JP2825383B2 - Improved anode for oxygen generation - Google Patents
Improved anode for oxygen generationInfo
- Publication number
- JP2825383B2 JP2825383B2 JP3344634A JP34463491A JP2825383B2 JP 2825383 B2 JP2825383 B2 JP 2825383B2 JP 3344634 A JP3344634 A JP 3344634A JP 34463491 A JP34463491 A JP 34463491A JP 2825383 B2 JP2825383 B2 JP 2825383B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- coating
- titanium
- plasma
- electrode
- 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.)
- Expired - Lifetime
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 6
- 239000001301 oxygen Substances 0.000 title claims description 6
- 229910052760 oxygen Inorganic materials 0.000 title claims description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 77
- 239000002184 metal Substances 0.000 claims abstract description 77
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 238000007750 plasma spraying Methods 0.000 claims abstract description 12
- 230000003746 surface roughness Effects 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005363 electrowinning Methods 0.000 claims description 3
- 229910000765 intermetallic Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000002345 surface coating layer Substances 0.000 claims description 2
- 238000007743 anodising Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 29
- 150000002739 metals Chemical class 0.000 abstract description 16
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000005530 etching Methods 0.000 description 16
- 238000011282 treatment Methods 0.000 description 13
- 239000007921 spray Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000010285 flame spraying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- -1 platinum group metals Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000007751 thermal spraying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011262 electrochemically active material Substances 0.000 description 2
- 238000005323 electroforming Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011416 infrared curing Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- IANUMTRPEYONHL-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) titanium(4+) Chemical compound [O-2].[Ti+4].[Ru+3] IANUMTRPEYONHL-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000010992 reflux 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
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- 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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- General Chemical & Material Sciences (AREA)
- Coating By Spraying Or Casting (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Pinball Game Machines (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、バルブ金属より成り、
その表面の一部が使用時にえぐりとられ、平滑度を失っ
た使用済み電極材料と、その表面に、被覆接着強化のた
め、プラズマ溶射により平らにされ且つ所望の表面粗さ
を付与されたバルブ金属からなるプラズマ溶射塗布被覆
層と、その表面に白金族金属又はその酸化物を含有する
電気化学的に活性な表面被覆層を有する酸素発生用陽極
に関する。The present invention relates to a valve metal.
A used electrode material whose part of the surface is cut off during use and loses smoothness, and a valve whose surface is flattened by plasma spraying and has a desired surface roughness to enhance coating adhesion. The present invention relates to an anode for oxygen generation having a plasma sprayed coating layer made of a metal and an electrochemically active surface coating layer containing a platinum group metal or an oxide thereof on the surface thereof.
【0002】[0002]
【従来の技術】電極基材金属表面に直接塗付される被覆
の接着は、その被覆された金属を厳しい産業環境で使用
する際に特に重大なものである。普通、被覆前の表面処
理及び予備処理の操作は注意深く行われる。そのような
処理又は予備処理の操作では、清浄な表面にすることが
一番重要である。BACKGROUND OF THE INVENTION The adhesion of coatings applied directly to electrode substrate metal surfaces is particularly critical when the coated metal is used in harsh industrial environments. Usually, the surface treatment and pre-treatment operations before coating are performed carefully. In such treatment or pre-treatment operations, it is most important to have a clean surface.
【0003】電極基材に直接塗付される被覆の代表例は
電解触媒の被覆であり、これは頻々白金族の貴金属を含
有し、バルブ金属等の金属上に直接塗付される。電極基
材に塗付される電解触媒被覆の技術分野では、金属を単
に洗浄して極めて平滑な表面にする(米国特許第4,7
97,182号明細書)。フッ素化合物処理は表面を平
滑にする(米国特許第3,864,163号明細書)。
洗浄には、化学脱脂、電解脱脂又は酸化性の酸による処
理が含まれる(米国特許第3,864,163号明細
書)。洗浄後に機械的粗化により被覆用の表面を調製す
る(米国特許第3,778,307号明細書)。機械的
処理がサンドブラスト処理である場合には、その後エッ
チングする(米国特許第3,878,083号明細
書)。或いはその後に金属粉末の微粒混合物を火炎溶射
塗付してもよい(米国特許第4,849,085号明細
書)。A typical example of a coating applied directly to an electrode substrate is an electrocatalytic coating, which frequently contains a platinum group noble metal, and is applied directly on a metal such as a valve metal. In the field of electrocatalyst coating applied to electrode substrates, metals are simply washed to a very smooth surface (US Pat. No. 4,7,738).
97,182). Fluorine compound treatment smoothes the surface (US Pat. No. 3,864,163).
Cleaning includes chemical degreasing, electrolytic degreasing or treatment with an oxidizing acid (US Pat. No. 3,864,163). The surface for coating is prepared by mechanical roughening after washing (US Pat. No. 3,778,307). If the mechanical treatment is a sandblasting treatment, it is then etched (US Pat. No. 3,878,083). Alternatively, a fine-grained mixture of metal powders may then be applied by flame spraying (US Pat. No. 4,849,085).
【0004】新しい被覆を電極基材に固定するための別
法は、電極基材上に多孔質酸化物の層を形成することで
あり、これはバルブ金属に電解触媒被覆を塗付する際に
有用なることが見出されていた。例えば、米国特許第
4,140,813号明細書に開示されているように、
電極基材金属上に酸化チタンを火炎溶射又はプラズマ溶
射した後に活性物質を電気化学的に塗付することができ
る。或いは米国特許第4,392,927号明細書に教
示されているように、電解触媒として活性な粒子を予か
じめ塗付する熱溶射材料は金属酸化物、窒化物等であっ
てもよい。[0004] An alternative to fixing the new coating to the electrode substrate is to form a layer of porous oxide on the electrode substrate, which is used when applying an electrocatalytic coating to the valve metal. It has been found to be useful. For example, as disclosed in U.S. Pat. No. 4,140,813,
The active substance can be applied electrochemically after flame or plasma spraying of titanium oxide on the electrode substrate metal. Alternatively, as taught in U.S. Pat. No. 4,392,927, the thermal spray material pre-coated with active particles as an electrocatalyst may be a metal oxide, nitride, or the like.
【0005】しかしながら、最も厳しい商業的環境例え
ば電気メッキ、電気錫メッキ、電気鋳造又は電解採取で
現在商業的に用いられている酸素発生用陽極に供するた
めの長寿命の被覆電極の提供は困難である。上記の操作
は連続操作であり、表面損傷の可能性を含む厳しい条件
に係わるものである。このような操作で被覆の接合を卓
越した状態に保ちつつ長期にわたり安定に操作できる電
極として被覆金属基材を提供できるようならば最も望ま
しいであろう。このような電極を新金属からだけでな
く、再被覆された金属から提供できることも極めて望ま
しいことである。However, it is difficult to provide a long-life coated electrode for use in the most demanding commercial environments such as the oxygen generating anodes currently used commercially in electroplating, electrotinning, electroforming or electrowinning. is there. The above operation is a continuous operation and involves severe conditions including possible surface damage. It would be most desirable if such a procedure could provide a coated metal substrate as an electrode that could be operated stably for a long period of time while maintaining excellent bonding of the coating. It would also be highly desirable to be able to provide such electrodes not only from new metals, but also from recoated metals.
【0006】[0006]
【発明が解決しようとする課題】今や卓越した被覆接着
である固定被覆(locked on coatin
g)を与える金属表面が知見されたのである。斯く被覆
された電極基材は、最も厳しい産業環境でも極めて望ま
しい長寿命を持つことができる。本発明によれば、使用
時に表面の一部がえぐりとられ、平滑度を失った使用済
み電極材料の表面に均一な平面性をもち十分に固定され
た被覆を付与することができる。SUMMARY OF THE INVENTION Locked on coating, which is now an excellent coating adhesive
The metal surface giving g) was found. Such coated electrode substrates can have a very desirable long life even in the harshest industrial environments. ADVANTAGE OF THE INVENTION According to this invention, a part of the surface is cut off at the time of use, and it is possible to apply a sufficiently fixed coating having uniform flatness to the surface of the used electrode material which has lost its smoothness.
【0007】本発明は、被覆接着性の強化に適した表面
粗さを有する電極基材表面を有する電極であり、斯かる
表面とは前記の基材上にプラズマ溶射塗付されたバルブ
金属表面であり、このプラズマ溶射塗付された表面は、
プロフィルメータ(profilometer)による
測定で、約6.4μm(250マイクロインチ)以上の
平均表面粗さ並びにプロフィルメータ上限閾値10.2
μm(400マイクロインチ)及びプロフィルメータ下
限閾値7.6μmを基準として、センチメートル当たり
平均約15.7個(40個/インチ)以上の表面ピーク
を有する。前記のプロフィルメータは、市販の表面粗さ
の測定装置である。その構造は、探触子アームが表面を
横切ると、表面粗さに比例した電流が誘起されて表面粗
さが測定できる。表面粗さは、プロフィルメータの測定
に基づいて、平均平面粗さ(Ra)、平均表面ピーク
(Nr)、最大ピークと最大谷部との平均距離(R
m)、平均ピーク高さ(Rz)で示す。前記の平均表面
ピーク数(Nr)を求めるには、断面曲線について可変
の予め決めた上限と下限の基準値(上限閾値と下限閾
値)を基準として、センチメートル当たりのピーク数
(Nr)を測定する。The present invention relates to an electrode having an electrode substrate surface having a surface roughness suitable for enhancing the coating adhesiveness, wherein said surface is a valve metal surface coated by plasma spraying on said substrate. And the plasma sprayed surface is
Average surface roughness greater than or equal to about 6.4 μm (250 microinches) as measured by a profilometer and an upper profile meter threshold of 10.2.
It has an average of about 15.7 (40 / inch) or more surface peaks per centimeter, based on μm (400 microinches) and the lower threshold of the profilometer 7.6 μm. The above profile meter is a commercially available surface roughness measuring device. In the structure, when the probe arm crosses the surface, a current proportional to the surface roughness is induced, and the surface roughness can be measured. The surface roughness is determined based on the measurement of the profile meter by the average plane roughness (Ra), the average surface peak (Nr), and the average distance (R) between the maximum peak and the maximum valley.
m) and the average peak height (Rz). In order to obtain the average surface peak number (Nr), the number of peaks per centimeter (Nr) is measured with reference to variable upper and lower reference values (upper threshold value and lower threshold value) that are variable for the cross-sectional curve. I do.
【0008】本発明は、使用時にえぐりとられて平面性
を失った表面に被覆接着性強化のためのプラズマ金属表
面を整える方法であり、この方法は斯かる表面のえぐり
とられた部分にバルブ金属をプラズマ溶射して金属表面
の平面性を確立し、その後にプラズマ溶射して所望の表
面粗さを形成し、被覆接着性を強化したものである。The present invention is a method of arranging a plasma metal surface to enhance coating adhesion on a surface that has been cut out and loses planarity during use, the method comprising providing a valve on the cut-out portion of such a surface. The metal is plasma-sprayed to establish the flatness of the metal surface, and then plasma-sprayed to form the desired surface roughness and enhance the coating adhesion.
【0009】本発明による酸素発生用陽極は、連続的な
電気亜鉛メッキ、電気錫メッキ、銅箔メッキ、電気鋳造
又は電解採取及び硫酸ナトリウム電解を含む厳しい商業
操作下でも、斯かる電極は極めて望ましい使役寿命をも
つことができるのである。The anode for oxygen generation according to the present invention is highly desirable even under severe commercial operations including continuous electrogalvanizing, electrotinning, copper foil plating, electroforming or electrowinning and sodium sulfate electrolysis. It can have a working life.
【0010】[0010]
【課題を解決するための手段】電極基材は常にチタン、
タンタル、アルミニウム、ジルコニウム及びニオブを含
むバルブ金属が用いられる。凸凹性、耐食性及び入手性
の点で特に興味がもたれるものはチタンである。基材と
して好適な金属には、通常入手できる元素金属の他に、
一種以上のバルブ金属を含有する合金や金属間化合物並
びにセラミックやサーメットが包含される。例えば、チ
タンをニッケル、コバルト、鉄、マンガン又は銅の合金
にすることができる。更に詳しく述べると、グレード5
チタンは6.75重量%までのアルミニウムと4.5重
量%のバナジウムを含み、グレード6チタンは6%まで
のアルミニウムと3%の錫を含み、グレード7チタンは
0.25重量%までのパラジウムを含み、グレード10
チタンは10乃至13%のモリブデンと4.5乃至7.
5重量%のジルコニウムを含む等々である。The electrode base material is always titanium,
Valve metals including tantalum, aluminum, zirconium and niobium are used. Of particular interest in terms of roughness, corrosion resistance and availability is titanium. Metals suitable as a substrate, in addition to the commonly available elemental metals,
Alloys and intermetallics containing one or more valve metals as well as ceramics and cermets are included. For example, titanium can be an alloy of nickel, cobalt, iron, manganese or copper. More specifically, grade 5
Titanium contains up to 6.75% by weight of aluminum and 4.5% by weight of vanadium, Grade 6 titanium contains up to 6% of aluminum and 3% tin, Grade 7 titanium contains up to 0.25% by weight of palladium Grade 10
Titanium is 10-13% molybdenum and 4.5-7.
Containing 5% by weight of zirconium and so on.
【0011】元素金属、合金及び金属間混合物を使用す
るという意味は、詳しくいえば通常入手できる条件の金
属すなわち少量の不純物を含む金属を使用することであ
る。すなわち、特に興味ある金属であるチタンでは、そ
の他の成分が合金であったり合金プラス不純物であるよ
うなものを含み、各種グレードが入手可能である。チタ
ンのグレードは、ASTM B265−79のチタンの
標準仕様に更に詳しく説明されている。The use of elemental metals, alloys and intermetallic mixtures means, in particular, the use of metals of generally available conditions, ie metals containing small amounts of impurities. That is, for titanium, which is a metal of particular interest, various grades are available, including those whose other components are alloys or alloy plus impurities. Titanium grades are further described in the ASTM B265-79 standard specification for titanium.
【0012】電極基材用の金属に何を選ぶか、その後金
属表面にどのような処理を施すかに関係なく、電極基材
金属の表面は清浄であることが有利である。これは、電
極基材の金属表面を清浄にする何れの処理にても達成さ
れるが、古い被覆の除去が必要でなかったり、エッチン
グを用いるような場合には、以下で詳しく説明するよう
に、機械的清浄は最小にされるのが普通である。すなわ
ち、化学脱脂又は電解脱脂による普通の清浄化方法、或
いはその他の化学的清浄化操作を有利に用いることがで
きる。Regardless of the choice of metal for the electrode substrate and the subsequent treatment of the metal surface, it is advantageous for the surface of the electrode substrate metal to be clean. This can be achieved by any process that cleans the metal surface of the electrode substrate, but if removal of old coatings is not necessary or if etching is used, as described in detail below. Usually, mechanical cleaning is minimized. That is, a conventional cleaning method by chemical degreasing or electrolytic degreasing, or other chemical cleaning operations can be advantageously used.
【0013】電極基材の金属表面上に古い被覆が存在す
る場合には、再被覆の前に上記の清浄化が必要かどうか
をチェックする必要がある。本発明に係る酸素発生用陽
極を使用する際に性能を最高度にするには、古い被覆を
除去することが好ましい。バルブ金属上の電気化学的に
活性な被覆に関する本発明の技術分野では、被覆除去の
化学的手段は周知である。すなわち、米国特許第3,5
73,100号明細書に教示されているように、本質的
に塩基性の材料の溶融物で処理した後すぐに酸洗いする
と、金属表面は好適に再構成される。また、米国特許明
細書第3,706,600号明細書に記載されているよ
うに、アルカリ金属水素化物を含有するアルカリ金属水
酸化物の溶融物で処理した後に鉱酸で処理すると有用で
ある。通常のゆすぎ工程や乾燥工程もこれらの操作の一
部を構成することができる。If there is an old coating on the metal surface of the electrode substrate, it is necessary to check whether the above-mentioned cleaning is necessary before recoating. For maximum performance when using the anode for oxygen generation according to the present invention, it is preferable to remove the old coating. Chemical means of coating removal are well known in the art of the present invention for electrochemically active coatings on valve metal. That is, US Pat.
Pickling immediately after treatment with a melt of an essentially basic material, as taught in U.S. Pat. No. 73,100, suitably reconstructs the metal surface. Also, as described in U.S. Pat. No. 3,706,600, it is useful to treat with a melt of an alkali metal hydroxide containing an alkali metal hydride and then with a mineral acid. . Normal rinsing and drying steps can also form part of these operations.
【0014】本発明の実施に於いて、表面を清浄にした
後又は表面を調製して清浄にした後でバルブ金属に電解
触媒被覆を施こす場合、表面が粗くなる。これは、プラ
ズマ溶射塗付、普通は微粒状バルブ金属とくにチタン粉
を用いる手段により達成される。しかしながら、以下で
説明するように、金属は微粒形態で塗付されるとは云う
ものの、供給金属すなわち塗付される金属がワイヤ形態
等別の形態であってもよいのである。塗付法を代表とし
て微粒状金属の塗付で説明するのは、便宜上の理由であ
ると解されたい。このプラズマ溶射法では、金属を溶融
し、任意選択成分として少量の水素を含む不活性ガス例
えばアルゴンや窒素を電気アークで高温に加熱し、それ
により発生したプラズマ流中に溶融金属を散布するので
ある。本発明で使用する「プラズマ溶射」なる語は、プ
ラズマ溶射法が好適なのではあるが、一般に熱的溶射法
たとえば電磁流体力学的溶射法、火炎溶射法及びアーク
溶射法も含むものであると解されなければならない。In the practice of the present invention, if the electrocatalytic coating is applied to the valve metal after the surface has been cleaned or after the surface has been prepared and cleaned, the surface becomes rough. This is achieved by means of plasma spray coating, usually using finely divided valve metals, especially titanium powder. However, as described below, although the metal is applied in finely divided form, the supply metal, that is, the metal to be applied, may be in another form, such as a wire form. It should be understood that the reason why the application of the fine metal particles is described as a typical application method is for convenience. In this plasma spraying method, the metal is melted, and an inert gas containing a small amount of hydrogen as an optional component, such as argon or nitrogen, is heated to a high temperature by an electric arc, and the molten metal is sprinkled in the plasma flow generated thereby. is there. The term "plasma spraying" as used in the present invention, although plasma spraying is preferred, should generally be understood to also include thermal spraying, such as magnetohydrodynamic spraying, flame spraying and arc spraying. Must.
【0015】溶射パラメータ、例えば火炎溶射流又はプ
ラズマ溶射流の容積及び温度、微粒金属構成要素の供給
速度等は、その微粒金属構成要素が溶射流中でそれによ
り溶融し、実質的に溶融した形態のまま基材金属上に沈
着し、従って有孔構造を有する本質的に連続な被覆(す
なわち、溶射された粒子が見分けられない被覆)になる
ように選択される。代表的には、実施例で用いるような
溶射パラメータが満足な被覆を与える。普通、溶融溶射
時の基材金属は常温近くの温度に維持される。これは、
溶射時に基材上に空気流を当てたり、基材を溶射パス間
に空冷する等の手段により達成される。The spray parameters, such as the volume and temperature of the flame or plasma spray stream, the feed rate of the fine metal component, etc., may vary depending on the form in which the fine metal component is melted and substantially molten in the spray stream. It is selected so as to deposit on the substrate metal as it is, and thus have an essentially continuous coating having a perforated structure (ie, a coating in which the sprayed particles are indistinguishable). Typically, spray parameters as used in the examples provide satisfactory coatings. Usually, the base metal during melt spraying is maintained at a temperature close to room temperature. this is,
This is achieved by means such as applying an air flow onto the substrate during thermal spraying, or air cooling the substrate between thermal spray passes.
【0016】使用される微粒状金属、例えばチタン粉の
代表的粒径範囲は20−100ミクロンであり、表面を
効率的に粗くするには全粒子が40−80ミクロンの範
囲に入ることが好ましい。相異なる粒径をもった金属粒
子も、容易にプラズマ溶射塗付される限り等しく好適で
ある。粒子金属の組成は、基材金属に関して前述したこ
とと同様であり、例えばチタンは幾つかのグレードの一
種であり、普通はグレード1チタンである。混合物例え
ば金属の混合物又は金属と他成分との混合物を塗付する
ことも考えられる。他成分には金属酸化物も含まれる。
金属と他成分との混合物では、例えば金属が過半量であ
って他成分が未半量である。このようなプラズマ溶射塗
付を基材金属表面のエッチングと組み合わせて用いるこ
とも考えられる。その際の夫々の処理は殆ど常に表面の
相異なる部分に施される。エッチングを使用する場合に
は、金属表面を激しくエッチングして粒界を深く出し、
三次元結晶粒を十分に露出させることが重要である。粒
界近傍の不純物が斯かる操作によりエッチングされるこ
とが好ましいのである。特に古い被覆が存在していて、
その被覆された基材が例えば電気メッキの陽極として使
用されている場合には、その金属製品は形状を損ない、
表面の平面性を失う可能性がある。代表的には、そのよ
うな形くずれは表面の欠損やえぐりとられた部分であろ
う。便宜上、欠損、引っかき傷及びえぐりとられた部分
を含む表面形くずれ並びに金属が実際に溶融・再固化す
る焼けを、全て本発明ではえぐりとられた部分と称す
る。これらのえぐりとられた部分は金属で充たされたり
充たされなかったりする。続いて再被覆の前に全表面を
エッチングする場合、充填域のエッチング効果は不良に
なることがあると予想される。また、基材のえぐりとら
れた部分が伸びたり、或いは基材が熱履歴及び/又は化
学的な作用を受けてエッチングに望ましい結果をもたら
さないこともある。従って、単に全表面をプラズマ溶射
することが特に望ましく、それによりこれらの基材欠陥
を克服することができる。場合によっては、プラズマ溶
射とエッチングとの組み合わせが有用になることも考え
られる。すなわち、えぐりとられた部分をプラズマ溶射
技術で埋めるのである。普通、形くずれしてない表面域
を先ずエッチングし、次にこの平らなエッチングされた
表面にマスクをかけて、残っているえぐりとられた部分
をプラズマ溶射塗付により埋め及び/又は表面処理す
る。つまり、プラズマ溶射を用いてえぐりとられた部分
を埋め且つ再活性化させることもできるし、或いは必ず
しも表面の平面性を回復させずに単にえぐりとられた部
分を再活性化させるためにプラズマ溶射を使用すること
もできる。再活性化とは、次に処理のためえぐりとられ
た部分を整えるプラズマ溶射塗付を意味する。このよう
にして、表面全体が被覆に必要な粗さをもつようにな
る。所望ならば、この同一処理時に望ましい平面度まで
磨き直してもよい。The typical particle size range of the finely divided metal used, for example titanium powder, is 20-100 microns, with all particles preferably in the range of 40-80 microns for efficient surface roughening. . Metal particles having different particle sizes are equally suitable as long as they are easily plasma sprayed. The composition of the particulate metal is similar to that described above for the base metal, for example titanium is one of several grades, usually grade 1 titanium. It is also conceivable to apply a mixture, for example a mixture of metals or a mixture of metals and other components. Other components include metal oxides.
In the mixture of the metal and the other component, for example, the metal is the majority and the other component is the non-half. It is also conceivable to use such plasma spray coating in combination with etching of the base metal surface. The respective treatments are almost always applied to different parts of the surface. When using etching, the metal surface is violently etched to deepen grain boundaries,
It is important that the three-dimensional crystal grains are sufficiently exposed. It is preferable that impurities near the grain boundaries be etched by such an operation. Especially old coatings are present,
If the coated substrate is used, for example, as an electroplating anode, the metal product will lose its shape,
Surface flatness may be lost. Typically, such shape defects will be surface defects or cut-outs. For the sake of convenience, surface irregularities including defects, scratches and perforated portions, and burns where the metal actually melts and re-solidifies are referred to in the present invention as perforated portions. These excavated parts may or may not be filled with metal. If the entire surface is subsequently etched before recoating, it is expected that the etching effect in the filled area may be poor. Also, the cut-out portions of the substrate may be stretched or the substrate may be subject to thermal history and / or chemical action that will not produce the desired results for etching. It is therefore particularly desirable to simply plasma spray the entire surface, so that these substrate defects can be overcome. In some cases, a combination of plasma spraying and etching may be useful. That is, the excavated portion is filled with the plasma spraying technique. Usually, the non-deformed surface area is first etched, and then the flat etched surface is masked, and the remaining undercut is filled and / or surface treated by plasma spraying. . That is, plasma spraying can be used to fill and re-activate the excavated area, or simply to re-activate the excavated area without necessarily restoring the planarity of the surface. Can also be used. Reactivation means a plasma spray application which then prepares the cutout for processing. In this way, the entire surface has the roughness required for coating. If desired, it may be re-polished to the desired flatness during this same process.
【0017】エッチングを使用する際に、その金属の熱
処理履歴が重要になることがある。例えば、チタン等の
金属のエッチング準備には、焼きなまし等により不純物
を粒界に拡散させる状態調整が最も有用である。例え
ば、グレード1チタンを適正に焼きなますと、粒界にお
ける鉄不純物の濃度が増大する。好適調整が焼きなまし
であって、金属がグレード1チタンである場合、チタン
を約500℃以上の温度で約15分以上の時間にわたり
焼きなますことができる。操作効率の点からは、例えば
600−800℃といった高めの焼きなまし温度が有利
である。When using etching, the heat treatment history of the metal can be important. For example, in preparation for etching a metal such as titanium, it is most useful to adjust the condition of diffusing impurities to the grain boundaries by annealing or the like. For example, properly annealing grade 1 titanium increases the concentration of iron impurities at grain boundaries. If the preferred adjustment is annealing and the metal is grade 1 titanium, the titanium can be annealed at a temperature of about 500 ° C. or more for a time of about 15 minutes or more. Higher annealing temperatures, e.g., 600-800 <0> C, are advantageous in terms of operating efficiency.
【0018】エッチングを使用する場合には、粒界を激
しく攻撃する十分に活性なエッチング溶液で行う。代表
的エッチング溶液は酸性溶液であり、塩酸、硫酸、過塩
素酸、硫酸、シュウ酸、酒石酸及びリン酸並びにそれら
の混合物たとえば王水とすることができる。その他の使
用できるエッチング剤には、苛性エッチング剤たとえば
水酸化カリウム/過酸化水素混合溶液又は水酸化カリウ
ムと硝酸カリウムとの溶融物がある。操作効率の点か
ら、エッチング溶液は例えば18−22重量%塩酸溶液
のように強い即ちの濃厚な溶液であると有利である。更
には、この溶液はエッチング時に水溶液の場合には80
℃以上といった昇温に維持されると有利であり、頻々沸
騰条件若しくはその近傍、或いはそれより高い温度たと
えば還流状態に維持される。エッチングの後、エッチン
グされた金属表面をゆすぎ及び乾燥の工程に付して被覆
用の表面を準備することができる。エッチング及び焼き
なましに関する更に詳しい説明は米国特許出願第37
4,429号明細書に記載されており、その開示を引用
する。If etching is used, it is performed with a sufficiently active etching solution that violently attacks the grain boundaries. A typical etching solution is an acidic solution, which may be hydrochloric acid, sulfuric acid, perchloric acid, sulfuric acid, oxalic acid, tartaric acid and phosphoric acid and mixtures thereof, such as aqua regia. Other etchants that can be used include caustic etchants, such as a mixed solution of potassium hydroxide / hydrogen peroxide or a melt of potassium hydroxide and potassium nitrate. In terms of operating efficiency, it is advantageous if the etching solution is a strong or concentrated solution, for example a 18-22% by weight hydrochloric acid solution. Furthermore, this solution may be used in the case of an aqueous solution at the time of etching.
It is advantageous if the temperature is maintained at an elevated temperature of not less than 0 ° C., and the temperature is frequently maintained at or near the boiling condition or at a higher temperature, for example, a reflux state. After etching, the etched metal surface can be subjected to a rinsing and drying step to prepare the surface for coating. For a more detailed description of etching and annealing, see U.S. Pat.
No. 4,429, the disclosure of which is cited.
【0019】プラズマ溶射塗付された表面粗さに関して
は、その金属表面が約6.4μm(250マイクロイン
チ)以上の平均粗さ(Ra)及びセンチメートル当たり
平均約15.7個(40個/インチ)以上の表面ピーク
(Nr)を有する必要がある。センチメートル当たりの
表面ピーク数は、代表的には下限閾値7.6μm(30
0マイクロインチ)及び上限閾値10.2μm(400
マイクロインチ)を基準にして測定することができる。
約6.4μm(250マイクロインチ)未満の平均粗さ
を有する表面は、必要とされる被覆接着性の実質的強化
に望ましくない程平滑であり、センチメートル当たり平
均約15.7個未満の表面ピークを有する表面も同様で
ある。約10.2μm(400マイクロインチ)以上、
例えば約19.1乃至38.1μm(750−1500
マイクロインチ)までの範囲の平均粗さを有し、約5.
1μm(200マイクロインチ)未満の低いスポットを
含んでいない表面が有利である。表面平滑をうまく回避
するには、約5.3乃至5.6μm(210乃至220
マイクロインチ)未満の低いスポットを含まない表面で
あることが有利である。約7.6乃至約12.7μm
(300乃至500マイクロインチ)の表面粗さを有す
る表面が好適である。表面のセンチメートル当たりの平
均ピーク数は約23.6個(60個/インチ)以上であ
ると有利であって、約51.1個(130個/インチ)
以上であってもよいが、平均約31.4乃至約47.2
個/センチメートル(80乃至120個/インチ)であ
ることが好ましい。最大ピークと最大谷部との平均距離
(Rm)が約25.4μm(1000マイクロインチ)
以上であり、かつ、平均ピーク高さ(Rz)が約25.
4μm(1000マイクロインチ)である表面が更に有
利である。前記の表面特性は全てプロフィロメータによ
り測定される。Rm値が約38.1乃至88.9μm
(1500乃至3500マイクロインチ)であり、最大
谷部特性が約38.1乃至88.9μm(1500乃至
3500マイクロインチ)である被覆用表面が更に望ま
しい。Regarding the plasma sprayed surface roughness, the metal surface has an average roughness (Ra) of about 6.4 μm (250 microinches) or more and an average of about 15.7 (40 / cm) per centimeter. Inches) or more. The number of surface peaks per centimeter is typically lower than 7.6 μm (30 μm).
0 microinches) and an upper threshold of 10.2 μm (400
Microinches).
Surfaces having an average roughness of less than about 6.4 μm (250 microinches) are undesirably smooth for the substantial enhancement of required coating adhesion, with an average of less than about 15.7 surfaces per centimeter. The same applies to a surface having a peak. About 10.2 μm (400 micro inches) or more,
For example, about 19.1 to 38.1 μm (750-1500
Micron inches) and have an average roughness in the range of about
Surfaces that do not contain low spots of less than 1 μm (200 microinches) are advantageous. To avoid surface smoothing, it is necessary to use about 5.3 to 5.6 μm (210 to 220 μm).
Advantageously, the surface does not contain low spots of less than microinches. About 7.6 to about 12.7 μm
Surfaces having a surface roughness of (300 to 500 microinches) are preferred. Advantageously, the average number of peaks per centimeter of the surface is about 23.6 (60 / inch) or more, and about 51.1 (130 / inch).
The average may be about 31.4 to about 47.2.
It is preferably 80/120 pieces / cm. The average distance (Rm) between the maximum peak and the maximum valley is about 25.4 μm (1000 micro inches)
And the average peak height (Rz) is about 25.
Surfaces that are 4 μm (1000 microinches) are even more advantageous. All of the above surface properties are measured with a profilometer. Rm value of about 38.1 to 88.9 μm
(1500 to 3500 microinches) and more desirably a coating surface having a maximum valley characteristic of about 38.1 to 88.9 μm (1500 to 3500 microinches).
【0020】基材が必要な表面粗さに達した後、その表
面は被覆される前に予備処理を含む種々の操作に付され
る。例えば、表面は溶剤洗浄等の清浄化操作に付され
る。或いは次のエッチングに付されたり、水素化処理や
窒化処理に付される。電気化学的に活性な材料で被覆す
る前に、米国特許第3,234,110号明細書に記載
されているように、基材を空気中で加熱したり或いはア
ノード酸化することにより酸化物層を付与することが提
案されている。ヨーロッパ特許出願第0,090,42
5号明細書は、基材に白金を電気メッキし、続いてそれ
にルテニウム、パラジウム又はイリジウムの酸化物を化
学沈着させることを提案している。主に保護中間部及び
導電中間部の役目をする下層上に電気化学的に活性な材
料の外層を沈着させる各種提案もなされている。英国特
許第1,344,540号明細書は、ルテニウム−チタ
ン酸化物又は同様な活性外層の下にコバルト又は鉛の酸
化物の電着層を使用することを開示している。米国特許
第4,272,354号明細書、同第3,882,00
2号明細書及び同第3,950,240号明細書には、
各種酸化錫ベースの下層が開示されている。After the substrate has reached the required surface roughness, the surface is subjected to various operations including pretreatment before being coated. For example, the surface is subjected to a cleaning operation such as solvent cleaning. Alternatively, it is subjected to the next etching, hydrogenation treatment or nitridation treatment. Prior to coating with the electrochemically active material, the oxide layer may be heated or anodized in air as described in U.S. Pat. No. 3,234,110. It has been proposed to provide European Patent Application No. 0,090,42
No. 5 proposes electroplating platinum on a substrate, followed by chemical deposition of ruthenium, palladium or iridium oxide on it. Various proposals have also been made for depositing an outer layer of an electrochemically active material on a lower layer which mainly serves as a protective intermediate and a conductive intermediate. GB 1,344,540 discloses the use of an electrodeposited layer of cobalt or lead oxide under a ruthenium-titanium oxide or similar active outer layer. U.S. Pat. Nos. 4,272,354 and 3,882,00
No. 2 and 3,950,240,
Various tin oxide based underlayers are disclosed.
【0021】必要な表面粗さを付与して何等かの予備処
理を行った後に本発明が最も考慮する被覆は、電気化学
的に活性な被覆、代表的には白金又はその他の白金族金
属から付与されるものであり、それらを白金族金属酸化
物酸化物、マグネタイト、フェライト、コバルトスピネ
ル又は混合金属酸化物の被覆のような活性酸化物被覆と
表すことができる。このような被覆は、代表的には、電
気化学工業における陽極被覆用に開発されたものであ
る。これらは、水又は例えばアルコール溶剤を用いて被
覆する。この型の好適被覆は米国特許第3,265,5
26号明細書、同第3,632,498号明細書、同第
3,711,385号明細書及び同第4,528,08
4号明細書に一般的に記載されている。混合金属酸化物
被覆には、頻々、白金、パラジウム、ロジウム、イリジ
ウム及びルテニウム又はそれらの混合物を含む白金族金
属の酸化物並びにその他の金属を含むバルブ金属酸化物
の一種以上が包含される。上に列挙したものに加えて更
なる被覆には、二酸化マンガン、二酸化鉛、MxPt3
O4(Mはアルカリ金属であり、xは代表的には約0.
5を目標とする)のような白金酸塩の被覆、ニッケル−
酸化ニッケル及びニッケル−ランタニド酸化物がある。The coatings that the present invention most considers after applying any necessary surface roughness and any pre-treatment are electrochemically active coatings, typically platinum or other platinum group metals. And they can be referred to as active oxide coatings, such as coatings of platinum group metal oxides, magnetite, ferrite, cobalt spinel or mixed metal oxides. Such coatings have typically been developed for anode coatings in the electrochemical industry. These are coated with water or, for example, an alcoholic solvent. A preferred coating of this type is disclosed in U.S. Pat. No. 3,265,5.
No. 26, 3,632,498, 3,711,385 and 4,528,08
No. 4, generally described. Mixed metal oxide coatings frequently include one or more oxides of the platinum group metals, including platinum, palladium, rhodium, iridium and ruthenium or mixtures thereof, and valve metal oxides including other metals. Further coatings in addition to those listed above include manganese dioxide, lead dioxide, MxPt 3
O 4 (M is an alkali metal and x is typically about 0.
Platinate coatings such as
There are nickel oxide and nickel-lanthanide oxide.
【0022】被覆物は、液体被覆組成物を金属基材に塗
付するために有用な何れの手段によっても金属に塗付さ
れると考えられる。このような方法には、浸漬・スピン
(dip spin)法や浸漬・排液(dip dra
in)法、ブラシ塗付法、ロール被覆法並びに静電スプ
レー等のスプレー塗付法がある。更には、スプレー塗付
法との組み合わせ技術、例えば浸漬・排液法とスプレー
塗付法との組み合わせを使用することもできる。電気化
学的に活性な被覆を与える前記の被覆組成物に関して
は、浸漬・排液変更法が最も有用である。前記の何れか
の被覆操作の後、液体被覆組成物から取り出し、被覆さ
れた金属表面を浸漬・排液するか、或いは強制空気乾燥
等その他の処理に付する。It is contemplated that the coating is applied to the metal by any means useful for applying the liquid coating composition to a metal substrate. Such methods include a dip spin method and a dip drain method.
In) method, brush coating method, roll coating method, and spray coating method such as electrostatic spraying. Furthermore, a combination technique with a spray coating method, for example, a combination of a dipping / draining method and a spray coating method can also be used. For those coating compositions that provide an electrochemically active coating, dipping and drainage modification methods are most useful. After any of the above coating operations, the coating is removed from the liquid coating composition and the coated metal surface is immersed and drained or subjected to other treatments such as forced air drying.
【0023】電解触媒被覆の代表的硬化条件は、硬化温
度が約300乃至約600℃なることである。硬化時間
は各被覆層によって異なり、僅か数分から1時間以上ま
で変化する。例えば数層の被覆層を塗付した場合には硬
化時間は長めになる。しかしながら、昇温下での焼きな
まし条件及び斯かる昇温への長期露出と重複するような
硬化操作は、経済性の点から一般に回避される。一般
に、使用される硬化技術は、金属基材上の被覆の硬化に
使用できるものなら何れも可である。すなわち、コンベ
アオーブンを含むオーブン硬化が使用できる。更には、
赤外線硬化技術を使用することもできる。最も経済的な
硬化を行うには、オーブン硬化の使用が好適であり、電
解触媒被覆に用いられる硬化温度は約450乃至約55
0℃の範囲内である。このような温度であると、各々の
塗付された被覆層の硬化時間は、殆ど常に僅か数分、例
えば3乃至10分である。 以下の実施例は、本発明の
実施方法及び比較例を示すものである。しかしながら、
本発明の実施方法を示すこの実施例が、本発明を限定す
ると解されてはならない。Typical curing conditions for the electrocatalyst coating are a curing temperature of about 300 to about 600 ° C. The curing time varies for each coating layer and varies from just a few minutes to over one hour. For example, when several coating layers are applied, the curing time becomes longer. However, curing operations that overlap with annealing conditions at elevated temperatures and prolonged exposure to such elevated temperatures are generally avoided from an economic standpoint. Generally, the curing technique used can be any that can be used to cure a coating on a metal substrate. That is, oven curing including a conveyor oven can be used. Furthermore,
Infrared curing technology can also be used. For most economical curing, the use of oven curing is preferred, and curing temperatures used for electrocatalytic coating are from about 450 to about 55.
Within the range of 0 ° C. At such temperatures, the curing time of each applied coating is almost always only a few minutes, for example 3 to 10 minutes. The following examples illustrate the practice of the present invention and comparative examples. However,
This example, which illustrates how to practice the invention, should not be construed as limiting the invention.
【0024】[0024]
【参考例1】合金化されていないグレード1チタン製の
約7.5cm2の試料表面を有する各試料板の裏面にチ
タンのナットを溶接した。次にこの試料板を大きな裏打
ち用板金に載せて試料板をモザイク状に配した。この積
載配列は、以下の諸操作で一単位として取り扱いできる
試料板大型アレイとして機能した。この試料板を酸化ア
ルミニウムでグリットブラスト処理を施した後、アセト
ンでゆすいで乾燥した。REFERENCE EXAMPLE 1 A titanium nut was welded to the back of each sample plate made of unalloyed grade 1 titanium and having a sample surface of about 7.5 cm 2 . Next, the sample plate was placed on a large backing sheet metal, and the sample plates were arranged in a mosaic shape. This loading array functioned as a large sample plate array that could be handled as one unit in the following operations. This sample plate was subjected to grit blasting with aluminum oxide, and then rinsed with acetone and dried.
【0025】平均粒径50−60ミクロンのチタン粉を
用いて、試料板上にチタン粉末の被覆を形成した。GH
スプレーノズルを備えたメトコ(Metoco)プラズ
マ溶射ガンを用いて試料板をこの粉末で被覆した。溶射
条件は、電流500アンベア;電圧45−50ボルト;
プラズマガス アルゴンとヘリウム;チタン供給速度1
−36kg(3ポンド)/時;溶射バンド幅 6.7ミ
リメートル;及び溶射距離64mmであり、その結果得
られたチタン試料板上のチタン層の厚みは約150ミク
ロンであった。A coating of titanium powder was formed on a sample plate using titanium powder having an average particle size of 50-60 microns. GH
A sample plate was coated with this powder using a Metoco plasma spray gun equipped with a spray nozzle. Thermal spraying conditions are: 500 ampere current; voltage 45-50 volts;
Plasma gas argon and helium; titanium supply rate 1
The spray bandwidth was 6.7 millimeters; and the spray distance was 64 mm. The resulting titanium layer on the titanium sample plate was approximately 150 microns thick.
【0026】次に、試料板の被覆された表面を、ホンメ
ルベルク社(HommelwerkGmbH)製のホン
メルモデルT1000C装置を用いて表面プロフィルメ
ータ測定に付した。試料板表面のプロフィルメータ測定
値は、装置を試料板の被覆された平らな面を横切るラン
ダムな向きに走らせて行った3個の別々の測定から平均
値を計算して決定した。この結果、三試料で測定した表
面粗さ(Ra)の平均値は夫々11.4、12.4及び
13.9μm(448、490及び548マイクロイン
チ)であり、ピーク数/cm(Nr)はこの三試料板の
夫々で29.9、24.8及び29.9(76.63及
び76個/インチ)であった。センチメートル当たりの
ピーク数は、7.6μm(300マイクロインチ、下
限)と10.2μm(400マイクロインチ、上限)の
閾値限界内で測定した。Next, the coated surface of the sample plate was subjected to a surface profilometer measurement using a Hommel model T1000C apparatus manufactured by Hommelwerk GmbH. The sample plate surface profilometer measurements were determined by calculating the average from three separate measurements made by running the instrument in a random orientation across the coated flat surface of the sample plate. As a result, the average values of the surface roughness (Ra) measured for the three samples were 11.4, 12.4 and 13.9 μm (448, 490 and 548 microinches), respectively, and the number of peaks / cm (Nr) was The values for the three sample plates were 29.9, 24.8 and 29.9 (76.63 and 76 pieces / inch), respectively. The number of peaks per centimeter was measured within the threshold limits of 7.6 μm (300 microinches, lower limit) and 10.2 μm (400 microinches, upper limit).
【0027】[0027]
【実施例1】予め電気化学的に活性な被覆で被覆した酸
素発生用陽極であって、使用済みの試料で表面がえぐり
とられ平滑度を失った電極基材表面をアルミナ粉でブラ
スト処理して前の被覆を除去した。この研磨法により前
の被覆が除去されたことが、蛍光X線により測定され
た。研磨処理の残渣を除去した後、得られた試料板をエ
ッチング処理した。95℃に加熱された20重量%の塩
酸水溶液に約1時間浸漬するとエッチング除去された。
試料板を熱塩酸から取り出した後、再度脱イオン水でゆ
すいて空気乾燥した。参考例1の方法で行ったプロフィ
ルメータ測定によると、試料の平らな表面での平均値
は、Ra4.6μm(180マイクロインチ)及びNr
12.2個/cm(31個/インチ)であった。EXAMPLE 1 A surface of an electrode substrate, which was previously coated with an electrochemically active coating and which had lost its smoothness because the surface was cut off with a used sample, was blasted with alumina powder. To remove the previous coating. The removal of the previous coating by this polishing method was measured by fluorescent X-rays. After removing the residue of the polishing treatment, the obtained sample plate was subjected to an etching treatment. When it was immersed in a 20% by weight aqueous hydrochloric acid solution heated to 95 ° C. for about 1 hour, it was etched away.
After removing the sample plate from the hot hydrochloric acid, it was rinsed again with deionized water and air-dried. According to the profile meter measurement performed by the method of Reference Example 1, the average value on the flat surface of the sample was Ra 4.6 μm (180 micro inches) and Nr
12.2 pieces / cm (31 pieces / inch).
【0028】次に、参考例1に記載のチタン粉及び塗布
法を用い、試料にプラズマ溶射塗付チタンの被覆を施し
た。参考例1の方法で行ったプロフィルメータ測定によ
ると、試料の平らな表面での平均値は、Ra16.5μ
m(650マイクロインチ)及びNr27.2個/cm
(69個/インチ)であった。Next, using the titanium powder and the coating method described in Reference Example 1, the sample was coated with plasma sprayed titanium. According to the profilometer measurement performed by the method of Reference Example 1, the average value on the flat surface of the sample was Ra16.5 μm.
m (650 micro inches) and Nr 27.2 pcs / cm
(69 pieces / inch).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C25D 17/10 101 C25D 17/10 101A (72)発明者 リチャード・シー・カールソン アメリカ合衆国オハイオ州44123,ユー クリッド,イースト・トゥハンドレッド シックスティーンス・ストリート 51 (72)発明者 ケネス・エル・ハーディー アメリカ合衆国オハイオ州44062,ミド ルフィールド,ジョージア・ロード 15818 (56)参考文献 特開 昭59−50195(JP,A) (58)調査した分野(Int.Cl.6,DB名) C25D 17/10 - 17/12,1/04 C25B 11/10 C25C 7/02────────────────────────────────────────────────── 6 Continuation of the front page (51) Int.Cl. 6 Identification symbol FI C25D 17/10 101 C25D 17/10 101A (72) Inventor Richard Sea Carlson 44123, Ohio, USA United States of America, East Tohand Red Sixties Street 51 (72) Inventor Kenneth El Hardy 15818 Georgia Road, Middlefield 44062, Ohio, United States 1556 (56) References JP-A-59-50195 (JPA) Field (Int.Cl. 6 , DB name) C25D 17/10-17 / 12,1 / 04 C25B 11/10 C25C 7/02
Claims (3)
る、電気化学的に活性な表面被覆層を有し、チタン、タ
ンタル、ニオブ、ジルコニウム、その合金及び金属間化
合物からなる群から選択された少なくとも1種を含有す
るバルブ金属からなり、その表面の一部が使用時にえぐ
りとられ、平滑度を失った使用済み電極材料と、 前記平滑度を失った電極材料の表面が、被覆接着強化の
ため、プラズマ溶射により、平らにされ且つ表面粗さを
付与された、チタン、タンタル、ニオブ、ジルコニウ
ム、その合金及び金属間化合物からなる群から選択され
た少なくとも1種を含有するバルブ金属からなるプラズ
マ溶射塗布被覆層と、 前記プラズマ溶射塗布被覆層の表面に被覆された、白金
族金属、又はその酸化物を含有する、電気化学的に活性
な表面被覆層とよりなり、 前記プラズマ溶射塗布被覆層がプロフィルメータによる
測定で6.4μm(250マイクロインチ)以上の平均
表面粗さ並びにプロフィルメータ上限閾値10.2μm
(400マイクロインチ)及びプロフィルメータ下限閾
値7.6μm(300マイクロインチ)を基準として、
センチメートル当たり15.7個(40個/インチ)以
上の平均表面ピークを有し、且つ前記プラズマ溶射塗布
被覆層のバルブ金属の粒子の大きさが20〜100ミク
ロンであることを特徴とする酸素発生用陽極。1. An electrochemically active surface coating layer containing a platinum group metal or an oxide thereof, selected from the group consisting of titanium, tantalum, niobium, zirconium, alloys and intermetallic compounds. A part of the surface is cut off during use, and the used electrode material which has lost smoothness, and the surface of the electrode material which has lost smoothness, has enhanced coating adhesion. A valve metal containing at least one selected from the group consisting of titanium, tantalum, niobium, zirconium, alloys and intermetallic compounds thereof, which has been flattened and surface-roughened by plasma spraying. A plasma spray coating layer, and an electrochemically active surface containing a platinum group metal or an oxide thereof coated on the surface of the plasma spray coating layer Becomes more and covering layer, wherein the plasma spray coating the coating layer is 6.4μm as measured by profilometer (250 microinches) or more the average surface roughness and profilometer upper threshold 10.2μm
(400 micro inches) and the lower limit threshold of the profile meter 7.6 μm (300 micro inches)
Oxygen having an average surface peak of not less than 15.7 (40 / inch) per centimeter, and the particle size of the valve metal of the plasma sprayed coating is 20-100 microns. Anode for generation.
槽又は電解採取槽の陽極である請求項1の電極。2. The electrode according to claim 1, wherein said electrode is an anode of an anodizing tank, an electroplating tank, or an electrowinning tank.
メッキ、硫酸ナトリウム電解又は銅箔メッキの陽極であ
る請求項1の電極。3. The electrode according to claim 1, wherein said electrode is an anode of electrogalvanization, electrotin plating, sodium sulfate electrolysis or copper foil plating.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63391490A | 1990-12-26 | 1990-12-26 | |
US633914 | 1990-12-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04301062A JPH04301062A (en) | 1992-10-23 |
JP2825383B2 true JP2825383B2 (en) | 1998-11-18 |
Family
ID=24541661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3344634A Expired - Lifetime JP2825383B2 (en) | 1990-12-26 | 1991-12-26 | Improved anode for oxygen generation |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0493326B1 (en) |
JP (1) | JP2825383B2 (en) |
KR (1) | KR100235378B1 (en) |
AT (1) | ATE154834T1 (en) |
AU (1) | AU643350B2 (en) |
CA (1) | CA2056943C (en) |
DE (1) | DE69126656T2 (en) |
DK (1) | DK0493326T3 (en) |
ES (1) | ES2104684T3 (en) |
GR (1) | GR3024677T3 (en) |
MX (1) | MX9102511A (en) |
TW (1) | TW197475B (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5314601A (en) * | 1989-06-30 | 1994-05-24 | Eltech Systems Corporation | Electrodes of improved service life |
JP3228644B2 (en) * | 1993-11-05 | 2001-11-12 | 東京エレクトロン株式会社 | Material for vacuum processing apparatus and method for producing the same |
DE59507977D1 (en) * | 1995-11-08 | 2000-04-13 | Fissler Gmbh | METHOD FOR PRODUCING AN NON-STICK COATING AND ITEMS PROVIDED WITH SUCH A PROCESS |
US20070071921A1 (en) * | 2005-09-20 | 2007-03-29 | James Coulas | Process for hardfacing a progressing cavity pump/motor rotor |
FI118159B (en) * | 2005-10-21 | 2007-07-31 | Outotec Oyj | Method for forming an electrocatalytic surface of an electrode and electrode |
ITMI20070980A1 (en) * | 2007-05-15 | 2008-11-16 | Industrie De Nora Spa | ELECTRODE FOR ELECTROLYTIC MEMBRANE CELLS |
EP2022447A1 (en) | 2007-07-09 | 2009-02-11 | Astra Tech AB | Nanosurface |
ITMI20102354A1 (en) * | 2010-12-22 | 2012-06-23 | Industrie De Nora Spa | ELECTRODE FOR ELECTROLYTIC CELL |
CN104073842A (en) * | 2011-10-13 | 2014-10-01 | 金川集团有限公司 | Negative plate used for electrodepositing electrolyzing nickel |
US9683300B2 (en) | 2012-06-18 | 2017-06-20 | Asahi Kasei Kabushiki Kaisha | Bipolar alkaline water electrolysis unit and electrolytic cell |
JP6234754B2 (en) * | 2013-09-18 | 2017-11-22 | 株式会社神戸製鋼所 | Electrode metal plate and electrode |
WO2015116123A2 (en) * | 2014-01-31 | 2015-08-06 | Hewlett-Packard Development Company, L.P. | Surface treatments of metal substrates |
JP7334095B2 (en) * | 2019-01-21 | 2023-08-28 | Dowaメタルマイン株式会社 | Tin electrowinning method |
DE102020120412A1 (en) | 2020-08-03 | 2022-02-03 | Canon Production Printing Holding B.V. | Device for heating a recording medium with a print image printed on the recording medium |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2320329A (en) * | 1942-08-06 | 1943-05-25 | Metallizing Engineering Co Inc | Spray metal coated, metal surfaced articles |
DE2300422C3 (en) * | 1973-01-05 | 1981-10-15 | Hoechst Ag, 6000 Frankfurt | Method of making an electrode |
JPS5137837A (en) * | 1974-09-27 | 1976-03-30 | Tokyo Metarikon Kk | HIMAKUKEISEIHO |
DE3106587C2 (en) * | 1981-02-21 | 1987-01-02 | Heraeus Elektroden GmbH, 6450 Hanau | Electrode and its use |
JPS60159199A (en) * | 1984-01-27 | 1985-08-20 | Plasma Giken Kogyo Kk | Lead dioxide electrode |
JPS63176453A (en) * | 1987-01-16 | 1988-07-20 | Dainippon Toryo Co Ltd | Production of thermally sprayed metal film |
DE3712684A1 (en) * | 1987-04-14 | 1988-10-27 | Castolin Sa | METHOD FOR PRODUCING A SPRAYED SURFACE WITH DEFINED ROUGHNESS, AND USE THEREOF |
JPH01150000A (en) * | 1987-12-07 | 1989-06-13 | Nippon Steel Corp | Insoluble anode for electroplating |
JPH01152294A (en) * | 1987-12-09 | 1989-06-14 | Nippon Mining Co Ltd | Production of material for insoluble anode |
JPH01177399A (en) * | 1988-01-07 | 1989-07-13 | Kawasaki Steel Corp | Pb-base insoluble anode for electroplating |
JPH02200799A (en) * | 1989-01-27 | 1990-08-09 | Kobe Steel Ltd | Insoluble electrode for electrolysis and cation electrodeposition coating method using this electrode |
GB8903322D0 (en) * | 1989-02-14 | 1989-04-05 | Ici Plc | Electrolytic process |
TW214570B (en) * | 1989-06-30 | 1993-10-11 | Eltech Systems Corp |
-
1991
- 1991-12-03 TW TW080109498A patent/TW197475B/zh active
- 1991-12-04 CA CA002056943A patent/CA2056943C/en not_active Expired - Fee Related
- 1991-12-11 MX MX9102511A patent/MX9102511A/en unknown
- 1991-12-20 AU AU89954/91A patent/AU643350B2/en not_active Ceased
- 1991-12-20 DK DK91810992.7T patent/DK0493326T3/en active
- 1991-12-20 ES ES91810992T patent/ES2104684T3/en not_active Expired - Lifetime
- 1991-12-20 EP EP91810992A patent/EP0493326B1/en not_active Expired - Lifetime
- 1991-12-20 AT AT91810992T patent/ATE154834T1/en not_active IP Right Cessation
- 1991-12-20 DE DE69126656T patent/DE69126656T2/en not_active Expired - Lifetime
- 1991-12-26 KR KR1019910024456A patent/KR100235378B1/en not_active IP Right Cessation
- 1991-12-26 JP JP3344634A patent/JP2825383B2/en not_active Expired - Lifetime
-
1997
- 1997-09-10 GR GR970402323T patent/GR3024677T3/en unknown
Also Published As
Publication number | Publication date |
---|---|
JPH04301062A (en) | 1992-10-23 |
DE69126656T2 (en) | 1998-01-02 |
KR920011628A (en) | 1992-07-24 |
DK0493326T3 (en) | 1997-12-29 |
AU643350B2 (en) | 1993-11-11 |
KR100235378B1 (en) | 1999-12-15 |
EP0493326B1 (en) | 1997-06-25 |
GR3024677T3 (en) | 1997-12-31 |
ES2104684T3 (en) | 1997-10-16 |
AU8995491A (en) | 1992-07-02 |
EP0493326A3 (en) | 1993-03-17 |
MX9102511A (en) | 1992-06-01 |
CA2056943C (en) | 1997-11-11 |
CA2056943A1 (en) | 1992-06-27 |
EP0493326A2 (en) | 1992-07-01 |
TW197475B (en) | 1993-01-01 |
ATE154834T1 (en) | 1997-07-15 |
DE69126656D1 (en) | 1997-07-31 |
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