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أخواني في الله أحضرت لكم كتاب Fluorinated Ionomers Second Edition Walther Grot C. G. Processing, Inc., Chadds Ford, Pennsylvania
![كتاب Fluorinated Ionomers Second Edition F_l_2_10](https://i.servimg.com/u/f61/15/36/74/14/f_l_2_10.jpg) 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![:registered: ®](https://cdn.jsdelivr.net/emojione/assets/png/00ae.png?v=2.2.7) 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![:registered: ®](https://cdn.jsdelivr.net/emojione/assets/png/00ae.png?v=2.2.7) 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, 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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