WO2002017421A2 - Composition isolante et d'etancheite - Google Patents

Composition isolante et d'etancheite Download PDF

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Publication number
WO2002017421A2
WO2002017421A2 PCT/US2001/026069 US0126069W WO0217421A2 WO 2002017421 A2 WO2002017421 A2 WO 2002017421A2 US 0126069 W US0126069 W US 0126069W WO 0217421 A2 WO0217421 A2 WO 0217421A2
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WO
WIPO (PCT)
Prior art keywords
coating precursor
fuel cell
ultraviolet radiation
coating
acrylated
Prior art date
Application number
PCT/US2001/026069
Other languages
English (en)
Other versions
WO2002017421A3 (fr
Inventor
Brent R. Boldt
Original Assignee
Dana Corporation
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Filing date
Publication date
Application filed by Dana Corporation filed Critical Dana Corporation
Priority to KR10-2003-7002596A priority Critical patent/KR20030024905A/ko
Priority to MXPA03001375A priority patent/MXPA03001375A/es
Priority to AU2001285128A priority patent/AU2001285128A1/en
Priority to EP01964251A priority patent/EP1312126A2/fr
Priority to CA002420449A priority patent/CA2420449A1/fr
Priority to JP2002521384A priority patent/JP2004507062A/ja
Publication of WO2002017421A2 publication Critical patent/WO2002017421A2/fr
Publication of WO2002017421A3 publication Critical patent/WO2002017421A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1062—UV-curable materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/068—Containing also other elements than carbon, oxygen or nitrogen in the polymer main chain
    • C09K2200/0685—Containing silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to reactive coating compositions for insulating and sealing surfaces.
  • a fuel cell is a device that converts chemical energy of fuels directly to electrical energy and heat.
  • a fuel cell comprises two electrodes — an anode and a cathode — separated by an electrolyte.
  • a gas distribution system supplies the anode and the cathode with fuel and oxidizer, respectively.
  • fuel cells use the oxygen in the air as the oxidizer and hydrogen gas (including H 2 produced by reforming hydrocarbons) as the fuel.
  • Other viable fuels include reformulated gasoline, methanol, ethanol, and compressed natural gas, among others.
  • the fuel undergoes oxidation at the anode, producing protons and electrons.
  • the protons diffuse through the electrolyte to the cathode where they combine with oxygen and the electrons to produce water and heat. Because the electrolyte acts as a barrier to electron flow, the electrons travel from the anode to the cathode via an external circuit containing a motor or other electrical load that consumes power generated by the fuel cell.
  • PEM fuel cells use an electrolyte composed of a solid organic polymer, which is typically a poly-perfluorosulfonic acid.
  • Other fuel cell technologies include electrolytes comprised of solid zirconium oxide and yttrium (solid oxide fuel cells) or a solid matrix saturated with a liquid electrolyte.
  • Liquid electrolytes include aqueous potassium hydroxide (alkaline fuel cells), phosphoric acid (phosphoric acid fuel cells), and a mixture of lithium, sodium, and/or potassium carbonates (molten carbonate fuel cells).
  • phosphoric acid fuel cells (PAFC) operate at higher temperatures than PEM fuel cells (about 175 °C to about 200 °C)
  • PAFCs also find use in vehicle applications because of their higher efficiency and their ability to use impure hydrogen gas as fuel.
  • the core of a typical PEM fuel cell is a three-layer membrane electrolyte assembly
  • the MEA is comprised of a sheet of the polymeric electrolyte, which is about 50 ⁇ to about 175 ⁇ thick and is sandwiched between relatively thin porous electrodes (anode and cathode).
  • Each of the electrodes usually consists of porous carbon bonded to platinum particles, which catalyze the dissociation of hydrogen molecules to protons and electrons at the anode and the reduction of oxygen to water at the cathode. Both electrodes are porous and therefore permit gases (fuel and oxidizer) to contact the catalyst.
  • gases fuel and oxidizer
  • platinum and carbon conduct electrons well so that electrons move freely throughout the electrodes.
  • An individual fuel cell generally includes backing layers that are placed against the outer surfaces of the anode and the cathode layers of the MEA.
  • the backing layers allow electrons to move freely into and out of the electrode layers, and therefore are often made of electrically conductive carbon paper or carbon cloth, usually about 100 ⁇ to 300 ⁇ thick. Since the backing layers are porous, they allow fuel gas or oxidizer to uniformly diffuse into the anode and cathode layers, respectively.
  • the backing layers also assist in water management by regulating the amount of water vapor entering the MEA with the fuel and oxidizer and by channeling liquid water produced at the cathode out of the fuel cell.
  • a complete fuel cell includes a pair of plates pressed against the outer surfaces of the backing layers. Besides providing mechanical support, the plates define fluid flow paths within the fuel cell, and collect current generated by oxidation and reduction of the chemical reactants.
  • the plates are gas-impermeable and have channels or grooves formed on one or both surfaces facing the backing layers. The channels distribute fluids (gases and liquids) entering and leaving the fuel cell, including fuel, oxidizer, water, and any coolants or heat transfer liquids.
  • each plate may also have one or more apertures extending through the plate that distribute fuel, oxidizer, water, coolant and any other fluids throughout a series of fuel cells.
  • Each plate is made of an electron conducting material including graphite, aluminum or other metals, and composite materials such as graphite particles imbedded in a thermosetting or thermoplastic polymer matrix.
  • individual fuel cells are connected in series or are "stacked" to form a fuel cell assembly.
  • a single fuel cell typically generates an electrical potential of about one volt or less. Since most applications require much higher voltages — for example, conventional electric motors normally operate at voltages ranging from about 200 N to about 300 N — individual fuel cells are stacked in series to achieve the requisite voltage.
  • a single plate separates adjacent fuel cells in the stack.
  • Such plates which are known as bipolar plates, have fluid flow channels formed on both major surfaces — one side of the plate may carry fuel, while the other side may carry oxidizer.
  • conventional fuel cell assemblies employ resilient o-rings or planar inserts disposed between adjacent fuel cell plates to seal flow channels and apertures.
  • conventional fuel cell assemblies also provide electrical insulating sheets between adjacent plates to prevent individual fuel cells from short-circuiting.
  • seals and insulators are generally satisfactory, they suffer certain disadvantages. For example, freestanding o-rings and planar inserts must be carefully aligned with channels and apertures to ensure proper sealing and insulation, which is time consuming.
  • planar inserts used in fuel cell assemblies are typically made by injection molding, compression molding, or transfer molding, which require expensive, one-of-a-kind tooling.
  • many of the resilient materials used to make o-rings and planar inserts do not have the requisite chemical resistance and low modulus to adequately seal fuels cells operating at higher temperatures or employing hydrocarbon-based heat transfer fluids and coolants.
  • the present invention helps overcome, or at least mitigate one or more of the problems described above.
  • the present invention provides a process for sealing and insulating a fuel cell assembly comprised of two or more fuel cell plates.
  • the process includes providing a fuel cell plate having first and second surfaces and applying a coating precursor on at least the first surface of the fuel cell plate. Since the coating precursor is capable of polymerizing (curing) in response to radiation, the method also includes exposing the coating precursor on the fuel cell plate to radiation to initiate polymerization.
  • Useful coating precursors include those that can polymerize in response to ultraviolet radiation. Such coating precursors include those that contain an acrylated oligomer and a photoinitiator.
  • the invention also provides an insulated fuel cell plate comprised of a plate having first and second surfaces and a coating precursor applied to at least one of the first and second surfaces of the plate.
  • the coating precursor is generally an acrylate resin made up of an acrylated aliphatic urethane oligomer, an acrylated epoxy oligomer, a mono- functional monomer for reducing viscosity of the coating precursor, a multi-functional monomer for increasing cross-link density, an adhesion promoter, and a photoinitiator.
  • the present invention provides an ultraviolet radiation or electron beam- curable coating precursor.
  • the coating precursor includes an acrylated aliphatic urethane oligomer, an acrylated epoxy oligomer, a mono-functional monomer, a multi-functional monomer, an adhesion promoter, and a photoinitiator.
  • a particular useful coating precursor includes from about 25 wt. % to about 65 wt. % of the acrylated aliphatic urethane oligomer; from about 5 wt. % to about 20 wt. % of the acrylated epoxy oligomer; from about 20 wt. % to about 40 wt. % of the mono-functional monomer; from about 1 wt.
  • the present invention offers certain advantages over conventional methods and designs for insulating and sealing fuel cell plates and fuel cell assemblies.
  • the disclosed coating precursors can be quickly and precisely applied to fuel cell plates (e.g., by screen printing) resulting in substantial cost savings.
  • many of the disclosed coating precursors once cured, combine good chemical resistance with excellent mechanical properties.
  • Fig. 1 is a sketch of an exploded cross sectional view of a fuel cell assembly (not to scale).
  • Fig. 2 is plan view of one of the fuel cell plates having a coating for sealing and insulating the fuel cell assembly of Fig. 1.
  • the present invention is a composition for sealing and insulating mating surfaces of manufactured parts.
  • the coating can be used as an electrical insulation and a thermal insulation in many different products, including fuel cell assemblies and automotive gaskets used in internal combustion engines. Although described in relation to a PEM fuel cell assembly, the disclosed coating precursors can be used to seal and insulate other types of fuel cells, including, but not limited to alkaline fuel cells and phosphoric acid fuel cells.
  • Fig. 1 shows an exploded cross sectional view (not to scale) of a representative fuel cell assembly 100.
  • the fuel cell assembly 100 includes a stack of six individual fuel cells 102, although the number of fuel cells 102 can vary depending upon the desired voltage.
  • Each of the fuel cells 102 includes a multi-layer active portion 104 sandwiched between a pair of bipolar plates 106 or between a single bipolar plate 106 and an end plate 108.
  • Each active portion 104 includes a membrane electrolyte assembly (MEA) 110 disposed between a pair of backing layers 112.
  • the MEA 110 includes a polymer electrolyte membrane (PEM) 114 interposed between an anode 116 and a cathode 118.
  • Fig. 2 shows a plan view of one of the bipolar plates 106, and with Fig. 1, illustrates fluid flow paths within the fuel cell assembly 100.
  • Each of the plates 106, 108 shown in Fig. 1 have apertures 120 that extend between first 122 and second 124 major surfaces of the plates 106, 108.
  • the apertures 120 of adjacent plates 106, 108 align, forming cavities (not shown) that extend throughout the fuel cell assembly 100.
  • Some of the cavities deliver fluids (fuel, oxidizer) to individual fuel cells 102, or deliver fluids (coolant, heat transfer fluid) to cooling areas 126 between individual fuel cells 102.
  • Other cavities serve as collection regions for fluids (reaction products, coolant, heat transfer fluid).
  • the plates 106, 108 also have grooves or channels 130 formed on either or both of the first 122 and second 124 surfaces, and evenly distribute reactants or heat transfer fluid across the active portion 104 and the cooling area 126 of each of the fuel cells 102.
  • the plates 106, 108 include a resilient coating 132, which is applied on either or both of the major surfaces 122, 124 of the plates 106, 108.
  • the coating 132 prevents mixing of disparate fluid streams during operation of the fuel cell assembly 100, and prevents electrical conduction among adjacent plates 106, 108.
  • the coating 132 is chemically resistant to heat transfer fluids and electrolytes used in the various types of fuel cells, does not substantially interfere with fuel cell chemistry, is thermally stable at operating temperatures, and exhibits good adhesion to the plates 106, 108.
  • the thickness and mechanical properties of the coating 132 will depend on the dimensions and properties of the plates 106, 108 and the active portion 104 of each of the fuel cells 102. Typically, however, the coating 132 is about 50 ⁇ to 250 ⁇ thick, has a tensile strength greater than about 500 psi, an elongation greater than about 100 percent, and a Shore A hardness between about 45 and about 85.
  • the coating 132 which is applied on the plates 106, 108 in a fluid state and then solidified in situ, comprises a blend of one or reactive coating precursors that are subsequently polymerized and/or cross-linked.
  • reactive means that the components of the coating 132 react with one another other or self -react to cure (solidify); such materials are also referred to as thermosetting resins.
  • the coating 132 can be cross-linked and/or polymerized using any number of mechanisms, including oxidative curing, moisture curing, thermal curing, high energy radiation curing (e.g., ultraviolet curing, electron beam curing), condensation and addition polymerization, and the like.
  • Useful reactive precursors include, but are not limited to acrylate resins such as acrylated urethanes, vinyl acrylates, acrylated epoxies, acrylated polyesters, acrylated acrylics, acrylated polyethers, acrylated olefins, acrylated oils, and acrylated silicones. These reactive precursors can be cured using mechanisms described above, typically in less than 45 minutes. Rapidly acting forms of radiation, which require application for less than about 30 seconds and preferably for less than about 5 seconds are particularly useful.
  • Useful forms of radiation include ultraviolet (UN) radiation, infrared radiation, microwave radiation, and electron beam radiation.
  • the coating 132 precursor can include a catalyst, an initiator, or curing agent to help initiate and/or accelerate curing.
  • "resins” or “resin systems” refer to polydisperse systems containing monomers, oligomers, polymers, or combinations thereof. Exposing the coating precursor to high energy radiation represents a particular useful method of polymerizing the reactive components in coating precursors, offering additional advantages for fuel cell coatings 132 over thermally-cured reactive coating precursors. For instance, radiation cured coating precursors can be cross-linked at much lower temperatures (e.g., ambient temperature) than heat-cured reactive coating precursors.
  • Radiation curing can proceed via at least two mechanisms. In a first mechanism, radiation provides fast and controlled generation of highly reactive species (free radicals) that initiate polymerization of unsaturated materials. In a second mechanism, radiation (UN/electron beam) activate certain cationic photoinitiators that decompose to yield an acid catalyst that propagates the cross-linking reaction.
  • Examples of reactive precursors that can be cured using high energy radiation include, but are not limited to the acrylate resins. These reactive precursors include acrylates and methacrylates, and can be monomers or oligomers (i.e., moderately low molecular weight polymers typically containing 2-100 monomer units, and often 2-20 monomer units) of varying molecular weight (e.g., 100- 2000 weight average molecular weight).
  • Useful reactive coating precursors include, but are not limited to acrylated urethanes, acrylated epoxies, acrylated olefins, and mixtures thereof.
  • the acrylate resins typically comprise from about 30 wt. % to about 80 wt. % of the coating precursor, and preferably comprise from about 45 wt. % to about 60 wt. % of the coating precursor.
  • Acrylated urethanes are diacrylate esters of hydroxy terminated ⁇ CO extended polyesters or polyethers. They can be aliphatic or aromatic, although acrylated aliphatic urethanes are generally more useful in fuel cell applications because they are less susceptible to attack by the heat transfer fluids and electrolytes and because they appear to provide better mechanical properties (tensile, elongation, hardness).
  • the acrylated urethane provides the "backbone" of the cured coating, and therefore is usually present in the highest concentration, though too high a concentration may result in an unacceptably soft coating exhibiting insufficient thermal and chemical resistance.
  • the acrylated urethanes typically comprise from about 25 wt. % to about 65 wt.
  • % of the coating precursor and preferably comprise from about 40 wt. % to about 47 wt. % of the coating precursor.
  • useful acrylated urethanes include those commercially available from Henkel Corp. under the trade name PHOTOMER (e.g., PHOTOMER 6010) and from UCB Radcure Inc. under the trade names EBECRYL (e.g., EBECRYL 220, 284, 4827, 4830, 6602, 8400 and 8402), RXO (e.g., RXO 1336), andRSX (e.g., RSX 3604, 89359, 92576).
  • Other useful acrylated urethanes are commercially available from Sartomer Co.
  • SARTOMER e.g., SARTOMER 9635, 9645, 9655, 963-B80, and 966- A80
  • UVITHANE e.g., UVITHANE 782
  • Acrylated epoxies are diacrylate esters of epoxy resins, such as the diacrylate esters of bisphenol A epoxy resin, and include epoxy resins having a pendent nitrile moiety.
  • Acrylated epoxy resins generally improve the thermal stability and chemical resistance of the fuel cell coating 132, and increase its tensile strength. However, including an excessive amount of an acrylated epoxy may degrade the coating's adhesion to the plates 106, 108 and may also adversely impact its ability to seal.
  • the acrylated epoxies typically comprise from about 5 wt. % to about 20 wt. % of the coating precursor, and preferably comprise from about 8 wt. % to about 13 wt. % of the coating precursor.
  • acrylated epoxies examples include those commercially available from UCB Radcure Inc. under the EBECRYL and RXO trade names (e.g., EBECRYL 600, 629, 860 and 3708, RXO 2034) and from Henkel Corp. under the PHOTOMER trade name (e.g., PHOTOMER 3016, 3038 and 3071).
  • Acrylated acrylics are acrylic oligomers or polymers that have reactive pendant or terminal acrylic acid groups capable of forming free radicals for subsequent reaction, and include acrylic resins having a pendant nitrile moiety.
  • the acrylated acrylics Like the acrylated epoxies, the acrylated acrylics (especially those having pendant nitrile groups) generally improve the thermal stability of the fuel cell coating 132 and increase its tensile strength.
  • the acrylated acrylics typically can comprise from about 0 wt. % to about 25 wt. % of the coating precursor, and preferably comprise from about 0 wt. % to about 13 wt. % of the coating precursor.
  • Examples of useful acrylated acrylics are those commercially available from UCB Radcure under the EBECRYL trade name (e.g., EBECRYL 745, 754, 767, 1701, and 1755), from Sartomer Co.
  • acrylated olefins are unsaturated oligomeric or polymeric materials having reactive pendant or terminal acrylic acid groups capable of forming free radicals for cross-linking or chain extension. Like the acrylated epoxies and acrylics, the acrylated olefins generally improve the thermal stability of the fuel cell coating 132 and increase its tensile strength.
  • the acrylated olefins typically can comprise from about 0 wt. % to about 20 wt.
  • the coating precursor preferably comprise from about 0 wt. % to about 13 wt. % of the coating precursor.
  • useful acrylated olefins include polybutadiene acrylic oligomers, which are commercially available from Sartomer Co. under the trade name SARTOMER CN302, and from Ricon Resins under the trade name FX9005.
  • the reactive precursors ordinarily include a reactive diluent for controlling viscosity, for increasing cross-link density, and for promoting adhesion.
  • the reactive diluent includes at least one mono- or multi-functional monomer.
  • mono-functional refers to a compound that contains one carbon-carbon double bond
  • multi-functional refers to a compound that contains more than one carbon-carbon double bond or another chemically reactive group that can cross-link.
  • Reactive diluents are generally acrylate monomers, although non-acrylates such as n-vinyl pyrrolidone, limonene, and limonene oxide, can also be used, as long as the monomers are ethylenically unsaturated.
  • the mono- functional monomers decrease the viscosity of the coating precursor without substantially degrading the properties of the coating.
  • the mono-functional monomers can, in some cases, improve bulk mechanical properties (adhesion, tensile strength, elongation) as well.
  • the mono-functional monomers typically comprise from about 20 wt. % to about 40 wt. % of the coating precursor, and preferably comprise from about 25 wt. % to about 35 wt. % of the coating precursor.
  • useful mono- functional monomers include, but are not limited to ethyl acrylate, methyl methacrylate, isooctyl acrylate, oxethylated phenol acrylate, 2-ethylhexyl acrylate, 2-phenoxyethyl acrylate, 2-(ethoxyethoxy)ethyl acrylate, ethylene glycol methacrylate, tetrahydroxy furfuryl acrylate, caprolactone acrylate, and methoxy tripropylene glycol monoacrylate.
  • Particularly useful mono-functional monomers include isobornyl acrylate monomer and octyldecyl acrylate monomer, which are available from UCB Radcure under the trade names D3OA and ODA, respectively.
  • multi-functional monomers decrease the viscosity of the coating precursor, but also accelerate the rate of cure, and increase the cross-link density, which improves chemical resistance and increases tensile strength while decreasing elongation. Since the multi-functional monomers increase cross-link density, they are useful at lower concentrations than the mono-functional monomers, typically comprising from about 1 wt. % to about 5 wt. % of the coating precursor, and preferably comprising from about 2 wt. % to about 4 wt. % of the coating precursor.
  • Examples of useful multi-functional monomers include, but are not limited to triethylene glycol diacrylate, methoxyethyoxylated trimethylpropane diacrylate, pentaerythritol triacrylate, glycerol triacrylate, glycerol trimethacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, tetramethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and 1,6-hexane diacrylate.
  • mono- and multi-functional monomers include vinyl acetate, n- vinyl formamide, limonene oxide, and n- vinyl pyrrolidinone.
  • Particularly useful multi-functional monomers include propoxylated glycerol triacrylate monomer and trimethylolpropane ethoxy triacrylate monomer, which are available from UCB Radcure under the trade names OTA-480, and TMPEOTA, respectively.
  • the adhesion promoter includes at least one radiation curable material, such as mono- or multi-functional monomers or oligomers.
  • One particularly useful adhesion promoter is a methacrylated polyol adhesion promoter available from UCB Radcure under the trade name EBECRYL 168.
  • the adhesion promoter comprises from about 1 wt. % to about 15 wt. % of the coating precursor, and preferably comprises from about 7 wt. % to about 11 wt. % of the coating precursor.
  • Most of the disclosed reactive mono- functional and multi-functional acrylate monomers are commercially available from UCB Radcure under the EBECRYL trade name, from Henkel Corp. under the PHOTOMER trade name, and from Sartomer Co. under the SARTOMER trade name.
  • the reactive precursor includes at least one mono-functional monomer, at least one multi-functional monomer, and at least one multi-functional oligomer.
  • the reactive precursors include mono-functional and multi-functional acrylated monomers having molecular weights no greater than about 1000 (usually between about 100-1000) and a multi-functional oligomeric acrylated urethane having a weight average molecular weight of at least about 500, but generally between about 500-7000.
  • increasing the fraction of mono-functional monomers tends to lower the viscosity of the coating precursor blend and improve wet-out on the surfaces 122, 124 of the plates 106, 108.
  • multi-functional monomers and oligomers e.g., diacrylates and triacrylates
  • increasing the fraction of multi-functional monomers and oligomers tends to increase cross-linking, resulting in stronger adhesion, higher tensile strength, improved chemical resistance, but lower elongation.
  • the coating precursor normally includes one or more photoinitiators when it is cross-linked or polymerized with ultraviolet radiation.
  • photopolymerization initiators include, but are not limited to organic peroxides, azo compounds, quinones, benzophenones, nitroso compounds, acryl halides, hydrozones, mercapto compounds, pyrylium compounds, triacrylimidazoles, bisimidazoles, chloroalkytriazines, benzoin ethers, benzil ketals, thioxanthones, and acetophenone derivatives, and mixtures thereof.
  • benzil methyl o-benzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone-tertiary amine, acetophenones such as 2,2-diethoxyacetophenone, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-l-phenylpropan-l- one, l-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l-one, 2-benzyl-2-N,N- dimethylamino-l-(4-morpholinophenyl)-l-butanone, 2,4,6-trimethylbenzoyl- diphenylphosphine oxide, 2-methyl-l-4(methylthio), phenyl-2-morpholino-l-propanone, bis(2,6-dimethoxybenzoyl)(2,4,4-
  • the amount of the photoinitiators should be sufficient to generate the desired rate of curing and to produce the requisite coating properties and typically comprises from about 0.1 wt. % to about 10 wt. % of the coating precursor, and preferably comprises from about 1 wt. % to about 8 wt. %.
  • a particularly useful blend of photoinitiators comprises from about 1 wt. % to about 4 wt. % benzophenone and from about 1.5 wt. % to about 5 wt. % of l-phenyl-2- hydroxy-2-methyl-l-propanone of the coating precursor.
  • Benzophenone is commercially available from Sartomer Co.
  • the propanone is commercially available from Ciba- Geigy Corp.
  • the coating precursors may contain additives such as fillers, defoamers, flattening agents, wetting agents, slip aids, stabilizers, plasticizers, air-release agents, and the like.
  • the additives can be reactive or non-reactive, but are typically non-reactive.
  • useful non-reactive air-release agents include polydimethyl siloxanes, such as various DC- series silicone oils commercially available from Dow Corning, and SAG 47, which is commercially available from OSI Specialties.
  • additives including air- release agents
  • the coating precursors may also contain various solvents other than the reactive diluent monomers to help dissolve or swell the higher molecular weight reactive resins (e.g., the acrylated oligomers).
  • solvents are referred to as non-reactive diluents or non-reactive monomers because they do not significantly polymerize or cross-link with the reactive resin components.
  • Useful solvents include ketone solvents, tetrahydrofuran, xylene, and the like, although preferably the coating precursors contain no solvents.
  • the coating may also contain colorants (i.e., pigments and dyes).
  • Suitable colorants include TiO 2 , phthalocyanine blue, phthalocyanine green, carbon black, basic carbonate white lead, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, lead sulfochromate, bismuth vanadate, bismuth molybdate, iron oxide magnetite, Fe 3 O 4 , and iron (III) oxide, Fe 2 O 3 , among others.
  • Pigments can comprises from 0 wt. % to about 5 wt. % of the coating precursor.
  • the acrylate resins are typically cured using radiation such as ultraviolet light.
  • the fuel cell plates are placed on a conveyer that transports the plates under one or more sets of ultraviolet lamps, resulting in successive in-line exposure of the coating precursor to ultraviolet radiation.
  • the sets of ultraviolet lamps have nominal radiant wavelengths that are the same or different.
  • the length of exposure is controlled by the conveyor speed, which is typically in the range of 10 to 40 feet per minute and results in exposure times in the range of about 0.5 to about 5 seconds for each set of lamps.
  • the UV lamps typically have power ratings from about 300 to about 600 watts per linear inch.
  • Useful UV lamps include those employing type D, type V, type H, or type H bulbs, which are commercially available from Fusion UV Curing Systems and have nominal wavelengths of 375 nm, 425 nm, 250 nm, and 220 nm, respectively.
  • Other useful UV lamps include arc-type UV lamps having a mercury spectrum similar to Fusion type H bulbs.
  • One useful curing process employs two sets of arc-type UV lamps or UV lamps having type H bulbs.
  • Another useful curing process uses a first set of UV lamps having type D bulbs (longer wavelength UV light), and a second set of UV lamps having type H or H* bulbs (shorter wavelength UV light).
  • an initial exposure to UV lamps having type D bulbs cures the interior portions of the coating layer and adheres the coating to the surface of the fuel cell plate.
  • Subsequent exposure to UV lamps having type H or FT bulbs cures the outer portions of the coating layer.
  • the two-step curing process produces a satisfactory coating, curing under an inert nitrogen atmosphere may enhance coating properties. A flow rate of 20 cubic feet per minute of nitrogen through the curing equipment has been found in some instances to improve surface curing.
  • each of the disclosed reactive coating precursors can be applied using coating techniques known to persons of ordinary skill in the art, including roller coating, dipping, brushing, spraying, stenciling, screen printing, and the like. However, of these coating techniques, screen printing is preferred because of its low cost, speed, and accuracy.
  • the coating precursors may be applied to one or both sides of the fuel cell plate and as a cover- all coating or in selected continuous or discontinuous patterns depending on the insulating and sealing requirements of the fuel cell assembly. As noted above, the coating thickness for fuel cell plates is typically from about 50 ⁇ to about 250 ⁇ .
  • Table 1 lists coating precursor compositions (formulations A-P) for insulating and sealing fuel cell plates.
  • Each of the compositions includes an acrylated aliphatic or aromatic urethane oligomer, an isobornyl acrylate mono-functional monomer, a pair of photoinitiators (l-phenyl-2-hydroxy-2-methyl-l-propanone and benzophenone), and a polydimethylsiloxane air-release agent.
  • all of the formulations include a multifunctional monomer — either propoxylated glycerol triacrylate (formulations A-I, K-O) or trimethylolpropane ethoxy triacrylate monomer (formulations J, P).
  • formulations also include an acrylated olefinic oligomer (formulations B-E, G, I, L-O), an acrylated epoxy oligomer (formulations B, C, E, F, H-O), an acrylated epoxy monomer (formulation O), a methacrylated polyol adhesion promoter (formulations A-D, F-H, -O), or an octyldecyl mono-functional monomer (formulation O).
  • an acrylated olefinic oligomer formulations B-E, G, I, L-O
  • an acrylated epoxy oligomer formulations B, C, E, F, H-O
  • an acrylated epoxy monomer formulation O
  • a methacrylated polyol adhesion promoter formulations A-D, F-H, -O
  • octyldecyl mono-functional monomer formulations
  • the formulations listed in Table 1 were prepared by introducing the urethane oligomers and the polydimethylsiloxane air-release agent in a vessel. The mixture was stirred with heating to lower the viscosity of the mixture. The methacrylated polyol adhesion promoter (if present) was then added to the mixture. Once the adhesion promoter was fully dispersed, the non-urethane oligomers, and the mono-functional monomers (isobornyl acrylate and octydecyl acrylate monomer) were added (in order). In a separate vessel, benzophenone was dissolved in l-phenyl-2-hydroxy-2-methyl-l-propanone and in the multi-functional monomers with heating. The resulting blend of photoinitiators and multi-functional monomers were then admixed with the other coating precursor components.
  • Test samples were prepared on various substrates by screen printing (110 mesh polyester screen, nominal 0.001-inch and 0.005 inch pad heights) or by casting (fixed clearance draw down knife). Depending on the test, the nominal coating thickness was 0.001 inches (adhesion, mandrel flex, coolant blisters) or 0.005-0.006 inches (tensile strength, elongation, Shore A hardness). However, the coating thickness of adhesion test samples of formulations H and P was 0.005-006 inches. Each of the example formulations was cured by successive exposure to 375 watts/inch UV lamps having Fusion type D bulbs (375 nm) and type FT 4" bulbs (220 nm), respectively, at line speeds of 15-25 feet per minute. The test samples were used to measure various properties, including tensile strength, elongation, Shore A hardness, adhesion (scratch, blistering), and temperature resistance (mandrel flex).
  • Table 1 lists scratch adhesion results for test samples immersed in fuel cell coolant (formulations H, P), automotive coolant (A-P), or automotive oil (formulations J, K).
  • Test samples of formulation H were immersed in three different heat transfer fluids at ambient temperature for 70 hours.
  • the heat transfer fluids used were an isoparaffinic fluid commercially available from Solutia Inc. under the trade name THERMTNOL D12, a proprietary fluid commercially available from Dynalene Heat Transfer Fluids under the trade name DYNALENE FC-1, and a fluorinated hydrocarbon fluid commercially available from 3M under the trade name PF-5080.
  • Test samples of formulations A-P were immersed in a 50:50 v/v mixture of GM LONG LIFE COOLANT and water for 72 hours at 100 °C; test samples I and K were immersed in ASTM IRM 903 oil for 72 hours at 150 °C. Following immersion, adhesion was measured using a RPM 516 scratch test method.
  • a coated substrate was secured on a translatable stage and a "needle" was lowered onto the surface of the coated substrate.
  • a 500-gram dead weight load was applied to one end of the needle so that the other end of the needle penetrated the coating.
  • the needle executed a circular motion while the specimen was translated at a rate of about 2.5 mm/cycle, producing a series of 10-mm diameter, overlapping circular scratch marks in the coating.
  • the appearance of the coating was ranked on a scale of 1 (poor adhesion) to 10 (best adhesion).
  • Table 1 represents the average of three test samples per fluid; the designation "dry” refers to test samples that were not immersed in coolant or oil prior to the scratch test.
  • Table 1 also lists tensile strength, elongation, and Shore A hardness for each of the coating formulations.
  • tensile strength and elongation 1 inch by 4 inch specimens were die-cut from samples that were cast on polyester film using a fixed clearance draw down knife. The sample thickness was measured at multiple points on the film (minimum of six places near the center of the specimen), and the samples were pulled at ambient temperature on an Instron tester at a crosshead speed of 0.2 inches per minute.
  • Table 1 reports average tensile strength and elongation at break based on five samples.
  • Shore A hardness 0.5 inch by 1.5 inch specimens were cut from samples cast on polyester film. Specimens from a single formulation were stacked to obtain an overall sample thickness of 0.125 inches. The hardness of the "stacked" test sample was measured using a table mounted Shore A hardness tester. Five hardness measurements were obtained for each formulation.
  • Table 1 also lists temperature resistance data (denoted "temperature mandrel”) and viscosity data. Temperature resistance was measured using a modified version of ASTM D573. Each test specimen (screen-printed coating on a 0.008 inch thick stainless steel coupon) was heat aged for 22 hours at 185 °C, bent around a 6-inch diameter mandrel, and then visually inspected for cracks in the coating or for loss of bond between the coupon and the coating. The appearance of the coating was ranked on a scale of 1 (many cracks, loss of bond) to 10 (few or no cracks, little or no loss of bond); data in Table 1 represent the average of three test specimens. The viscosity entries are based on a subjective assessment of the flow characteristics of the coating precursor. A ranking of 1 indicates the coating precursor would be difficult to screen print, and a ranking of 10 indicates that the coating precursor would be easy to screen print.
  • Coolants tested THERMINOL D12, DYNALENE FC-1, PF-5080 (in order shown); all other formulations tested with a 50:50 v/v mixture of GM LONG LIFE COOLANT. 2 Contains 0.03 wt. % Fe 3 O 4 and 0.32 wt. % Fe 2 O 3 . Table 1 — Continued

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Abstract

L'invention concerne une composition et un procédé d'étanchéification et d'isolation de surfaces entre des pièces s'adaptant mutuellement. Le procédé peut être appliqué pour isoler et étanchéifier des plaques de piles à combustible, et consiste à appliquer un précurseur de revêtement sur au moins une surface de ladite plaque, et à durcir le précurseur de revêtement par exposition à un rayonnement. Les précurseurs de revêtement décrits comprennent ceux qui renferment un oligomère acrylé et un photo-initiateur capables de se polymériser sous l'effet d'un rayonnement ultraviolet ou d'un faisceau d'électrons. Les procédés et les précurseurs selon l'invention procurent certains avantages par rapport aux procédés et aux systèmes conventionnels pour l'isolation et l'étanchéification des plaques de piles à combustible, du fait que les précurseurs selon l'invention peuvent être appliqués rapidement et avec précision sur lesdites plaques, par exemple, par impression par masquage.
PCT/US2001/026069 2000-08-23 2001-08-21 Composition isolante et d'etancheite WO2002017421A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR10-2003-7002596A KR20030024905A (ko) 2000-08-23 2001-08-21 절연 및 밀봉 조성물
MXPA03001375A MXPA03001375A (es) 2000-08-23 2001-08-21 Composicion de aislamiento y sellado.
AU2001285128A AU2001285128A1 (en) 2000-08-23 2001-08-21 Insulating and sealing composition
EP01964251A EP1312126A2 (fr) 2000-08-23 2001-08-21 Composition isolante et d'etancheite
CA002420449A CA2420449A1 (fr) 2000-08-23 2001-08-21 Composition isolante et d'etancheite
JP2002521384A JP2004507062A (ja) 2000-08-23 2001-08-21 絶縁および密封組成物

Applications Claiming Priority (2)

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US64431600A 2000-08-23 2000-08-23
US09/644,316 2000-08-23

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WO2002017421A3 WO2002017421A3 (fr) 2003-01-03

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004206986A (ja) * 2002-12-25 2004-07-22 Toyota Motor Corp 燃料電池のシール構造
DE102012014756A1 (de) * 2012-07-26 2014-01-30 Daimler Ag Verfahren und Vorrichtung zum Verbinden zumindest zweier Bestandteile einer Brennstoffzelle
US20150240413A1 (en) * 2014-02-24 2015-08-27 Gary S. Selwy Composition and process for applying hydrophobic coating to fibrous substrates
US11414512B2 (en) 2017-04-14 2022-08-16 Threebond Co., Ltd. Photocurable resin composition, fuel cell using same, and sealing method

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8197990B2 (en) * 2006-01-17 2012-06-12 Henkel Corporation Sealant integrated fuel cell components and methods and systems for producing the same
JP6956840B1 (ja) * 2020-09-30 2021-11-02 住友理工株式会社 燃料電池用部材およびその製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609686A (en) * 1985-04-19 1986-09-02 The Standard Oil Company 100 percent solids epoxy, nitrile coating compositions and method of making same
EP0385779A1 (fr) * 1989-03-03 1990-09-05 Westinghouse Electric Corporation Résine durcissable à la lumière-UV
WO1996028396A1 (fr) * 1995-03-13 1996-09-19 Dsm N.V. Composition de revetement de fibre optique, durcissable au rayonnement
EP0902040A1 (fr) * 1997-09-11 1999-03-17 Basf Aktiengesellschaft Compositions durcissables par rayonnement à base de prépolymères aliphatiques contenant des groupes uréthanes ayant des double liaisons à insaturation éthylénique
US5945463A (en) * 1994-09-30 1999-08-31 Zeon Rize Co., Ltd. Composition for a gasket and process for producing a gasket using the composition
DE19829142A1 (de) * 1998-06-30 2000-01-05 Manhattan Scientifics Inc Gasdichter Verbund aus Bipolarplatte und Membran-Elektroden-Einheit von Polymerelektrolytmembran-Brennstoffzellen
US6057054A (en) * 1997-07-16 2000-05-02 Ballard Power Systems Inc. Membrane electrode assembly for an electrochemical fuel cell and a method of making an improved membrane electrode assembly
EP1009052A1 (fr) * 1998-06-02 2000-06-14 Matsushita Electric Industrial Co., Ltd. Cellule electrochimique a electrolyte en polymere et procede de fabrication

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609686A (en) * 1985-04-19 1986-09-02 The Standard Oil Company 100 percent solids epoxy, nitrile coating compositions and method of making same
EP0385779A1 (fr) * 1989-03-03 1990-09-05 Westinghouse Electric Corporation Résine durcissable à la lumière-UV
US5945463A (en) * 1994-09-30 1999-08-31 Zeon Rize Co., Ltd. Composition for a gasket and process for producing a gasket using the composition
WO1996028396A1 (fr) * 1995-03-13 1996-09-19 Dsm N.V. Composition de revetement de fibre optique, durcissable au rayonnement
US6057054A (en) * 1997-07-16 2000-05-02 Ballard Power Systems Inc. Membrane electrode assembly for an electrochemical fuel cell and a method of making an improved membrane electrode assembly
EP0902040A1 (fr) * 1997-09-11 1999-03-17 Basf Aktiengesellschaft Compositions durcissables par rayonnement à base de prépolymères aliphatiques contenant des groupes uréthanes ayant des double liaisons à insaturation éthylénique
EP1009052A1 (fr) * 1998-06-02 2000-06-14 Matsushita Electric Industrial Co., Ltd. Cellule electrochimique a electrolyte en polymere et procede de fabrication
DE19829142A1 (de) * 1998-06-30 2000-01-05 Manhattan Scientifics Inc Gasdichter Verbund aus Bipolarplatte und Membran-Elektroden-Einheit von Polymerelektrolytmembran-Brennstoffzellen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004206986A (ja) * 2002-12-25 2004-07-22 Toyota Motor Corp 燃料電池のシール構造
DE102012014756A1 (de) * 2012-07-26 2014-01-30 Daimler Ag Verfahren und Vorrichtung zum Verbinden zumindest zweier Bestandteile einer Brennstoffzelle
US20150240413A1 (en) * 2014-02-24 2015-08-27 Gary S. Selwy Composition and process for applying hydrophobic coating to fibrous substrates
US9790640B2 (en) * 2014-02-24 2017-10-17 Gary S Selwyn Composition and process for applying hydrophobic coating to fibrous substrates
US11414512B2 (en) 2017-04-14 2022-08-16 Threebond Co., Ltd. Photocurable resin composition, fuel cell using same, and sealing method

Also Published As

Publication number Publication date
MXPA03001375A (es) 2003-06-06
AU2001285128A1 (en) 2002-03-04
EP1312126A2 (fr) 2003-05-21
WO2002017421A3 (fr) 2003-01-03
KR20030024905A (ko) 2003-03-26
JP2004507062A (ja) 2004-03-04
CA2420449A1 (fr) 2002-02-28

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