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 |  موضوع: كتاب Fluorinated Ionomers Second Edition الجمعة 17 نوفمبر 2023, 11:51 am | |
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أحضرت لكم كتاب
Fluorinated Ionomers Second Edition
Walther Grot
C. G. Processing, Inc.,
Chadds Ford, Pennsylvania
و المحتوى كما يلي :
Table of contents
Series Page
Plastics Design Library
PDL Fluorocarbon Series Editor’s Preface
Preface
Acknowledgements
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
Index
Suppliers and Resources
Aldrich Chemicals Retailer of Nafion products (precut sheets
20×25 and 30×30 cm, solution and powder),
www.sigmaaldrich.com
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.
mb@om.asahi-kasei.co.jp
Ballard Power Systems Supplies PEM fuel cells, www.ballard.com,
604-454-0900.
C.G. Processing, Inc. Distributor of Nafion products (custom cut
sheets), custom fabrication of Nafion by heat
sealing, w.grot@juno.com, 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,
www.thechlorinegenie.com
E.I. DuPont de Nemours Manufacturer of Nafion perfluorinated
ionomer products;
JEFFREY.L.JONES@USA.DUPONT.COM,
910-678-1651.
ElectroCell A/S Supplier of general-purpose electrolytic cells,
small chlorine generators, 45-9737-4499;
www.electrocell.com, ec@electrocell.com,
Europe and USA; contacts: Gusten Eklund
46-83-65-095; Dr. D.J. Mazur, 746-
564-1414; g.eklund@electrocell.com,
duane.mazur@electrocell.com
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,
www.eltechsystems.com
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:
office@fumatech.de, 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
www.thyssenkrupp.com/uhde,
Info.uhde@thyssenkrupp.com, 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, Davini@quiverltd.it;
(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.
3m.com/about3M/technologies/fuelcells/
index.htm
Yeoh, Ray Chlor-Alkali Consultant
Bangkok : 66852125110,
China : 8613708232653
E-mail : rayeoh@singnet.com.sg &
rayeoh03@gmail.com279
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/
Dictionary-D.htmhttps://electrochem.cwru.edu/ed/encycl/index.html
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
technique.
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/
images/prakash.pdf
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
conductivity.
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
polymerization.
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,
146–150
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
6-Carboethoxy-perfluoro-2-methyl-3-
oxa-hexanoyl fluoride, 20
6-Carbomethoxy-perfluoro-2-methyl-
3-oxa-hexanoyl fluoride, 21–22
9-Carboethoxy-perfluoro-2,5-
dimethyl-3,6-dioxa-nonanoyl
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,
123–124
Chlorine Engineers, 277
Chromic acid
production, 127
regeneration system, 130–132,
247–248
components, 131
nickel–zinc plating, 133
Commercial 5-kW fuel cell stack,
164–165
characteristics, 164–165
control, 165
emissions, 165
fuel, 164
operation, 164
performance, 164
physical, 164
safety, 164
sensors, 165
Commercial membrane types,
185–188
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,
144–146
Donnan dialysis, 145–146
Nafion carboxylate polymer, 146
pervaporation, 146
Dictionaries of Electrochemistry,
279
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),
173–176
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,
265
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,
81–140
chromic acid regeneration,
130–132
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
Europe
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,
226–227
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,
229–230
pervaporation rates measurement,
230–231
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,
226–227
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
entry
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),
112–117
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,
239–240
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),
58
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,
225–226
Ionomer stability in fuel cells,
165–173
CO/air bleed and fluoride ion
release, 168
hydroxyl radicals as degraders,
167
membrane decay, 169
mechanical properties loss due
to, 170
mechanism, 169
using hydrogen peroxide vapors,
171
oxidative attack at the cathode,
167
Ionomers, composite materials of,
42–44
dopant/filler incorporation into, 43
Ion-Power, Inc., 278
Japan, 6
membrane technology, 7
Krupp-Uhde, 278
Liquid compositions of fluorinated
ionomers
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,
11–26
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,
34–35
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
(Continued)
DuPont, 11
perfluorinated vinyl ether, 11
tetrafluoroethylene (TFE), 11
polymerization, 26–30
remanufactured membranes,
45–46
Mechanical damage, 239
Melt fabrication of fluorinated
ionomers, 235
Melt flow (MF) determination,
224–225
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
Nafion
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,
19–22
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
entry
methyl perfluoro 5-oxa heptenoate,
19–23
methyl perfluoro-3,6-dioxa-4-
methyl noneoate, 25
perfluoro,6-dioxa-4-methyl-7-
octene sulfonyl fluoride, 15–16
Perfluoro-3-oxa-4-pentene sulfonyl
fluoride, 24
perfluoro-4-(fluorosulfonyl)
butylvinyl ether, 23
perfluoro-4,7-dioxa-5-methyl-8-
nonene sulfonyl fluoride, 25
steps in, 13
tetrafluoroethylene (TFE), 11–16,
see also individual entry
Morphology, fluorinated ionomers,
68–74
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,
111–112
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,
170–171
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,
141–143
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,
153
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,
162–165
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),
117
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,
40–41
radiation grafted pTFE or FEP,
42
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
Manufacture
physical shapes, 2–3
Perfluorinated sulfonic acids
(PFSAs), 239, 243–245
Perfluorinated vinyl ether, 11
Perfluoro,6-dioxa-4-methyl-7-
octene sulfonyl fluoride, 15
safety, 16
Perfluoro dimethyl cyclobutane, 27
Perfluoro methyl vinyl ether (PMVE),
11
Perfluoro propyl vinyl ether (PPVE),
11
Perfluoro vinyl ethers, 5
Perfluoro-3-oxa-4-pentene sulfonyl
fluoride, 24
Perfluoro-4-(fluorosulfonyl)butylvinyl
ether, 23–24
Perfluoroalkyl Vinyl Ether (PAVE), 283
Perfluorosulfonic acid copolymer,
degradation products of, 244
PermaPure, Inc., 278
Permselectivity determination,
229–230
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,
30–31
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,
125–127
Potassium stannate electrolysis,
125–127
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,
49–77
ionic forms, 52–68, see also Ionic
forms
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,
227
Reinforced perfluorinated
membranes, 185–198Index 295
sulfonic acid membranes,
185–187, see also individual
entry
sulfonic/carboxylic membranes,
187–188, see also individual
entry
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),
244–245
skin contact, 243
thermal degradation products,
244
thermal stability, 243–244
ventilation, 245
Salt splitting, fluorinated ionomers
in, 127–129
chromic acid production, 127
sodium sulfate production, 128
Sensors, 140–144
4-decyloxy-2-(2-pyridylazo)-1-
naphthol, 143
carbon monoxide (CO) detector,
140
glucose determination, 142
hydrogen sulfide, 142
immobilized 2-(5-bromo-2-
pyridylazo)-5-(diethylamino)
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,
76–77
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,
187–188
Aciplex F 4221 (Asahi
Chemicals), 188
construction, 187
carboxylate polymer layer,
187
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),
16–19
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,
230
Titration, EW determination by,
223–224
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,
228
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,
137
ozone production, 137
Wetting property, of fluorinated
ionomers, 66–67
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