Fluorinated Ionomers Second edition

Fluorinated Ionomers Second edition
اسم المؤلف
C. G. Processing
17 نوفمبر 2023
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Fluorinated Ionomers Second edition
Walther Grot
C. G. Processing, Inc.,
Chadds Ford, Pennsylvania
Table of contents
Series Page
Plastics Design Library
PDL Fluorocarbon Series Editor’s Preface

  1. Introduction
    1.1. Polymers
    1.2. Physical Shapes
  2. History
  3. Manufacture
    3.1. Introduction
    3.2. Perfluorinated Ionomers
    3.3. Polymerization
    3.4. Fabrication
    3.5. Hydrolysis and Acid Exchange
    3.6. Finishing and Testing
    3.7. Liquid Compositions
    3.8. Fluorinated Ionomers with Phosphonic or Sulfonyl Imide Functional Groups
    3.9. Partially Fluorinated Ionomers
    3.10. Composite Materials of Ionomers and Inorganic Oxides
    3.11. Composite Materials of Ionomers and a Porous Matrix
    3.12. Remanufactured Membranes
  4. Properties
    4.1. Properties of the Precursor Polymers
    4.2. Properties of the Ionic Forms
    4.3. Morphology
    4.4. Transport Properties
    4.5. Optical Properties
    4.6. Thermal Properties
    4.7. Stability
  5. Applications
    5.1. Electrolysis
    5.2. Sensors and Actuators
    5.3. Dialysis
    5.4. Gas and Vapor Diffusion
    5.5. Protective Clothing
    5.6. Catalysis
  6. Fuel Cells and Batteries
    6.1. Introduction
    6.2. Operating Parameters
    6.3. Ionomer Stability
    6.4. Direct Methanol Fuel Cells (DMFCs)
    6.5. Manufacture of MEAs
    6.6. Rechargeable Flow Through Batteries
  7. Commercial Membrane Types
    7.1. Unreinforced Perfluorinated Sulfonic Acid Films
    7.2. Reinforced Perfluorinated Membranes
  8. Economic Aspects
    8.1. Chlor-Alkali Cells
    8.2. Fuel Cells
  9. Experimental Methods
    9.1. Infrared Spectra
    9.2. Hydrolysis, Surface Hydrolysis, and Staining
    9.3. Other Reactions of the Precursor Polymer
    9.4. Ion Exchange Equilibrium
    9.5. Determination of EW by Titration or Infrared Analysis
    9.6. Determining Melt Flow
    9.7. Distinguishing the Precursor Polymer from Various Ionic Forms
    9.8. Fenton’s Test for Oxidative Stability
    9.9. Examination of a Membrane
    9.10. Determining the Permselectivity
    9.12. Simple Electrolytic Cells
  10. Heat Sealing and Repair
  11. Handling, Storage, and Installation
    11.1. Handling the Film
    11.2. Pretreatment
    11.3. Installation
  12. Toxicology, Safety, and Disposal
    12.1. Toxicology
    12.2. Safety
    12.3. Disposal
    Appendix A. A Chromic Acid Regeneration System
    Appendix B. Laboratory Chlor-alkali Cell
    Appendix C. Solution Cast Nafion Film
    Appendix D. Plastic-Based Bipolar Plates
    DuPont™ Nafion® membranes: Membranes for Fuel Cells
    DuPont™ Nafion® PFSA Membranes N-112, NE-1135, N-115, N-117, NE-1110: perfluorosulfonic acid polymer
    Suppliers and Resources
    Glossary and Web Sites
    Suppliers and Resources
    Aldrich Chemicals Retailer of Nafion® products (precut sheets
    20×25 and 30×30 cm, solution and powder),
    Alfa Aesar Retailer of Nafion® products (precut sheets),
    www.alfa.com, 978-521-6417.
    Asahi Glass Manufacturer of Flemion® perfluorinated
    ionomer products, www.asg.co.jp
    Asahi Kasei Manufacturer of Aciplex® perfluorinated
    ionomer products. Supplier of large-scale
    chlor-alkali plants and cell technology;
    contact: Masanobu Wakizoe, wakizoe.
    [email protected]
    Ballard Power Systems Supplies PEM fuel cells, www.ballard.com,
    C.G. Processing, Inc. Distributor of Nafion® products (custom cut
    sheets), custom fabrication of Nafion by heat
    sealing, [email protected], 610-388-6201.
    ChemTech, Inc. Supplier of systems for chromic acid regeneration, 231-737-7433.
    Chlorine Engineers
    Chlorine Genie, Inc.
    Manufacturer of mono- and bi-polar electrolyzers, www.chlorine-eng.co.jp
    Supplier of very small chlorine generators (for
    swimming pools etc.), 5031 Blum Road,
    Martinez, CA 94553. Phone: 925 723 0400,
    E.I. DuPont de Nemours Manufacturer of Nafion® perfluorinated
    ionomer products;
    [email protected],
    ElectroCell A/S Supplier of general-purpose electrolytic cells,
    small chlorine generators, 45-9737-4499;
    www.electrocell.com, [email protected],
    Europe and USA; contacts: Gusten Eklund
    46-83-65-095; Dr. D.J. Mazur, 746-
    564-1414; [email protected],
    [email protected]
    Electrochem, Inc. Supplier of fuel cell test stations,
    www.fuelcell.com278 Fluorinated Ionomers
    Electrosynthesis Co. Contract R&D in electrochemistry,
    supplier of electrochemical equipment,
    www.electrosynthesis.com, 716-684-0513,
    716-684-0511 (fax).
    Eltech Systems Supplier of anodes, particularly DSA®
    mixed metal oxide coated titanium anodes,
    E-Tek Supplier of ELAT® GDEs, MEAs, catalysts and
    related products, www.etek-inc.com; division
    of PEMEAS, www.pemeas.com
    Fumatech, GmbH Supplier of membranes and other fuel cell
    components, www.fumatech.de; contact:
    [email protected], 49-6894-9265-0.
    Ion-Power, Inc. Distributor of NAFION® products,
    www.ion-power.com; manufacturer of MEAs
    and solutions of Nafion®, 302-832-9550.
    Krupp-Uhde Manufacturer of bi-polar electrolyzers and large chlor-alkali plants
    [email protected], 49-231-547-0.
    PermaPure, Inc. Manufacturer of tubular humidity exchangers,
    www.permapure.com, 800-337-3762,
    732-244-8140 (fax).
    Plug Power Supplier of PEM fuel cell systems,
    www.plugpower.com, 518-782-7700.
    Quiver Ltd. Manufacturer of membrane leak testing and
    repair equipment, [email protected];
    (39)-02-66-50-34-63, www.quiverltd.it
    Solution Technology, Inc. Manufacturer of solutions of Nafion®,
    610-388-6201, 388-6974 (fax).
    3 M Manufacturer of MEAs, perfluorinated ionomer
    films and other fuel cell components; contact:
    Steven Hamrock, (651)-733-4254; www.
    Yeoh, Ray Chlor-Alkali Consultant
    Bangkok : 66852125110,
    China : 8613708232653
    E-mail : [email protected] &
    [email protected]
    Glossary and Web Sites
    Acyl Fluoride—An aliphatic acid fluoride.
    Carbon Black—A black colloidal carbon filler made by the partial combustion and/or thermal cracking of natural gas, oil, or another hydrocarbon.
    Depending on the starting material and the method of manufacture, carbon black can be called acetylene black, channel black, furnace black, etc.
    For example, channel black is made by impinging gas flames against steel
    plates or channel irons, from which the deposit is scraped at intervals. The
    properties and the uses of each carbon black type can also vary. Also called
    colloidal carbon.
    Carbon Fiber—Carbon fibers are high-performance reinforcement
    consisting essentially of carbon. They are made by a variety of methods including pyrolysis of cellulosic (e.g. rayon) and acrylic fibers,
    burning-off binder from a pitch precursor, and growing single crystals
    (whiskers) via thermal cracking of hydrocarbon gas. The properties of
    carbon fibers depend on the morphology of carbon in them and are at
    their highest levels for crystalline carbon (graphite). These properties
    include high modulus and tensile strength, high thermal stability, electrical conductivity, chemical resistance, wear resistance, and relatively
    low weight.
    Current Efficiency (CE)—The fraction of current used in the desired
    reaction. CE can be different at the anode, membrane and cathode (e.g. in
    “chromic acid regeneration”).
    Denier—Unit of yarn/fiber size described as the weight (in grams) of a
    length of 9000 yards.
    Dictionary of Electrochemistry—www.corrosion-doctors.org/Dictionary/
    Differential Scanning Calorimetry (DSC)—DSC is a technique in which
    the energy absorbed or produced is measured by monitoring the difference
    in energy input into the substance and a reference material as a function
    of temperature. Absorption of energy produces an endotherm; production280 Fluorinated Ionomers
    of energy results in an exotherm. May be applied to processes involving
    an energy change, such as melting, crystallization, resin curing and loss of
    solvents, or to processes involving a change in heat capacity, such as the
    glass transition.
    Diglyme—Diethylene glycol dimethyl ether.
    Dispersion—A dispersion is often defined as a uniform mixture of solid
    particles and a liquid. It may contain other agents such as a surfactant
    and a resin soluble in the liquid (solvent). An example of a dispersion is a
    house paint. A feature of most dispersions is stability, which means little
    or no settling of the solid particles.
    Dispersion Polymerization—This technique is a heterogeneous regime
    where a significant amount of surfactant is added to the polymerization
    medium. Characteristics of the process include small uniform polymer
    particles which may be unstable and coagulate if they are not stabilized.
    Hydrocarbon oil is added to the dispersion polymerization reactor to
    stabilize the polytetrafluoroethylene emulsion. Temperature and agitation control are easier in this mode than suspension polymerization.
    Polytetrafluoroethylene fine powder and dispersion are produced by this
    Donnan Dialysis—A process to selectively move and/or concentrate an
    ionic species from one electrolyte to another through a permselective
    membrane without the application of an external current. www.pwea.org/
    DSC—See Differential Scanning Calorimetry.
    Electrochemistry—See Dictionary of Electrochemistry.
    Electrode—An electronic conductor in contact with an ionic conductor or
    electrolyte. If electrons are transferred from the electrode to some components of the electrolyte, the electrode is called a cathode; in the opposite
    case it is the anode.
    Epoxides—Organic compounds containing three-membered cyclic
    group(s) in which two carbon atoms are linked with an oxygen atom as
    in an ether. This group is called an epoxy group and is quite reactive,
    allowing the use of epoxides as intermediates in the preparation of certainGlossary and Web Sites 281
    fluorocarbons and cellulose derivatives, and as monomers in the preparation of epoxy resins.
    EW—Grams of ionomer containing one equivalent of functional groups.
    Extrusion—Process for converting a polymer to lengths of uniform crosssection by melting or softening the material and forcing it to flow plastically through a die orifice, which determines the cross-section. Typically, a
    single or twin screw conveyor is used to provide the force and movement;
    however, many variations of this process are used widely in working metals and processing plastics.
    FEP—See Fluorinated Ethylene Propylene Copolymer.
    Fill—(In weaving) threads that run transverse back and forth between the
    two edges of the fabric. See also Warp.
    Fluorinated Ethylene Propylene Copolymer (FEP)—A random copolymer of tetrafluoroethylene and hexafluoropropylene.
    Free Radical—An atom or group of atoms with an odd or unpaired electron. Free radicals are highly reactive and participate in free radical chain
    reactions, such as combustion and polymer oxidation reactions. Scission
    of a covalent bond by thermal degradation or radiation in air can produce
    a molecular fragment named a free radical. Most free radicals are highly
    reactive because of their unpaired electrons, and have short half-lives.
    R – R′ →R· + R′
    FTIR (Fourier Transform Infrared Spectroscopy)—A spectroscopic
    technique in which a sample is irradiated with electromagnetic energy from
    the infrared region of the electromagnetic spectrum (wavelength ~0.7–
    500mm). The sample is irradiated with all infrared wavelengths simultaneously, and mathematical manipulation of the Fourier transform is used to
    produce the absorption spectrum or “fingerprint” of the material. Molecular absorptions in the infrared region are due to rotational and vibrational
    motion in molecular bonds, such as stretching and bending. FTIR is commonly used for the identification of plastics, additives, and coatings.
    Heat Sealing—A method of joining plastic films by the simultaneous
    application of heat and pressure to the areas in contact. Heat can be applied
    using hot plate welding, dielectric heating, or radiofrequency welding.282 Fluorinated Ionomers
    Hexafluoropropylene (HFP)—CF3–CF=CF2.
    HF (Hydrofluoric Acid)—It is a highly corrosive acid.
    HFP—See Hexafluoropropylene.
    HFPO (Hexafluoro propylene epoxide)—See Epoxides.
    Hydrophilic Surface—Surface of a hydrophilic substance that has a
    strong ability to bind, adsorb, or absorb water; a surface that is readily
    wettable with water.
    Hydrophobic—Water repellent.
    Leno Weave—A weave pattern using a double thread as warp. One thread
    passes over the fill threads and the other underneath. After each fill, the
    two warp threads are twisted 360°, thereby locking in the fill.
    Melt Processable Polymer—A polymer that melts when heated to its
    melting point and forms a molten material with definite viscosity value at
    or somewhat above its melting temperature. Such a melt should be pumpable and flow when subjected to shear rate using commercial processing
    equipment such as extruders and molding machines.
    Membrane Electrode Assembly—A component used primarily in
    fuel cells consisting of a central film of ionomer coated on both the
    surfaces with a catalyst. In addition to catalyst, this layer usually also
    contains carbon black and ionomer to provide both electronic and ionic
    Micron—A unit of length equal to 1 × 10–6m. Its symbol is the Greek
    lower case letter “mu” followed by meter m (μm).
    Molecular Weight—The molecular weight (formula weight) is the sum
    of the atomic weights of all the atoms in a molecule (molecular formula).
    Also called MW, formula weight, average molecular weight.
    Molecular Weight Distribution—The relative amounts of polymers of
    different molecular weights that comprise a given specimen of a polymer.
    It is often expressed in terms of the ratio between weight- and numberaverage molecular weights, Mw/Mn.Glossary and Web Sites 283
    Monomer—The individual molecules from which a polymer is formed
    (i.e. ethylene, propylene).
    Multifilament—In textiles, a fiber or yarn composed of several individual
    filaments, each of 75 denier or less, that are gathered into a single continuous bundle.
    Perfluoroalkyl Vinyl Ether (PAVE)—Rf–O–CF=CF2, where Rf is a perfluorinated alkyl group containing one or more carbon atoms.
    Perfluoro Ammonium Octanoate (C8)—A surfactant used in emulsion
    PMVE (Perfluoromethyl vinyl ether)—Comonomer for the production
    of fluoroelastomers.
    Polar—In molecular structure, a molecule in which the positive and negative electrical charges are permanently separated. Polar molecules ionize
    in solution and impart electrical conductivity to the solution. Water, alcohol and sulfuric acid are polar molecules; carboxyl and hydroxyl are polar
    functional groups.
    Polymer—Polymers are high-molecular-weight substances with molecules resembling linear, branched, cross-linked or otherwise shaped chains
    consisting of repeating molecular groups. Synthetic polymers are prepared
    by polymerization of one or more monomers. The monomers comprise
    low-molecular-weight reactive substances, containing one or more double
    bonds or other reactive molecular bond. Natural polymers have molecular structures similar to synthetic polymers but are not man made, occur
    in nature, and have various degrees of purity. Also called synthetic resin,
    synthetic polymer, resin, plastic.
    Polymer Fume Fever—A condition that occurs in humans as a result
    of exposure to degradation products of polytetrafluoroethylene and other
    fluoropolymers. The symptoms of exposure resemble those of flu and are
    temporary. After about 24h, the flu-like symptoms disappear.
    Porosity—Porosity is defined as the volume of voids per unit volume of
    a material or as the volume of voids per unit weight of material. In this
    book the term “pore” is used to describe a void that exists independent of
    its content. In this sense the water present in a swollen ionomer does not284 Fluorinated Ionomers
    occupy a pore, because the space occupied by the water collapses when
    the water is removed.
    PPVE (Perfluoro propyl vinyl ether)—Monomer for the production of
    melt-fabricable perfluorinated polymers (PFAs).
    Polytetrafluoroethylene (pTFE)—Thermoplastic prepared by radical polymerization of tetrafluoroethylene. It has low dielectric constant,
    superior chemical resistance, very high thermal stability, low friction
    coefficient, excellent antiadhesive properties, low flammability, and high
    weatherability. Impact resistance of pTFE is high, but permeability is also
    high whereas strength and creep resistance are relatively low. The very
    high melt viscosity of pTFE restricts its processing to sinter molding and
    powder coating. Uses include coatings for cooking utensils, chemical
    apparatus, electrical and nonstick items, bearings, and containers. Also,
    pTFE spheres are used as fillers and pTFE oil is used as a lubricant in various plastics. Also called TFE, PTFE, modified PTFE.
    pTFE—See Polytetrafluoroethylene.
    pTFE Fiber—This is a polytetrafluoroethylene (pTFE) yarn produced by
    spinning of a blend of pTFE and viscose (cellulose xanthate used for rayon
    manufacture), followed by chemical conversion, drying, and sintering. In
    the unbleached state this yarn is brown, due to cellulose char.
    Sintering—Consolidation and densification of particles of pTFE above its
    melting temperature is called sintering.
    Skiving—This is a popular method for producing films and tapes of
    polytetrafluoroethylene (pTFE). Also used to produce film on a scale too
    small for extrusion. Skiving resembles peeling of an apple where a sharp
    blade is used at a low angle to the surface of a billet (cylinder) of pTFE. A
    similar method is used in the production of wood veneer from trees.
    Surface Tension—The surface tension is the cohesive force at a liquid
    surface measured as a force per unit length along the surface or the work
    which must be done to extend the area of a surface by a unit area, for
    example, by a square centimeter. Also called free surface energy.
    Surfactant—Derived from surface active agent. Defined as substances
    that aggregate or absorb at the surfaces and interfaces of materials andGlossary and Web Sites 285
    change their properties. These agents are used to compatibilize two or
    more immiscible phases such as water and oil. In general, one end of a
    surfactant is water soluble and the other end is soluble in an organic liquid.
    Viscosity—The internal resistance to flow exhibited by a fluid, the ratio of
    shearing stress to rate of shear. A viscosity of 1 poise is equal to a force of
    1dyn/cm2 causing two parallel liquid surfaces 1cm2 in area and 1cm apart
    to move past one another at a velocity of 1cm/s.
    Voids—See Porosity.
    Warp—(In weaving) threads running lengthwise (= in the machine direction) through the entire length of the fabric. They are crossed by the fill (or
    weft) which runs transversely back and forth between the two edges of the
    fabric. See also Fill.
    Wettability—The rate at which a substance (particle, fiber) can be made
    wet under specified conditions.287
    Acetonitrile, 17
    Acid catalysis, 151
    Acid exchange, in fluorinated
    ionomers manufacture, 34–35
    Aciplex F 4221 (Asahi Chemicals),
    58, 188
    ACIPLEX®, 12
    Actuators, 140–144
    based on Nafion sulfonic
    ionomer, 141
    Acyl Fluoride, 279
    Adiponitrile, 17
    Aldrich Chemicals, 217
    Alfa Aesar, 277
    Alkalinity loop, 127–128
    Alkyl groups
    in perfluorinated ionomers
    manufacture, 11
    Alkylations, 151
    Anion exchange polymers, 42
    Anion/cation equilibrium
    (Donnan exclusion), 220–221
    Applications, of fluorinated
    ionomers, 81–153
    actuators, 140–144,
    see also individual entry
    catalysis, 151–153
    Dialysis, 144–146,
    see also individual entry
    electrolysis, 81–140,
    see also Electrolysis
    gas and vapor diffusion,
    protective clothing, 150–151
    sensors, 140–144,
    see also individual entry
    Asahi Chemicals
    perfluorinated ionomers
    manufacture, 11
    Asahi Glass, 277
    perfluorinated ionomers
    manufacture, 11
    Asahi Kasei, 277
    Asbestos cell, 121
    Ballard Power Systems, 42, 277
    Batteries, fuel cells and, 157–177,
    see also Fuel cells
    Bipolar plates, 259–262, see also
    Plastic-based bipolar plates
    C.G. Processing, Inc., 277
    oxa-hexanoyl fluoride, 20
    3-oxa-hexanoyl fluoride, 21–22
    fluoride, 21
    Carbon black catalyst, in fuel cells, 159
    Carbon Black, 279
    Carbon Fiber, 279
    Carbon monoxide (CO) detector, 140
    Carboxylic barrier layer, 7
    Carboxylic ester precursor, 215
    Casting, film, in fluorinated ionomers
    manufacture, 38–39
    Catalysis applications of fluorinated
    ionomers, 151–153
    acid catalysis, 151
    alkylations, 151
    Nafion as nitration catalyst, 152
    partially mercury-exchanged
    Nafion, 153
    perfluorinated sulfonic acid
    ionomers, 151
    Cation/cation equilibria, 221–223
    multistage separation of cations, 223
    Chemical contamination, 239–240
    ChemTech, Inc., 277
    Index288 Index
    Chlor-alkali cells, 5, 188
    economic aspects, 201
    laboratory chlor-alkali cell, 249
    membrane technology, 6–7
    Nafion® as a separator membrane
    in, 5–6
    plate and frame design of, 84
    Chlorides electrolysis, 123–125
    lithium chloride, 124
    potassium chloride, 123
    tetramethyl ammonium chloride,
    Chlorine Engineers, 277
    Chromic acid
    production, 127
    regeneration system, 130–132,
    components, 131
    nickel–zinc plating, 133
    Commercial 5-kW fuel cell stack,
    characteristics, 164–165
    control, 165
    emissions, 165
    fuel, 164
    operation, 164
    performance, 164
    physical, 164
    safety, 164
    sensors, 165
    Commercial membrane types,
    reinforced perfluorinated
    membranes, 185–188, see also
    individual entry
    unreinforced perfluorinated
    sulfonic acid films, 185–186
    Contact angle, of fluorinated
    ionomers, 66–67
    water contact angle as a function of
    pretreatment, 66
    Copolymerization, in fluorinated
    ionomers manufacture, 26
    Current Efficiency (CE), 279
    Cutting, 240
    Dehalocarbonylation, 23
    Dehalocarbonylation, 25
    Denier, 279
    Dialysis, fluorinated ionomers in,
    Donnan dialysis, 145–146
    Nafion carboxylate polymer, 146
    pervaporation, 146
    Dictionaries of Electrochemistry,
    Differential Scanning Calorimetry
    (DSC), 279–280
    Diglyme, 17, 280
    Dimethyl methylphosphonate, 61
    Dimethyl sulfoxide (DMSO), 34
    1,4-Diodo octafluoro butane, 19
    Direct methanol fuel cells (DMFCs),
    methanol crossover in, 174–175
    Nafion in reducing, 175
    Dispersion, 280
    dispersion polymerization, 280
    Disposal, 245
    Divinyl benzene (DVB), 41
    Donnan dialysis, 145, 280
    Donnan equation, 220–221
    Dow Chemicals, 7
    Dow synthetic route, 24
    DuPont Experimental Station, 5–6
    perfluorinated ionomers
    manufacture, 11
    DuPont™ Nafion® PFSA
    membranes NRE-211 and
    NRE-212, 251–257
    description, 251–252
    handling practices, 256
    order and packaging information,
    product labeling, 266
    properties, 264
    roll storage conditions, 266–267
    scrap disposal, 267
    static discharges, 268Index 289
    Dyes, 216
    Bromothymol blue, 216
    carboxylic polymer, 216
    crystal violet, 216
    malachite green, 216
    methyl violet, 216
    Methylene blue, 216
    Oil Red, 217
    Sevron® Brilliant Red 4G
    (DuPont), 216
    E.I. DuPont de Nemours, 277
    Economic aspects, 201–209
    chlor-alkali cells, 201–208
    fuel cells, 208–209
    World chlorine capacity by
    process, 207
    World chlorine capacity by type of
    process, 208
    World chlorine consumption by
    region, 207
    ElectroCells, 97–102
    Electrochem, Inc., 277
    Electrochemical fluorination
    for perfluorinated ionomers
    preparation, 7
    Electrode, 81
    Electrolysis, fluorinated ionomers in,
    chromic acid regeneration,
    of chlorides, 122–125
    electro-winning of metals, 133–134
    HCl electrolysis, 117–120
    hydroxylammonium nitrate
    prodcution, 139
    mercury or amalgam cell, 119–122
    NaCl electrolysis, 82–117, see also
    individual entry
    on-site generation of chlorine
    dioxide, 140
    Persulfates, 133
    Persulfuric acid, 133
    potassium gold cyanide and
    potassium stannate, 125–127
    salt splitting, 127–129,
    see also individual entry
    sodium hydrosulfite, 138–139
    water electrolysis, 134–137,
    see also individual entry
    Electrolytic cells, 137
    ElectroProd cell, 97–102
    Electrosynthesis Co., 278
    Electro-winning of metals, 133–134
    Eltech Systems, 278
    Entegris bipolar plates, 260–262
    Epoxides, 280
    E-Tek, 278
    Ethylene diamine (EDA), 147
    membrane technology in, 8
    EW determination by titration or
    infrared analysis, 223–224, 281
    Experimental methods, 211–233
    EW determination, 223–224,
    see also individual entry
    Fenton’s test for oxidative stability,
    hydrolysis, surface hydrolysis and
    staining, 215–218
    infrared spectra, 211–215,
    see also individual entry
    ion exchange equilibrium, 219–223,
    see also individual entry
    melt flow determination, 224–225
    membrane examination, 227–228
    Permselectivity determination,
    pervaporation rates measurement,
    precursor polymer versus ionic
    forms, 225–226
    simple electrolytic cells, 231–233
    Extrusion, 281
    Fabrication, in fluorinated ionomers
    manufacture, 30–34
    fabric reinforcement, 30
    vacuum lamination, 32
    Fenton’s reaction, 167290 Index
    Fenton’s test for oxidative stability,
    Finishing, in fluorinated ionomers
    manufacture, 35–37
    Flammability, 245
    FLEMION®, 12
    Fluorinated anion exchange
    polymers, 42
    Fluorinated cation exchange
    polymers, 216
    Fluorinated ethylene propylene
    (FEP), 11, 281
    Fluorinated ionomers, 1, see also
    Nafion® with phosphonic or
    sulfonyl imide functional groups,
    manufacture, 39–40
    Fuel cells
    and batteries, 157–182
    benzene into, 170
    carbon black catalyst, 159
    commercial 5-kW fuel cell stack,
    164–165, see also individual
    economic aspects, 201–209
    ESR studies on Nafion, 170
    ionomer stability in, 165–173, see
    also individual entry
    membrane development for, 8
    membrane electrode assembly
    (MEA), 160
    operating parameters, 162–165, see
    also individual entry
    types of, 157, see also Chlor-alkali
    cells; Direct Methanol Fuel Cells
    (DMFCs); Membrane electrode
    assembly (MEA); PEM fuel cells
    Fumatech, GmbH, 278
    Gas and vapor diffusion, fluorinated
    ionomers in, 146–150
    ethylene diamine (EDA), 147
    multi-tube dryers, 149
    silver ions, 147
    single tube dryer, 149
    tubular humidity exchanger, 148
    Gas-diffusion cathodes (GDCs),
    HCl electrolysis using, 118
    NaCl electrolysis with, 113
    structure of, 114
    Gas-diffusion electrode (GDE), in
    fuel cells, 159–160
    Glucose sensors, 142
    Hagen–Poiseuille equation, 224
    Handling, 239–240
    chemical contamination,
    cutting, 240
    installation, 241
    mechanical damage, 239
    pretreatment, 240
    HCl electrolysis, 117–119
    using a GDE, 118
    using ODC, 119
    Heat sealing, 235–237
    commercial heat-sealing
    equipment, 235
    melt fabrication of fluorinated
    ionomers, 235
    Quiver heat sealer, 235
    Heat Sealing, 243
    Hexafluoro propylene epoxide
    (HFPO), 12, 15, 23, 49
    addition to perfluorinated acid
    fluoride, 17
    Hexafluoropropylene (HFP), 15, 282
    Hydrogen peroxide, electrolytic
    generation, 136
    Hydrogen sulfide, 142
    Hydrogen/oxygen fuel cell system
    benzene into, 170
    Hydrolysis, 215–218
    in fluorinated ionomers
    manufacture, 11–26
    Hydroxylammonium nitrate
    prodcution, 139
    Hyflon-ion precursor polymer, 52
    heat of second fusion of, 53
    water uptake of, 63Index 291
    Infrared spectra methods, 211–215
    Dow precursor, 212
    EW determination by, 223–224
    Nafion 112F, 212
    Nafion carboxylate precursor,
    methyl ester form, 214
    Inorganic oxides, composite materials
    of, 42–44
    Installation, 241
    Ion exchange equilibrium, 220–223
    anion/cation equilibrium (Donnan
    exclusion), 220–221
    cation/cation equilibria, 221–223
    Ionic forms of fluorinated ionomers,
    properties, 52–68
    Aciplex F 4221 (Asahi Chemicals),
    contact angle, 66–67
    Nafion 117, 55
    Nafion 324, 55
    Nafion 350, 58
    Nafion 417, 57
    Nafion 424, 57
    Nafion 450, 58
    Nafion 90209, 58
    Nafion 954, 58
    Nafion® perfluorosulfonic acid
    membranes, 54
    solubility of gases, 68
    swelling in water and other
    solvents, 59–66, see also
    Swelling property
    wetting, 66–67
    Ionic forms versu precursor polymer,
    Ionomer stability in fuel cells,
    CO/air bleed and fluoride ion
    release, 168
    hydroxyl radicals as degraders,
    membrane decay, 169
    mechanical properties loss due
    to, 170
    mechanism, 169
    using hydrogen peroxide vapors,
    oxidative attack at the cathode,
    Ionomers, composite materials of,
    dopant/filler incorporation into, 43
    Ion-Power, Inc., 278
    Japan, 6
    membrane technology, 7
    Krupp-Uhde, 278
    Liquid compositions of fluorinated
    manufacture, 37–39
    film casting, 38–39
    morphology, 68–74
    film-forming ability, 70
    viscosity, 70
    Lithium chloride, 124
    3M, 2, 10, 62, 76–77, 170, 211
    Manufacture, fluorinated ionomers,
    composite materials of ionomers
    and inorganic oxides, 42–44
    fabrication, 30–34, see also
    individual entry
    finishing and testing, 35–37
    leak testing, 36–37
    fluorinated ionomers with
    phosphonic or sulfonyl imide
    functional groups, 39–40
    hydrolysis and acid exchange,
    liquid compositions, 37–39
    film casting, 38–39
    monomer synthesis, 12–15, see
    also Monomer synthesis
    partially fluorinated ionomers,
    40–41, see also individual entry
    perfluorinated ionomers, 11–25
    alkyl groups used in, 12
    Asahi Chemicals, 11
    Asahi Glass, 11292 Index
    Manufacture, fluorinated ionomers
    DuPont, 11
    perfluorinated vinyl ether, 11
    tetrafluoroethylene (TFE), 11
    polymerization, 26–30
    remanufactured membranes,
    Mechanical damage, 239
    Melt fabrication of fluorinated
    ionomers, 235
    Melt flow (MF) determination,
    Melt indexer, 224
    Melt Processable Polymer, 282
    Membrane damage, in NaCl
    electrolysis, 108, 111
    Membrane electrode assembly
    (MEA), 160, 282
    components, 176
    in fuel cells, 171
    manufacture of, 176–177
    continuous process for, 176
    hot pressing, 176
    Membrane examination, 227–228
    Reinforced membrane, 227
    unreinforced films, 228
    Membrane technology, 6–7
    Membranes, 185–188, see also
    individual entries; Commercial
    membrane types chlor-alkali
    cells, 102
    fluorinated ionomers as, 102–104
    fuel cells, 167–171, see also under
    Fuel cells
    Mercury or amalgam cell, 119–122
    sodium amalgam, 121
    Methanol as fuel, 173, see also
    Direct methanol fuel cells
    Methyl perfluoro 5-oxa heptenoate,
    Methyl perfluoro-3,6-dioxa-4-methyl
    noneoate, 25
    Microemulsion process, 27
    Monomer synthesis, in fluorinated
    ionomers manufacture, 12–25
    hexafluoro propylene epoxide
    (HFPO), 12, see also individual
    methyl perfluoro 5-oxa heptenoate,
    methyl perfluoro-3,6-dioxa-4-
    methyl noneoate, 25
    octene sulfonyl fluoride, 15–16
    Perfluoro-3-oxa-4-pentene sulfonyl
    fluoride, 24
    butylvinyl ether, 23
    nonene sulfonyl fluoride, 25
    steps in, 13
    tetrafluoroethylene (TFE), 11–16,
    see also individual entry
    Morphology, fluorinated ionomers,
    of liquid compositions, 70–74, see
    also Liquid compositions
    Nafion, 68
    Mylar® films, 6
    NaCl electrolysis, fluorinated
    ionomers in, 82–117
    bipolar electrolyzers, 84
    ElectroCells, 97–102
    electrodes, 106–107
    anodes, 106
    cathodes, 107
    electrode spacing, 107
    ElectroProd cell, 97–102
    membranes, 102–105
    monopolar electrolyzers, 85
    process description, 108–117
    brine purification process, 108
    calcium, 108–110
    gas-diffusion cathodes or
    electrodes, 112–117
    magnesium, 108–110Index 293
    membrane damage, 108,
    nanofiltration, 108
    Uhde Cell, 92–97
    Nafion®, 1–2, 5–8, see also Solution
    cast Nafion film, 251–257
    applications, 7
    discovery, 7, see also DuPont
    Experimental Station
    in chlor-alkali cell, 5–6
    in fuel cells, 160, 163, 165,
    ESR studies, 170
    liquid compositions of, 8
    Nafion 1100 EW precursor, 50–51
    Nafion 117, 55
    Nafion 324, 185–186
    Nafion 324, 55
    Nafion 350, 187
    Nafion 350, 58
    Nafion 417, 186
    Nafion 417, 57
    Nafion 424, 57
    Nafion 450, 187
    Nafion 450, 58
    Nafion 90209, 188
    Nafion 90209, 58
    Nafion 954, 188
    Nafion 954, 58
    Nafion carboxylate polymer, in
    dialysis, 146
    Nafion electrolytes in sensors,
    Nafion precursor polymer, 50–51
    heat of second fusion of, 53
    stress and strain curves for, 50
    tensile properties, 50–51
    Nafion sulfonic ionomer
    actuators based on, 144
    Nafion® perfluorosulfonic acid
    membranes properties, 54
    as nitration catalyst, 152
    partially mercury-exchanged
    Nafion, 153
    trimethylsilyl ester of Nafion,
    in reducing methanol crossover in
    DMFCs, 175
    swelling in water and trimethyl
    phosphate, 59
    swelling, 60
    in organic solvents and water
    mixture, 59
    water uptake of, 63–64
    NAFION®, 12
    Nickel–zinc plating, 133
    On-site generation of chlorine
    dioxide, 140
    Operating parameters, of fuel cells,
    current density, 161, 173, 177
    gas humidification, 163
    gas pressure and purity, 162
    gas stoichiometry, 162
    temperature, 163
    Optical properties, of fluorinated
    ionomers, 75–76
    Oxygen depolarized cathode (ODC),
    cell construction using, 119
    HCl electrolysis using, 119
    Ozone production, electrolytic
    generation, 137
    Partially fluorinated ionomers
    manufacture, 40–42
    fluorinated anion exchange polymers, 42
    non-fluorinated monomers
    grafting on fluorinated films,
    radiation grafted pTFE or FEP,
    polymerization, 41–42
    Partially fluorinated polymers, 1
    PEM fuel cells, 158
    activity by function, 209
    global applications for, 208
    principle, 158294 Index
    Perfluorinated acid fluoride
    HFPO addition to, 17
    Perfluorinated ionomers, 1
    commercial uses, 1–2
    containing phosphonic acid,
    synthesis, 1
    electrochemical fluorination for
    preparation, 7
    manufacture, 11–12, see also
    physical shapes, 2–3
    Perfluorinated sulfonic acids
    (PFSAs), 239, 243–245
    Perfluorinated vinyl ether, 11
    octene sulfonyl fluoride, 15
    safety, 16
    Perfluoro dimethyl cyclobutane, 27
    Perfluoro methyl vinyl ether (PMVE),
    Perfluoro propyl vinyl ether (PPVE),
    Perfluoro vinyl ethers, 5
    Perfluoro-3-oxa-4-pentene sulfonyl
    fluoride, 24
    ether, 23–24
    Perfluoroalkyl Vinyl Ether (PAVE), 283
    Perfluorosulfonic acid copolymer,
    degradation products of, 244
    PermaPure, Inc., 278
    Permselectivity determination,
    Persulfates, 133
    Persulfuric acid, 133
    Pervaporation, 145
    rates measurement, 230–231
    Thwing Albert pervaporation
    cup, 230
    Plastic-based bipolar plates, 259–262
    Entegris bipolar plates, 260
    Plug Power, 278
    Poly tetrafluoro ethylene (pTFE), 26,
    Polyethylene, 6
    Polymer fume fever (PFF), 244–245
    Polymerization, in fluorinated
    ionomers manufacture, 26–30
    Polymers, 1–2, see also Partially
    fluorinated polymers;
    Perfluorinated ionomers
    Polytetrafluoroethylene (pTFE), 6,
    49, 284
    Potassium chloride, electrolysis, 123
    Potassium gold cyanide electrolysis,
    Potassium stannate electrolysis,
    Precursor polymers, 218–219
    properties, 49–52
    hyflon-ion precursor polymer, 52
    Nafion precursor polymer, 50
    uniaxial draw of, 51
    reactions of, 218–219
    with ammonia or amines, 218
    oxidative cleaving, 218
    reduction, 218
    versus ionic forms, 225–226
    Pretreatment, 240
    Properties, fluorinated ionomers,
    ionic forms, 52–68, see also Ionic
    morphology, 68–74, see also
    individual entry
    optical properties, 75–76
    of precursor polymers, 49–52,
    see also Precursor polymers
    stability, 76–77
    thermal properties, 76
    transport properties, 74
    Protective Clothing, fluorinated
    ionomers in, 150–151
    Quiver Ltd., 278
    Reinforced membrane examination,
    Reinforced perfluorinated
    membranes, 185–198Index 295
    sulfonic acid membranes,
    185–187, see also individual
    sulfonic/carboxylic membranes,
    187–188, see also individual
    Remanufactured membranes, 45–46
    Repair procedures, 235–237
    final steps of, 237
    first steps of, 236
    Reverse orientation, in fluorinated
    ionomers manufacture, 33
    Safety, 243–245
    flammability, 245
    Polymer fume fever (PFF),
    skin contact, 243
    thermal degradation products,
    thermal stability, 243–244
    ventilation, 245
    Salt splitting, fluorinated ionomers
    in, 127–129
    chromic acid production, 127
    sodium sulfate production, 128
    Sensors, 140–144
    naphthol, 143
    carbon monoxide (CO) detector,
    glucose determination, 142
    hydrogen sulfide, 142
    immobilized 2-(5-bromo-2-
    phenol, 143
    Nafion electrolytes in, 141
    optical sensors, 143
    Silver ions, 147
    Simple electrolytic cells, 231–233
    Sintering, 284
    Skin contact, 243
    Skiving, 284
    Sodium hydrosulfite, 138–139
    Sodium sulfate production, 128
    Solubility of gases in fluorinated
    ionomers, 68
    Solution cast Nafion film, 251–257
    DuPont™ Nafion® PFSA
    membranes NRE-211 and NRE-
    212, 251–257
    Solution Technology, Inc., 278
    Solvay-Solexis, 24
    Solvay-Solexis, 27
    Stability, of fluorinated ionomers,
    Staining, 215–218, 239–242
    Sulfonic acid membranes, 185–187
    Nafion 324, 185–186
    Nafion 350, 187
    Nafion 417, 186
    Nafion 450, 187
    Sulfonic/carboxylic membranes,
    Aciplex® F 4221 (Asahi
    Chemicals), 188
    construction, 187
    carboxylate polymer layer,
    pTFE filaments, 187
    sulfonate polymer layer, 187
    zirconium dioxide coating, 188
    Nafion 90209, 188
    Nafion 954, 188
    Surface hydrolysis, 215–218
    Surface tension, 284
    Surfactant, 284–285
    Swelling property, of ionic forms of
    fluorinated ionomers, 59–66
    dimethyl methylphosphonate, 61
    factors affecting, 61
    nature of counter-ion, 63
    Nafion swelling in a mixture of
    organic solvents and water, 59
    water and other solvents, 59–66
    water and trimethyl phosphate, 60
    water uptake of Hyflon and
    Nafion, 63–65
    temperature affecting, 65296 Index
    Teflon®, 216
    Testing, in fluorinated ionomers
    manufacture, 35–37
    leak testing, 36–37
    Tetrafluoroethylene (TFE), 11–12
    properties, 13–15
    TFE Sultone (3,4,4-tetrafluoro-
    1,2-oxathietane S, S-dioxide),
    Tetraglyme, 17
    Tetramethyl ammonium chloride,
    electrolysis, 123
    TFE Sultone (3,4,4-tetrafluoro-1,2-
    oxathietane S, S-dioxide), 16–19
    Thermal properties, of fluorinated
    ionomers, 76
    Thermal stability, 243–244
    Thwing Albert pervaporation cup,
    Titration, EW determination by,
    Toxicology, 243
    Transport properties, of fluorinated
    ionomers, 74
    driven by an electric current, 74–75
    driven by concentration
    difference, 75
    Tubular humidity exchanger, 148
    Tucker Products, 148
    Uhde cell, 92–96
    cell stack, 93
    design, 92
    Unreinforced films examination,
    Unreinforced perfluorinated sulfonic
    acid films, 185
    Vacuum lamination, in fluorinated
    ionomers manufacture, 32
    Ventilation, 245
    Vinyl ethers, 5
    Viscosity, 285
    Voids, 285
    Warp, 285
    Water electrolysis, 134–137
    electrode/ionomer contact, 135
    hydrogen peroxide production,
    ozone production, 137
    Wetting property, of fluorinated
    ionomers, 66–67

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