GB2287720A - Porous metal composite body - Google Patents
Porous metal composite body Download PDFInfo
- Publication number
- GB2287720A GB2287720A GB9505644A GB9505644A GB2287720A GB 2287720 A GB2287720 A GB 2287720A GB 9505644 A GB9505644 A GB 9505644A GB 9505644 A GB9505644 A GB 9505644A GB 2287720 A GB2287720 A GB 2287720A
- Authority
- GB
- United Kingdom
- Prior art keywords
- metal
- substrate
- plasma
- porous
- composite body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002905 metal composite material Substances 0.000 title claims description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 238000001465 metallisation Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- 239000004811 fluoropolymer Substances 0.000 claims description 4
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 13
- 239000002131 composite material Substances 0.000 abstract description 11
- 239000000446 fuel Substances 0.000 abstract description 5
- 229910002710 Au-Pd Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5826—Treatment with charged particles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
- H01M4/8871—Sputtering
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Abstract
A method of making a porous GpVIII metal body comprises metallising a porous substrate, oxidising the metallisation and reducing the metallisation is characterised in that the oxidation is performed in the gas phase by oxidative plasma and the reduction is performed in the gas phase by reducing plasma. The porous substrate may be ceramic or polymeric, eg PTFE whilst the metal may be Pt, Pd, Ni, Ag, Au-Pd, or Cu. The composite body formed may be used as a catalyst in a gas sensor, fuel cell or electrode; or as a chromatographic separator.
Description
D:\136V92\GB02SPECASF= 136392 2287720 POROU METAL C MPOSITE BODY This
invention relates to the production of a composite body comprising porous metal attached to a substrate.
There are applications for such composite bodies in the electrochemical field such as for gas sensors and fuel cells, as well as in the general field of catalysis of chemical reactions and catalytically acting surfaces generally, where high surface areas are required.
The substrate is therefore preferably of high surface area, for example it is porous (preferably microporous), and is advantageously of an inert material such as a polymeric material such as a fluoropolymer. Microp orous fluoropolymers are well known as chemically, thermally and biologically stable materials used in various phase separation situations, and are advantageously made, for the purposes of the invention, of microporous PTFE (polytetrafluoroethylene) membrane products as disclosed in European Patent 247771, which are useful in a range of applications, including metallised examples produced by for example sputter coating, electrolysis or spin coating. (In spin coating, typically, colloidal catalyst particles are impacted upon a PTFE membrane substrate by the hydrodynamic/centrifugal action of a spinning rotor immersed in the colloid.) Although many porous Gp VIII metal composite bodies are possible according to the invention, certain materials are of especial interest to workers in the fuel cell, gas sensor and air battery fields, for example the platinum group metals including platinum, palladium and nickel.
In the electrochemical field, it is known that interlocking structures of catalyst and PTFE can be made by simple admixture of dispersions of the materials (e.g. GB Patent 1556452), but the proportion of expensive catalyst to lower-cost PTFE is very high, e.g. 10:3 by mass.
This invention seeks to increase the metal surface area of a given composite body, for example to improve the catalytic activity per unit volume of the composite body or per unit mass of catalyst metal.
D 1.136392GB02SPEC\ASFILED US Patent 3715238 teaches the depolarisation of a fuel cell catalyst (e.g. Ru + Pt + some PTFE) by voltage-sweep-treating it in a selected electrolyte at 1 cycle per /-c20 minutes, whereby, gradually, catalytic metal is deposited at new surfaces so the catalytic metal surface area is gradually increasing. This is too slow as a production method, not to mention the need to rinse and dry or otherwise remove all traces of electrolyte, for some catalytic purposes. Again, the proportion of expensive metal to lower-cost PTFE is very high, nearly 104: 1.
US Patent 4540476 teaches the production of a nickel electrode from a porous nickel plaque by applying an alternating potential, such that the nickel dissolves on the oxidising part of the cycle and, on the reducing part of the cycle, oxidised nickel is precipitated as hydroxide. This is performed on nickel sintered on a wire mesh support, thus foregoing the economy, porosity and high surface area per unit volume which binding as a composite with PTFE would have allowed, and also suffers from the above-noted disadvantages of a wet electrolytic process.
According to the present invention, therefore, a porous Gp VIII metal composite body is made by metallising a porous (e.g. ceramic or polymeric) substrate, preferably in the gas phase, (the ratio metal:substrate being preferably less than Ll, preferably less than 100:1, optionally <j04:1), oxidising the metallisation and optionally or partly or wholly reducing the metallisation, characterised in that the oxidation is performed in the gas phase by oxidative plasma and the reduction is performed in the gas phase by reducing (e.g. ammonia, hydrazine or hydrogen) plasma. The oxidative plasma may be oxygen or other anion (uni- or multi-atomic e.g. bromine) which forms a volatile product with hydrogen. In either case, the gas in question may be present at a pressure of from 0.05 to 1 Torr. Plasma treatment may be performed at a power of from 1 to J30 (preferably 2 to 5) Watts/dm9 of substrate, and may continue for from 1 to 20 e.g. 3 to 10 minutes.
The substrate is therefore preferably of an inert material such as a ceramic or polymeric material such as a fluoropolymer such as PTFE or other material at least as stable towards plasma exposure, and may be microporous, with pore sizes of for example up to about 10 microns.
0 i 1 n D.\136\392XGB02SPEMASFRM The Gp VIII metal (by which we include alloys) may be a platinum group metal, e.g. platinum, palladium or nickel, or may for example be ruthenium or rhodium or silver.
The invention extends to the composite body so made and to its use as a catalyst, for example in a gas sensor, fuel cell, or electrode. The invention allows the manufacture of a (hitherto unknown) porous metal composite body comprising a porous substrate bearing less than I% by weight metal, the metal having a surface area at least ten times that of the substrate. The metal may be under 1 micron thick, e.g. 0.05 to 0. 1 microns or less, giving maximum catalytic activity at minimum materials cost.
The elements of inconvenience and lack of reproducibility of 'wet' methods such as electrolysis described earlier can be avoided by carrying out the metallisation, the oxidation and the reduction in the gas phase. Gas phase techniques are generally cleaner and quicker and allow greater control over product parameters.
Gas-phase metallisation may be carried out the same way as in the preparation of samples for electron microscopy where the metallic layer conducts away impinging electrons during analysis thus prolonging the life of non-conducting specimens.
Additionally the technique allows the production of certain decorative and protective coatings particularly of expensive materials in a costeffective way.
Good control can be exercised over metal purity and thickness (a major consideration in terms of cost) and hence over the metal loading of the resulting product, e.g. electrode.
Preferably, the next stage of the process of making a composite body according to the invention utilises a cold plasma - so called because the process temperature at the substrate is about 300K, and can be kept below 325K. The composite, let us suppose platinum on microporous PTFE, may be placed in an evacuated chamber and subjected to an oxygen plasma. A controlled amount of the platinum may be oxidised depending upon the ultimate electrical conductance required of the composite. At an appropriate stage the oxidation may be stopped and the oxidised composite subjected to a hydrogen plasma. Under these reducing conditions the oxide reverts to the metal and porosity is induced in D:%136\392GB02SPEC\ASFILED the metallisation layer as interstices are created at points previously occupied by oxide oxygen, the latter being removed by evacuation as water molecules.
This process could clearly be applied to other geometd-es as well as other metals and substrates. In general the most efficient use of the catalytic entity both in terms of cost and energetics can be made when the surface area is maximised. The disposition and amount of catalyst can be very closely controlled according to ultimate process requirements, for example electrodes for gas sensors, chromatographic separations on treated granules or planar separations with films or tubes.
The invention will now be described by way of example.
EXAMPLE 1: A cylindrical glass glow discharge reactor, 4.5 cm diameter and 112litre capacity, enclosed in a Faraday cage, is fitted with a gas inlet, a Pirani pressure gauge and a rotary pump attached to a liquid nitrogen cold trap. The reactor is cleaned with detergent, rinsed with isopropyl alcohol and oven dried, followed by a high power (50W) air plasma treatment for 30-40 minutes. A matching network is used to inductively couple a copper coil (4 mm diameter, 9 turns spanning 8 to 15 cm from the gas inlet) wound externally around the reactor to a 13.56 MHz radio frequency source, to generate this plasma. A sample of microporous PTFE is loaded into the reactor, within the region inside the coil. This sample is a sheet of size 100 mm x 150 mm coated by sputtering to a thickness of 1 micron with high purity platinum. The reactor is evacuated to a low pressure, typically 5 x 10-3 Torr, and oxygen of 99.9% purity is introduced at a pressure of 0.05 or 0.1 to 1 Torr, typically 0.1, 0.2 or 0.5 Torr, purged for about 5 minutes. The plasma is then ignited at -3) 0 watts for typically 10 minutes. The radio frequency is then switched off, the gas inlet closed and the reactor evacuated back to base pressure for at least 5 minutes. This introduces oxygen atoms into the platinum.
The second stage, a reduction step, is carried out similarly by introducing high purity (99.9%) hydrogen at about 0.05 or 0.1 to 1 Torr, e.g. 0.1, 0.2 or 0.5 Torr, purging for a few minutes, and the plasma ignited at 30 watts for typically 10 minutes. This causes hydrogen to react with the oxygen atoms. The radio frequency is then switched off, the gas inlet closed and the reactor evacuated for 5 minutes. This causes the reacted oxygen to 1W 3 evaporate as water vapour, leaving behind a platinum surface "roughened" by physical p v removal of the oxygen from sites where it had reacted and had displaced platinum atoms, hence increasing its surface area. The system is then brought back to atmospheric pressure and the specimen is removed for use.
Further examples of the invention were made using the foregoing apparatus but 5 varying the conditions as follows:- EXAMPLE 2: Platinum was deposited to various thicknesses, namely 5 gm, I gm, 0. 1 gm, and to lesser thicknesses, to which it is meaningless to ascribe an exact dimension but which were established to lie in the range 0.05-0.1 gm. After oxidation and reduction as above, all yielded successful catalysts.
EXAMPLE 2A: Example 2 was repeated but with the samples located not within the region inside the coil but in the "afterglow" region just outside. This removed the samples from the influence of the highest- energy charged particles and hence lessened ablation of deposited metal by over-energetic impacts from those particles. The remaining charged particles were found to be of an energy distribution which was highly apt for oxidation and reduction. The samples made successful catalysts.
EXAMPLE 3: Instead of just platinum, sputtering of a standard 60:40 gold/palladium alloy was carried out. It was deposited on the PTFE, broadly unchanged in composition, to a thickness of 1 gm. After oxidation and reduction as above, all samples yielded successful catalysts. It is believed that under these conditions the palladium in the deposited alloy has had its surface area increased, leaving the gold unchanged and still a good electrical conductor.
EXAMPLE 4: The sputtered substrate of Example 3 was oxidised under 0.2 Torr oxygen and reduced under 0. 1 Torr hydrogen. This was exceptionally successful.
EXAMPLE 5: Examples 3 and 4 were successfully repeated using gold-and-palladium, and (separately) using copper.
EXAMPLE 6: Examples 3 and 4 were successfully repeated using silver. Oxidation was successful with 0.2 Torr oxygen and only 3 Watts plasma (for 3 minutes).
D.136\392GB02SPECIASFILED EXAMPLE 7: Example 2 was repeated with oxidation and reduction both under 0. 1 Torr of the respective gas, both under a mild plasma (5 Watts) for 5 minutes. This mild treatment yielded an extremely effective electrochemical material for e.g. amperometric sensor use.
f D\136\392\GBO2SPEC\ASFILED
Claims (13)
- CLAIMS 1. A method of making a porous Gp VIII metal composite body,comprising metallising a porous substrate, oxidising the metallisation and reducing the metallisation, characterised in that the oxidation is performed in the gas phase by oxidative plasma and 5 the reduction is performed in the gas phase by reducing plasma.
- 2.
- 3.
- 4.gas phase.method according to Claim 1, wherein the substrate is ceramic or polymeric.method according to Claim 2, wherein the substrate is a fluoropolymer.method according to any preceding claim, wherein the body is metallised in the
- 5. A method according to any preceding claim, wherein the Gp VIH metal is platinum, palladium, silver or nickel.
- 6. A method according to any preceding claim, wherein the ratio metaksubstrate is less than 1: 1.
- 7.
- 8.A method according to Claim 6, wherein the ratio metal:substrate is less than 1: 100. A method according to any preceding claim, in which the metallisation is oxidised by oxygen plasma.
- 9. A method according to any preceding claim, wherein the reduction is performed by hydrogen plasma.
- 10. A method according to any preceding claim in which the substrate does not 20 exceed 325K during the plasma treatments.
- 11. A porous metal composite body made by a method according to any preceding claim.
- 12. A porous metal composite body comprising a porous substrate bearing less than 1 % by weight metal, the metal having a specific surface area at least ten times that of the substrate.
- 13. A catalyst comprising a body according to Claim 11 or 12.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9405518A GB9405518D0 (en) | 1994-03-21 | 1994-03-21 | Porous metal composite body |
Publications (3)
Publication Number | Publication Date |
---|---|
GB9505644D0 GB9505644D0 (en) | 1995-05-10 |
GB2287720A true GB2287720A (en) | 1995-09-27 |
GB2287720B GB2287720B (en) | 1997-11-05 |
Family
ID=10752220
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9405518A Pending GB9405518D0 (en) | 1994-03-21 | 1994-03-21 | Porous metal composite body |
GB9505644A Expired - Fee Related GB2287720B (en) | 1994-03-21 | 1995-03-21 | Porous metal composite body |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9405518A Pending GB9405518D0 (en) | 1994-03-21 | 1994-03-21 | Porous metal composite body |
Country Status (12)
Country | Link |
---|---|
US (1) | US5798148A (en) |
EP (1) | EP0751824B1 (en) |
JP (1) | JP3769295B2 (en) |
AT (1) | ATE166250T1 (en) |
AU (1) | AU685247B2 (en) |
DE (1) | DE69502599T2 (en) |
DK (1) | DK0751824T3 (en) |
ES (1) | ES2116735T3 (en) |
FI (1) | FI121532B (en) |
GB (2) | GB9405518D0 (en) |
HK (1) | HK1010999A1 (en) |
WO (1) | WO1995025588A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19817388A1 (en) * | 1998-04-20 | 1999-10-28 | Atotech Deutschland Gmbh | Metallizing a fluoropolymer substrate for forming conductor structures or a plasma etching mask on a circuit substrate |
US6245435B1 (en) | 1999-03-01 | 2001-06-12 | Moen Incorporated | Decorative corrosion and abrasion resistant coating |
US6682627B2 (en) | 2001-09-24 | 2004-01-27 | Applied Materials, Inc. | Process chamber having a corrosion-resistant wall and method |
WO2003042216A1 (en) * | 2001-11-09 | 2003-05-22 | Schering Corporation | Polycyclic guanine derivative phosphodiesterase v inhibitors |
US7026057B2 (en) | 2002-01-23 | 2006-04-11 | Moen Incorporated | Corrosion and abrasion resistant decorative coating |
JP3933058B2 (en) * | 2002-02-25 | 2007-06-20 | 日立化成工業株式会社 | Support unit for microfluidic system and method for manufacturing the same |
EP1738820B1 (en) * | 2004-02-18 | 2009-11-11 | Hitachi Chemical Co., Ltd. | Micro-fluidic unit having a hollow filament channel |
KR100679341B1 (en) * | 2004-09-15 | 2007-02-07 | 한국에너지기술연구원 | Preparation Method of Palladium Alloy Composite Membrane for Hydrogen Separation |
US8409515B2 (en) * | 2009-07-14 | 2013-04-02 | GM Global Technology Operations LLC | Exhaust gas treatment system |
EP2564455B1 (en) | 2010-04-26 | 2016-09-28 | 3M Innovative Properties Company | Annealed nanostructured thin film catalyst |
WO2014098774A1 (en) * | 2012-12-21 | 2014-06-26 | Agency For Science, Technology And Research | Porous metallic membrane |
DE102022203401A1 (en) | 2022-04-06 | 2023-10-12 | Robert Bosch Gesellschaft mit beschränkter Haftung | Method for cleaning at least one upper side of a substrate |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3715238A (en) * | 1969-03-20 | 1973-02-06 | American Cyanamid Co | Method of making a porous catalytic electrode |
EP0108188A2 (en) * | 1982-11-05 | 1984-05-16 | Nissan Motor Co., Ltd. | Method of producing electrode for liquid fuel cell |
GB2190399A (en) * | 1986-05-02 | 1987-11-18 | Nat Res Dev | Multi-metal electrode |
WO1990000208A1 (en) * | 1988-06-29 | 1990-01-11 | The City University | Process for the preparation of porous metal |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1865180A (en) * | 1931-06-15 | 1932-06-28 | Universal Oil Prod Co | Process for producing catalysts |
GB1556452A (en) * | 1977-10-25 | 1979-11-28 | Nat Res Dev | Catalysing hydrogen evolution |
JPS5684636A (en) * | 1979-12-08 | 1981-07-10 | Tanaka Kikinzoku Kogyo Kk | Palladium catalyst and its production |
US4540476A (en) * | 1982-12-10 | 1985-09-10 | At&T Bell Laboratories | Procedure for making nickel electrodes |
JPS60216458A (en) * | 1984-04-11 | 1985-10-29 | Matsushita Electric Ind Co Ltd | Regeneration method of negative electrode of high-temperature fuel cell |
DE3522287A1 (en) * | 1985-06-21 | 1987-01-02 | Moc Danner Gmbh | Open-pored body for filtering and/or catalytic treatment of gases or liquids and process for the production thereof |
GB8613015D0 (en) * | 1986-05-29 | 1986-07-02 | Thomas T R | Porous ptfe |
US4756964A (en) * | 1986-09-29 | 1988-07-12 | The Dow Chemical Company | Barrier films having an amorphous carbon coating and methods of making |
US4689111A (en) * | 1986-10-28 | 1987-08-25 | International Business Machines Corp. | Process for promoting the interlaminate adhesion of polymeric materials to metal surfaces |
US4933060A (en) * | 1987-03-02 | 1990-06-12 | The Standard Oil Company | Surface modification of fluoropolymers by reactive gas plasmas |
US4818745A (en) * | 1987-09-08 | 1989-04-04 | Phillips Petroleum Company | Catalyst for oxidation of carbon monoxide and process for preparing the catalyst |
JPH0760821B2 (en) * | 1991-05-17 | 1995-06-28 | インターナショナル・ビジネス・マシーンズ・コーポレイション | Conditioning method for polymer base material |
-
1994
- 1994-03-21 GB GB9405518A patent/GB9405518D0/en active Pending
-
1995
- 1995-03-21 ES ES95911450T patent/ES2116735T3/en not_active Expired - Lifetime
- 1995-03-21 DK DK95911450T patent/DK0751824T3/en active
- 1995-03-21 EP EP95911450A patent/EP0751824B1/en not_active Expired - Lifetime
- 1995-03-21 JP JP52448295A patent/JP3769295B2/en not_active Expired - Fee Related
- 1995-03-21 US US08/700,367 patent/US5798148A/en not_active Expired - Lifetime
- 1995-03-21 GB GB9505644A patent/GB2287720B/en not_active Expired - Fee Related
- 1995-03-21 DE DE69502599T patent/DE69502599T2/en not_active Expired - Lifetime
- 1995-03-21 AT AT95911450T patent/ATE166250T1/en active
- 1995-03-21 AU AU19020/95A patent/AU685247B2/en not_active Ceased
- 1995-03-21 WO PCT/GB1995/000620 patent/WO1995025588A1/en active IP Right Grant
-
1996
- 1996-09-20 FI FI963749A patent/FI121532B/en not_active IP Right Cessation
-
1998
- 1998-12-12 HK HK98112214A patent/HK1010999A1/en not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3715238A (en) * | 1969-03-20 | 1973-02-06 | American Cyanamid Co | Method of making a porous catalytic electrode |
EP0108188A2 (en) * | 1982-11-05 | 1984-05-16 | Nissan Motor Co., Ltd. | Method of producing electrode for liquid fuel cell |
GB2190399A (en) * | 1986-05-02 | 1987-11-18 | Nat Res Dev | Multi-metal electrode |
WO1990000208A1 (en) * | 1988-06-29 | 1990-01-11 | The City University | Process for the preparation of porous metal |
Also Published As
Publication number | Publication date |
---|---|
GB2287720B (en) | 1997-11-05 |
EP0751824B1 (en) | 1998-05-20 |
JPH09510506A (en) | 1997-10-21 |
AU1902095A (en) | 1995-10-09 |
HK1010999A1 (en) | 1999-07-02 |
DK0751824T3 (en) | 1998-10-07 |
GB9405518D0 (en) | 1994-05-04 |
WO1995025588A1 (en) | 1995-09-28 |
EP0751824A1 (en) | 1997-01-08 |
DE69502599D1 (en) | 1998-06-25 |
DE69502599T2 (en) | 1998-11-19 |
FI963749A0 (en) | 1996-09-20 |
AU685247B2 (en) | 1998-01-15 |
GB9505644D0 (en) | 1995-05-10 |
ATE166250T1 (en) | 1998-06-15 |
US5798148A (en) | 1998-08-25 |
JP3769295B2 (en) | 2006-04-19 |
FI121532B (en) | 2010-12-31 |
ES2116735T3 (en) | 1998-07-16 |
FI963749A (en) | 1996-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5798148A (en) | Porous metal composite body | |
US7838457B2 (en) | Process for production of conductive catalyst particles, process for production of catalyst electrode capable of gas diffusion, apparatus for production of conductive catalyst particles, and vibrating apparatus | |
Štulikova | The deposition and stripping of mercury on a glassy carbon rotating disk electrode | |
JP2001516135A (en) | Electrode catalyst deposition method and electrode formed by such method | |
WO1997003476A1 (en) | ELECTROCATALYTIC STRUCTURE COMPRISING A MATRIX OF SiOxCyHz HAVING DISPERSED THEREIN PARTICLES OF CATALYTIC MATERIAL | |
EP1807185A1 (en) | Preparation method of palladium alloy composite membrane for hydrogen separation | |
JPH09153366A (en) | Manufacture of composite catalyst compact | |
CA2183763C (en) | Porous metal composite body | |
Fang et al. | Protein retention on plasma-treated hierarchical nanoscale gold-silver platform | |
JPH06111828A (en) | Fuel electrode material for fuel cell, and manufacture thereof | |
JPS6238655B2 (en) | ||
EP0982412B1 (en) | Process for improving the adhesion of metallic particles on a carbon substrate | |
JP3755056B2 (en) | Hydrogen separation membrane, method for producing the same, and method for separating hydrogen | |
US20030021890A1 (en) | Process for making a fuel cell with cylindrical geometry | |
KR102139494B1 (en) | Method for manufacturing 3d porous thin film catalyst electrode for fuel cell | |
Wolf et al. | Ion implanted catalysts for fuel cell reactions | |
JP3452096B2 (en) | Method for manufacturing gas diffusion electrode for fuel cell | |
RU2749729C1 (en) | Method for production of multilayer metal nanostructured catalytic coatings | |
Qi et al. | PLATINUM NANOPARTICLES DISPERSED ON POLYPYRROLE NANO-/MICRO-PARTICLES | |
JP2013510394A (en) | Method for producing electrode layer containing catalyst | |
Enea et al. | Electrooxidation reactions on gas-diffusion electrodes catalyzed by DC sputtered Pt | |
JPH0812172B2 (en) | Electrode for potentiostatic electrolysis gas detector | |
RU2137262C1 (en) | Method for producing porous metal; porous metal and electrode for electrochemical charge accumulation and storage device | |
CA1124678A (en) | Exhaust electrode process for exhaust gas oxygen sensor | |
Hayase et al. | Formation of Porous Noble Metal Layer by Displacement Reactions with Porous Silicon |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20120321 |