    Disproportionation, 96
    Disuccinic acid peroxide, 102
    Double acting compression molding,
    189, 191f
    Drilling, 454
    E
    Elastomeric seals, 309
    Electrical applications, 470e471
    Electrical properties, 443, 444t
    Electrochemical fluorination (ECF)
    process, 78
    Electropolishing, 129e130
    Elevated temperature
    etching, 320e321
    shelf life of etch surfaces, 321
    storage and preparation, 320
    washing, 321
    Elongation, 442, 442f
    Emulsion polymerization
    ammonium sulfite, 126
    with APFO replacements
    fluorinated emulsifier, 127
    polymerization conditions and
    properties, 127, 127t
    autoclave, 122e123
    chlorendic acid, 120e121, 121f
    core-shell polymer, 123
    CTFE, 140, 140t
    dispersion stability, 121
    HFP and methanol modifiers,
    122, 122t
    mechanism
    accordion-shape crystal formation,
    130e131, 132f
    initiation step, 130e131, 131f
    micelle, 130e131, 132f
    particle size formation, 130e131,
    132f
    PTFE chain folding, 130e131, 132f
    single PTFE particle, 132, 133f
    surface tension, 132e133, 133f
    surfactant concentrations, 133, 134f
    modifier comonomers, Alfrey-Price Q
    and e values, 134e135, 135f, 135t
    perfluoroalkyl vinyl ether comonomers,
    123
    perfluorovinyl ether, 126
    polykettle, 125
    polymer properties, 123e124, 125t
    product finishing processes, 120, 120f
    reactor
    electropolished cage agitator, 130,
    131f
    paddle mixers, 130, 131f
    schematic diagram, 128e129, 129f
    SEM micrographs, 129, 130f
    stainless-steel surface, 129, 130f
    wall-sweeping agitator, cross-section,
    130, 131f
    recipe and polymerization data, 123,
    124t
    scanning electron micrograph,
    120, 120f
    tetrafluoroethylene, in stabilizers,
    121e122, 121t
    Environmental stress cracking (ESC),
    392e395
    fluoropolymers, 394e395
    ESC. See Environmental stress cracking
    (ESC)
    ETFE. See Ethylene tetrafluoroethylene
    copolymer (ETFE)
    Ethylene chlorotrifluoroethylene
    (ECTFE), 315, 316t
    Ethylene tetrafluoroethylene (ETFE), 18,
    322, 322f
    Excessive microporosity, 406
    Excessive treatment, 315
    Exhaust system, 482, 483f
    Extrusion, 305e306, 306t
    F
    Fabrication techniques
    adhesive bonding methods
    bonding adhesives, 456
    contact adhesives, 456
    machining, 453e455
    centerless grinding, 454, 454t
    drilling/tapping and threading, 454
    machining filled PTFE parts, 455
    sawing and shearing, 454
    skiving, 454e455
    turning and milling, 454
    other processes, 460, 460f
    thermoforming, 458e459, 459f
    welding and joining
    welding technique, 457e458, 457f
    Filled fluoropolymer compounds
    co-coagulated compounds, 350e353
    steps of, 351
    commercial products, 370, 371te375t,
    377te379t
    filled fluoropolymers, typical properties
    of, 355e362
    chemical properties, 356, 366t
    electrical properties, 356, 365t
    mechanical properties, 356, 358t
    thermal properties, 356
    tribological properties, 359e362
    fine powder-based compounds,
    346e350
    fillers and compounding methods,
    347
    reinforced gasketing material,
    fabrication of, 347e350
    granular-based compounds, 336e346
    filled PTFE, production techniques,
    340e346
    fillers, 336e340, 337t
    PTFE grade, selection of, 340
    processing compounds, 353e355, 354f
    PTFE, nanocomposites of, 362e370
    hydrophobicity, 368e369
    multifunctionality, 369e370
    wear, 366e368
    Fine powder polytetrafluoroethylene
    Asahi Glass Company’s Fluon fine
    powder PTFE, 171t
    Daikin’s fine powder PTFE, 172t
    DuPont Teflon fine powder PTFE,
    170t
    Dyneon’s Hostaflon fine powder PTFE,
    171t
    expanded PTFE manufacturing
    INDEX 693Fine powder polytetrafluoroethylene
    (Continued)
    air permeability-water entry pressure
    relationships, 274, 275f
    amorphous locking, 272e273
    biaxially expanded
    polytetrafluoroethylene, 273, 273f
    expanded vs. full density
    polytetrafluoroethylene, 274, 275t
    Gore-Tex, 272
    microporous polytetrafluoroethylene,
    274, 276f
    Poisson’s ratio, 276f
    porosity/pore-size relationships,
    273e274, 274f
    uniaxially expanded
    polytetrafluoroethylene, 273, 273f
    Young’s Modulus, 274e275, 276f
    extrusion aid/lubricant
    commercial lubricants, 239
    Isoparsolvents, 239, 240t
    Shell Corporation, 239, 242t
    paste extrusion
    abused, 237
    agglomerates, 236, 236f
    crystalline structure, 236, 237f
    definitions, 234
    DSC diagram, 237, 238f
    extrusion pressure and lubricant
    content, 238, 239f
    fibrilation, 236e237, 238f
    PTFE fibrils, 236e237, 237f
    structure of one particle, 236, 237f
    reduction ratio, 235f
    Daikin polytetrafluoroethylene, 254,
    255t
    definitions, 234
    and extrusion pressure, 254, 256f
    master die, 252f, 253
    TeflonCFP 6000 fluoropolymer
    resin, 254, 254t
    resin handling and storage
    fibrillation, 234
    temperature vs. cooling time, 235,
    235f
    treatment, 236
    resin selection, 276e277
    Solvay Solexis fine powder PTFE, 172t
    tubing extrusion
    blending lubricant and pigment/
    preforming, 256
    pressure hoses, 258e265, 260f, 261t
    spaghetti tubing, 257e258, 257f,
    258te259t
    types of, 255e256, 256t
    unsintered tape
    blending lubricant and pigment/
    preforming, 240t, 266
    calendaring process, 266e268,
    269fe270f
    drying and stretching, 268e272, 271f,
    271t, 272f
    final tape product, 272, 272f
    round and rectangular bead, 266,
    267f, 268t
    thread sealant tape, 265e266
    wire coating
    conductor, 254e255
    die, 244f, 248e250, 252f
    drying, 243t, 250e253
    pigment addition, 245
    polytetrafluoroethylene paste
    changes, 246, 250f
    preforming, 245e246, 247fe248f,
    248t
    properties, 242
    ram extruder, 248, 251fe252f
    reduction ratio, 246, 253e254
    resin blending, lubricant, 244e245,
    244fe245f
    sintering and cooling, 254te255t
    wire extruder, 246, 249f
    Fischer-Tropsch process, 313
    Fluorinated additives
    PTFE additives, 309, 309t
    applications of, 309, 310t
    feedstock for, 309e310
    grinding, 312
    modified waxes, 312e313
    radiation, 312
    thermal cracking, 312
    Fluorinated ethylene propylene (FEP)
    polymer, 17
    Fluorination
    polyolefin surfaces, 13
    SelectfluorTM, 13e14
    Fluorine, 315, 318f
    characteristics, 13e17, 14t
    extreme element, 14
    inorganic chemistry, 15e16
    and nature, 17
    organic chemistry, 16e17
    preparation, 14e15, 15f
    uniqueness, 12e13, 13t
    Fluoropolymers
    applications and uses, 20, 22t
    automotive and transportation
    industry, 9
    bond values of, 315, 316t
    characteristics, 8
    competition and industry structure, 11
    consumption of, 10, 10f
    evolution of, 5, 6f
    films, 322
    fundamental properties, 18, 18te19t
    growth waves, 5, 6f
    low friction and surface energy, 30e32,
    32t
    market for, 8
    PDL resistance rating, 1e3, 2t
    plasma treatment, 321e326
    polymer science, 1e3, 2f, 2t
    polytetrafluoroethylene, 3e5, 5t
    properties, 8
    regional consumption, 9e10, 9f
    Roy Plunkett, 3e4
    solvents effect, 30, 30te31t
    structure-rheology-fabrication process,
    46t
    vs. key processing/application
    trade-offs, 18, 19t
    Fluroxene, 16
    Forming lined piping, 462
    Freon, 3
    G
    Glass fabric, 462
    Glass fiber, 337, 338f
    Glow discharge treatment, 322, 323t
    Glyme-based etchant solution, 320
    Gore-Tex GR sheet gasketing,
    465e466, 467f
    Granular polytetrafluoroethylene
    automatic molding
    demolding, 199
    pressure/dwell period and specific
    gravity, 200, 201f
    steps of, 199, 200f
    commercial grades
    Asahi Glass Company Fluon, 159t
    Chenguang granular PTFE resins,
    163t
    Daikin Company Polyflon, 160t
    DuPont Teflon, 159t
    Dyneon Company Hostaflon, 160t
    Fuxin Hengtong granular PTFE
    resins, 164t
    granular fine-cut grouping, low-flow,
    157t
    granular pelletized grouping, freeflow, 158t
    Gujarat Fluorochemical Company
    Inoflon granular PTFE resins,
    167t
    Halopolymer Company
    Fluoropolast, 162t
    homopolymer polytetrafluoroethylene
    ram extrusion granular resins, 158t
    694 INDEXJiangsu Meilan granular PTFE resins,
    165t
    modified polytetrafluoroethylene
    granular resins, 158t
    Shandong Dongyue granular PTFE
    resins, 164t
    Shandong Huafu (Jinan 3F) granular
    PTFE resins, 166t
    Shanghai 3F granular PTFE resins,
    164t
    SinoFluoron Company granular PTFE
    resins, 166t
    Solvay Solexis Company Algoflon,
    161t
    Zhejiang Juhua granular PTFE resins,
    163t
    Zhejiang Jusheng granular PTFE
    resins, 165t
    compression molding. See Compression
    molding method
    fabrication process, 177, 177t
    free sintering, 177
    isostatic molding. See Isostatic molding
    process
    ram extrusion. See also Ram extrusion
    compaction, 220e223, 220fe222f
    cycles, 219, 220f
    definition, 218
    horizontal ram extruder, 219, 219f
    resin feed, 219e220
    steps for, 218e219
    vertical ram extruder, 218, 218f
    resin selection
    commercial free and low flow PTFE
    resins, 178, 179t
    dielectric strength vs. apparent
    density, 178, 178f
    filling example, in three dimensions,
    178, 179f
    free flow, 177
    property and apparent density vs. flow,
    177, 178f
    tensile strength vs. apparent density,
    178, 178f
    Graphite, 338, 339f
    Gylon sheet gasketing material, 465,
    466f
    H
    Halex reaction, 16
    Halogens, 12
    Hammer milling
    amoeboid and dendritic structures, 107,
    107f
    commercial products, 107, 108t
    PTFE powders, 107, 107f
    schematic diagram, 106e107, 106f
    temperature, 107, 108f
    HCFC-22, 48e49
    Hexafluoropropylene (HFP)
    properties, 67e68, 68t
    synthesis
    CFC-216ba, 67
    chlorofluorination, 64
    dimerization, 66, 66t
    perfluoroisobutylene, 65
    pyrolysis of R23, 65, 65te66t
    High-purity fluid handling components,
    468, 471f
    Hollow glass microspheres, 339, 340f
    Hot compression molding, 198e199,
    199t
    Hourglassing, 226
    Hydraulic presses, 181, 181f
    Hydrostatic molding. See Isostatic
    molding process
    Hysteresis loop, 284
    I
    Injection molding, 304e305,
    304f, 305t
    Irradiation behavior, 444e446
    Isochronous stress-strain, 416f
    Isostatic molding process
    bag exertion pressure, 203
    basics, 204, 204f
    bolt clamping, fluid sealing, 204e205,
    206f
    design
    bag attachment, 211, 211f
    flexible bag, 214, 215t
    mold and bag sealing, 211f, 213
    mold configuration and dimensions,
    212e213
    preform shape, 208e209, 208f
    pressurization direction, 209e210
    procedure, 214e217, 216t
    surface finish of preform, 209
    mandrel, 204e205
    molded parts, 203, 203t
    outer flexible bag and inner rigid part,
    205, 207f
    pressed samples, 201e202, 202f
    principle steps, 202e203, 202f
    PTFE resins, 193f, 217e218
    vs. fabrication techniques, 203e204
    wet and dry bag process, 205,
    206fe207f
    J
    Jennings international horizontal
    extruder, 251f
    K
    K-416, 4
    Kettle/polykettle, 98
    L
    Le Chatelier-Braun principles, 49e50
    Lethal concentration, 319
    Lethal dose, 319
    Limiting oxygen index (LOI), 384e387,
    430e431
    Liquid ammonia, 318
    M
    Machining, 453e455
    centerless grinding, 454, 454t
    drilling/tapping and threading, 454
    machining filled PTFE parts, 455
    sawing and shearing, 454
    skiving, 454e455
    turning and milling, 454
    Mechanical applications, 471e475
    Mechanical properties, 442
    Medical devices, 477
    Melt creep viscosity (MCV), 401, 401t
    Melt processible fluoropolymers, 463
    Melt processing, 38
    Milling, 454
    Modified waxes, 312e313
    Moissan’s reactions, 15, 15f
    Molecular weight (MW), 399e400
    Molybdenum disulfide (MoS2), 339,
    340f
    Monoglyme, 319
    N
    Natural waxes, 313
    Nonbioaccumulative fluorinated
    surfactants, 86
    O
    Orientation Index (OI), 263e264
    P
    PCTFE. See Polychlorotrifluoroethylene
    (PCTFE)
    Perfluorinated ethylene-propylene
    copolymer
    vs. polytetrafluoroethylene, 28t
    Perfluoroalkoxy (PFA), 17e18
    Perfluoroalkyl vinyl ethers (PAVEs)
    properties, 70, 71t
    synthesis
    1,1 DHPPTE, 69
    hexa-fluoropropylene oxide, 69e70
    specifications, 70t
    steps, 70t
    INDEX 695Perfluorobutane sulfonate (PFBS), 79
    Perfluoroisobutylene (PFiB), 65
    Perfluorooctane sulfonate (PFOS)
    chemical structure, 77f, 77t
    issues, 78e79
    perfluorinated surfactants, 77
    physical properties, 77t
    Perfluorooctanoic acid (PFOA)
    chemical structure, 77f, 77t
    commercial uses, 78t
    degradation, 80e82
    ECF process, 78
    physical structure, 77f, 77t
    problems, 79e83, 81t, 82f
    telomerization, 78
    toxicity, 82e83
    Perfluoroolefins, 29
    Permeation fundamentals
    measurement, 391e392, 391f
    testing by absorption, 392, 392f
    transmission, 393t
    variables, 389, 389t
    Plastics
    organic chemical effect, 43t
    physical and mechanical properties, 38,
    39te40t
    thermal and electrical properties, 41t
    water absorption effect, inorganic
    chemicals, 42t
    Plastics design library (PDL), 8e9,
    610te611t
    Poisson ratio, 419e420
    Poker chipping, 219
    Polychlorotrifluoroethylene (PCTFE),
    17, 17f
    application and uses, 24, 25te26t, 28t,
    30te31t
    chemical structure of, 25f
    Polymerization aid, 95
    Polymerization surfactants
    alternative surfactants
    APFO, 84, 84f
    chemical structures, 86e90
    requirements, 84e85, 85te86t
    emulsion and suspension
    polymerization, 76
    EPA action, 83e84
    perfluorooctane sulfonate
    chemical structure, 77f, 77t
    issues, 78e79
    perfluorinated surfactants, 77
    physical properties, 77t
    perfluorooctanoic acid
    chemical structure, 77f, 77t
    commercial uses, 78t
    degradation, 80e82
    ECF process, 78
    physical structure, 77f, 77t
    problems, 79e83, 81t, 82f
    telomerization, 78
    toxicity, 82e83
    Polytetrafluorethylene (PTFE), 309, 309t
    anti-drip applications, 296, 297t
    applications, 279, 279t, 297e298
    applications of, 309, 310t
    atmospheric pressure plasma treatment,
    328e333, 329t
    atomic resolution images, 34, 34f
    characterization
    dispersions, 148e149, 149te150t
    fine powder PTFE resins, 145e148,
    147te148t
    granular PTFE resins, 143e145,
    144te146t
    standard specification methods, 143,
    143t
    chemical compatibility, 382e387
    effect of ozone on, 382e384
    with halogenated chemicals, 385t
    with various chemicals, 385t
    coating technology
    processes, 282e283, 283f
    rheology, 283e285, 284fe285f
    surface energy, 285e286, 285f, 287t
    commercial grades
    Asahi Glass Company PTFE
    dispersions, 168t
    ASTM Method D 4441, 157
    Daikin PTFE Dispersions, 169t
    DuPont’s dispersions, 168t
    Dyneon’s Dispersions, 169t
    Solvay Solexis Algoflon PTFE
    dispersions, 170t
    commercialization, 4e5, 5t
    conformations and transitions, 32e35, 33f
    dedusting powders, 297
    dispersion formulation and
    characteristics, 286e289, 288f,
    288t, 289f, 289t, 290f
    emission during processing, 480e481,
    481t
    environmental protection and disposal
    methods, 486e487
    packaging disposal and recycling,
    486e487
    ESC, 392e395
    fluoropolymers, 394e395
    F and CeF bond, impact of
    comparative polarization, 24e25, 25f
    hydrogen and halogens, 24, 25t
    phase diagram of, 25, 25f
    polyethylene properties, 26, 26t
    feedstock for, 309e310
    filled bearings, 297
    film casting, 295e296, 295t, 296f, 296t
    flax and polyaramide impregnation,
    292
    porous metals and graphite, 293
    processing, 292e293
    fluoroplastics, sodium etching of,
    314e321
    description of, 315e319
    elevated temperature etching,
    320e321
    new chemistry, 319e320
    sodium etching chemistry, 315
    fluoropolymer scrap and recycling,
    485e486
    fluoropolymers, toxicology of, 479
    food contact, 485
    glass cloth coating, 289e290
    equipment, 290e291, 290fe292f
    processing, 291e292, 292t
    grinding, 312
    homopolymer, 12, 13te14t, 18te19t,
    21te22t, 652te654t
    melt creep viscosity, 38
    melting point, 38
    metal and hard surface coating,
    293e294
    modified, 12e13, 655t
    modified waxes, 312e313
    oxygen compatibility, 384e387
    PCTFE
    chemical compatibility of, 387, 388t
    perfluorinated ethylene-propylene
    copolymer, 27, 27f, 28t
    plasma treatment of, 321e326
    polychlorotrifluoroethylene
    CeCl and CeF bonds, comparative
    polarization, 27e28, 28f
    fluorine to chlorine atom ratio,
    28e29, 28f
    FTIR spectra, 28e29
    procedure, 38e40, 44f
    properties, 278, 278t
    PTFE yarn manufacturing, 294e295
    radiation, 312
    safety measures, 481e485, 481t
    degradation products, ventilation of,
    482
    equipment cleaning and maintenance,
    484
    fire hazard, 485
    material incompatibility, 485
    personal hygiene, 485
    processing and fabrication, 482e484
    protective clothing, 485
    696 INDEXspillage cleanup, 484
    scanning electron micrograph, 326, 326f
    scanning probe microscopy, 326, 327f
    solubility parameters, 395
    storage and handling, 279e280
    surfactant transition, 280e282
    fingering, 280e282
    fluoropolymers manufacturing, 280,
    281f
    Gendorf fluoropolymer
    manufacturing process, 280, 281f
    thermal cracking, 312
    thermal properties of, 479e480, 480f,
    480t
    X-ray diffraction, 35t
    Poly vinyl fluoride (PVF), 18, 315, 316t,
    383
    Polyvinylidene fluoride (PVDF), 18
    Porter process, 318
    Press, 304
    Pressure hoses
    applications, 260e261
    blending lubricant and pigment/
    preforming, 261
    commercial grades, 261, 261t
    convoluted and braided tubing,
    259e260, 260f
    crystallinity stiffness, 261, 261t
    extrusion/sintering and cooling,
    261e263
    liner extrusion, 264e265, 265f
    PTFE reinforcement, 258e259, 260f
    quality control, 263e264
    Protective colloid, 112e113
    PTFE
    applications and uses, 20, 22t
    China, 9
    India, 9e10
    United States, 9
    Western Europe, 9
    R
    Radiation, 312
    Ram extrusion
    compaction, 220e223, 220fe222f
    cycles, 219, 220f
    definition, 218
    equipment design, 223t, 228
    dies, 229e230
    drive system, 228e229
    extrusion ram, 229
    horizontal ram extruder, 219f, 228
    resin feed system, 230
    vertical ram extruder, 218f, 228
    horizontal ram extruder, 219, 219f
    M-24 molded cylindrical rods, 232t, 233
    M-24 multiple ram extrusion molding,
    3-rod extrusion, 232t, 233
    molding conditions and tensile
    properties, 231t, 233
    profile extrusions, 230f, 233
    resin feed, 219e220
    sintering and cooling, 200f, 220f
    cooling, 227
    die skin formation, 227e228
    heat requirements, 223e224, 223t,
    224f
    steps for, 218e219
    vertical ram extruder, 218, 218f
    Reinforced gasketing material,
    fabrication of
    process background, 348, 348f
    process description, 348e350, 349f
    Resin, 303
    Rotational lining, 463
    Rotolined transition component, 464f
    Roy Plunkett, 3e4
    S
    Safety measures, 481e485, 481t
    degradation products, ventilation of, 482
    equipment cleaning and maintenance,
    484
    fire hazard, 485
    material incompatibility, 485
    personal hygiene, 485
    processing and fabrication, 482e484
    protective clothing, 485
    spillage cleanup, 484
    Sawing, 454
    Seamless lining, 463, 463f
    SelectfluorTM, 13e14
    Self-supporting components, 466e467
    Semiconductor processing, 468e470
    Shearing, 454
    Simons Electro Chemical Fluorination,
    78
    Skiving, 454e455
    Sodium amide, 318
    Sodium-ammonia method, 318
    Sodium etching, time of, 315, 317t
    Sodium naphthalenide, 318e319, 319f
    Solubility parameters, 395
    Spaghetti tubing
    Daikin-polyflon TFE, 258, 259t
    extrusion conditions, 258, 258t
    hydraulic paste extruder, 257f
    tube extrusion die, 257, 257f
    Spectroscopic properties, 448
    SSG. See Standard specific gravity (SSG)
    Standard specific gravity (SSG), 400
    Stress, 302
    Stress relaxation, 413
    Stress-strain curves, 409, 409fe410f
    Stretch Void Index (SVI), 263e264
    Stretch void index (SVI), 148
    Surface chemistry, 315, 318f
    Suspension polymerization
    CTFE, 140
    evolution
    carboxylic acid effect, 102e103, 103t
    commercial comonomers,
    101e102
    disuccinic acid peroxide, 102
    finishing processes, 100, 100f
    Plunkett polymerization, 100e101,
    101f
    reactor for, 102, 103f
    scanning electron micrograph, 100,
    100f
    incubation period, 98
    pelletized granular PTFE, 109e118
    presintered granular PTFE
    ram extrusion and resistance,
    118e119, 119f
    800X series cutter and interior design,
    119, 119f
    process conditions, 98, 98f
    reactor and operations
    air milling, 105e106, 105fe106f
    automatic tank internal washer, 104,
    104f
    fine cut powders, 105, 105f
    hammer milling, 106e107,
    106fe108f, 108t
    schematic representation, 103, 103f
    temperature, 103e104
    surfactant micelle, 99f
    wet reactor bead
    slurry, 107e108
    Taylor Stiles cutters, 109f
    Synthesized hydrocarbons, 313
    Synthetic waxes, 313
    T
    Tapping, 454
    Tedlarby DupontA, 38
    Teflon, 396
    Telomerization process, 78
    Tetra-Etch, 317t
    Tetrafluoroethylene (TFE)
    chlorotrifluoroethylene. See
    Chlorotrifluoroethylene (CTFE)
    copolymers
    2,2-bis-trifluoromethyl-4,5-difluoro-
    1,3-dioxole, 45, 45f
    fluorinated vinyl ethers, 44e45, 45f
    hexafluoropropylene, 44
    INDEX 697Tetrafluoroethylene (TFE) (Continued)
    Lumiflonresins, cross-linking
    mechanism, 44e45, 45f
    crystallinity, 398e400
    melting point, 399e400, 400t
    structure, 396f, 398e399, 398fe399f
    dispersion grade PTFE
    Berry’s technique, 137
    electrodecantation, 138
    process variable, 137, 137t
    salting out, 136e137
    electrical properties, 422e424
    emulsion/dispersion polymerization. 95,
    95t. See also Emulsion
    polymerization)
    fatigue properties, 415e420
    abrasion and wear, 419
    friction, 415e416
    hardness, 415
    impact strength, 415
    poisson ratio, 419e420
    PV limit, 416e419
    fine powder PTFE
    agglomerates, 139
    coagulating agent, 138
    steps of, 138
    fine powder resins, 95, 95t, 100
    flammability characteristics, 430e431
    granular resins, 95, 95t
    homopolymers
    automatic molding, 38
    compression molding, 38
    dispersion and suspension processes,
    38, 40
    fine powder particles, 38, 44f
    granular particle, 38, 44f
    irradiation behavior, 431e432
    mechanical properties, 409e413
    deformation under load (creep) and
    cold flow, 411e413
    molecular weight, 400e402
    melt creep viscosity (MCV), 401, 401t
    Mn calculation using DHc, 401e402
    practical aspects of, 402, 402fe404f
    SSG, Mn calculation using, 401
    standard specific gravity (SSG), 400
    polymerization mechanism and
    reactions, 96e99, 96fe97f
    preparation
    chlorodifluoromethane, 48e49
    fluorspar, 48e49
    pyrolysis temperature and pressure,
    49, 49t
    R23, 48
    R12/F12, 48
    temperature effect, 50e51, 52fe53f
    processing, influence of, 403e407, 404t
    voids and flaws, 406e407
    properties, 63t
    HCl, 62
    heat reaction, 61
    oxygen, 61e62
    PTFE, microstructure and fracture of,
    407e409
    purification methods
    Daikin technology, 60
    preliminary distillation column, 60,
    61t
    second distillation column, 61, 61t
    starting material composition, 60, 61t
    refractive index, 438
    standard measurement methods, 438
    surface properties, 432e435
    suspension polymerization. See also
    Suspension polymerization
    evolution, 100e119, 100fe101f
    incubation period, 98
    process conditions, 98, 98f
    surfactant micelle, 99f
    synthesis
    C4F8, 57, 58t
    CF3-CHF2 to CF2¼CF2, 55, 56t
    final gaseous product, 55t
    gas chromatography, 54, 54t
    gases and conversion, 51e54, 54t
    graphite tube, 55
    HFP, 59t, 60
    hydrogen chloride, 59
    reaction gases, 54t
    solid reaction product analysis, 56,
    56t
    thermal behavior, 424e430
    heat deflection temperature, 430
    thermal conductivity and heat
    capacity, 429
    thermal expansion, 428e429
    thermal stability, 424e428
    van der Waals forces, 99
    Tetraglyme, 320
    Tetrahydrofuran, 319
    Thermal behavior, 424e430
    Thermal cracking, 312
    Thermal degradation, 444, 448f
    Thermal properties, 443e444, 447t
    Thermal stability, 424e428
    Thermoplastic fluoropolymers, 463
    Threading, 454
    Thread sealant tapes, 465, 465f
    1,1,2-Trichloro-1,2,2-trifluoroethane
    (TCTFE), 70e71
    Turbula Shaker Mixer, 245, 245f
    Turning, 454
    Turpentine, 14
    U
    Unlined valves, 465
    Unsintered tape
    blending lubricant and pigment/
    preforming, 240t, 266
    calendaring process, 266e268,
    269fe270f
    drying and stretching, 268e272, 271f,
    271t, 272f
    final tape product, 272, 272f
    round and rectangular bead, 266, 267f,
    268t
    thread sealant tape, 265e266
    V
    van der Waals forces, 30
    Vessels, 463
    Vinyl fluoride (VF) polymers, 45
    Vinylidene fluoride (VDF) polymers, 45
    Viscosity, 320
    Volume resistivity, 443, 446f
    W
    Weathering properties, 452
    Weep Test, 263, 264
    X
    Xanthate, 294
    Z
    Zero strength time (ZST), 149, 301, 301f,
    301t
    ZST. See Zero strength time (ZST)

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