EP0493326A2 - Substrate of improved melt sprayed surface morphology - Google Patents
Substrate of improved melt sprayed surface morphology Download PDFInfo
- Publication number
- EP0493326A2 EP0493326A2 EP91810992A EP91810992A EP0493326A2 EP 0493326 A2 EP0493326 A2 EP 0493326A2 EP 91810992 A EP91810992 A EP 91810992A EP 91810992 A EP91810992 A EP 91810992A EP 0493326 A2 EP0493326 A2 EP 0493326A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- article
- melt
- microinches
- micrometers
- 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
- 239000000758 substrate Substances 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 111
- 239000002184 metal Substances 0.000 claims abstract description 111
- 238000000576 coating method Methods 0.000 claims abstract description 69
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 22
- 150000002739 metals Chemical class 0.000 claims abstract description 16
- 238000007750 plasma spraying Methods 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 238000005530 etching Methods 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 14
- 230000003746 surface roughness Effects 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005363 electrowinning Methods 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- -1 platinum group metal oxides Chemical class 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- WZOZCAZYAWIWQO-UHFFFAOYSA-N [Ni].[Ni]=O Chemical compound [Ni].[Ni]=O WZOZCAZYAWIWQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating 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
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 238000007743 anodising Methods 0.000 claims 1
- 239000011195 cermet Substances 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- 239000012768 molten material Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000004140 cleaning Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005259 measurement Methods 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
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000011247 coating layer 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
- 238000005238 degreasing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 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
- 238000010285 flame spraying Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000132092 Aster Species 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 206010061619 Deformity Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910018974 Pt3O4 Inorganic materials 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
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 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
- 238000004873 anchoring Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 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
- 238000004845 hydriding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- IANUMTRPEYONHL-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) titanium(4+) Chemical compound [O-2].[Ti+4].[Ru+3] IANUMTRPEYONHL-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000010970 precious metal Substances 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
- 238000007761 roller coating Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000007751 thermal spraying Methods 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
- 238000004876 x-ray fluorescence Methods 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
Definitions
- a coating applied directly to a base metal is an electrocatalytic coating, often containing a precious metal from the platinum metal group, and applied directly onto a metal such as a valve metal.
- the metal may be simply cleaned to give a very smooth surface.
- Treatment with fluorine compounds may produce a smooth surface.
- Cleaning might include chemical degreasing, electrolytic degreasing or treatment with an oxidizing acid.
- Another procedure for anchoring the fresh coating to the substrate that has found utility in the application of an electrocatalytic coating to a valve metal, is to provide a porous oxide layer which can be formed on the base metal.
- titanium oxide can be flame or plasma sprayed onto substrate metal before application of electrochemically active substance, as disclosed in U.S. Patent No. 4,140,813.
- the thermally sprayed material may consist of a metal oxide or nitride or so forth, to which electrocatalytically active particles have been pre-applied, as taught in U.S. Patent No. 4,392,927.
- the coated metal substrate can have highly desirable extended lifetime even in most rigorous industrial environments.
- the invention can provide for well anchored coatings of uniform planarity, even when utilizing gouged and similarly disfigured substrate metal.
- the invention is directed to a metallic article of a substrate having a metal-containing surface adapted for enhanced coating adhesion, such surface comprising a plasma spray applied valve metal surface on said substrate, which plasma spray applied surface provides a profilometer-measured average surface roughness of at least about 250 microinches and an average surface peaks per inch of at least about 40, basis a profilometer upper threshold limit of 400 microinches and a profilometer lower threshold limit of 300 microinches.
- the invention is directed to the method of preparing a plasma metal surface for enhanced coating adhesion which surface has been gouged and thereby exhibits loss of planarity, which method comprises:
- the invention is directed to a cell for electrolysis having at least one electrode of a metal article as further defined herein.
- the metal articles are electrocatalytically coated and used as oxygen evolving electrodes, even under the rigorous commercial operations including continuous electrogalvanizing, electrotinning, copper foil plating, electroforming or electrowinning, and including sodium sulfate electrolysis such electrodes can have highly desirable service life.
- the invention is also directed to such metal articles as are utilized as electrodes.
- the metals of the substrate are broadly contemplated to be any coatable metal.
- the substrate metals might be such as nickel or manganese, but will most always be valve metals, including titanium, tantalum, aluminum, zirconium and niobium. Of particular interest for its ruggedness, corrosion resistance and availability is titanium.
- the suitable metals of the substrate can include metal alloys and intermetallic mixtures, as well as ceramics and cermets such as contain one or more valve metals.
- titanium may be alloyed with nickel, cobalt, iron, manganese or copper.
- Grade 5 titanium may include up to 6.75 weight% aluminum and 4.5 weight% vanadium, grade 6 up to 6% aluminum and 3% tin, grade 7 up to 0.25 weight% palladium, grade 10, from 10 to 13 weight% molybdenum plus 4.5 to 7.5 weight% zirconium and so on.
- metals in their normally available condition, i.e., having minor amounts of impurities.
- metal of particular interest i.e., titanium
- various grades of the metal are available including those in which other constituents may be alloys or alloys plus impurities. Grades of titanium have been more specifically set forth in the standard specifications for titanium detailed in ASTM B 265-79.
- the substrate metal advantageously is a cleaned surface. This may be obtained by any of the treatments used to achieve a clean metal surface, but with the provision that unless called for to remove an old coating, and if etching might be employed, as more specifically detailed hereinbelow, mechanical cleaning is typically minimized. Thus the usual cleaning procedures of degreasing, either chemical or electrolytic, or other chemical cleaning operation may be used to advantage.
- plasma spraying the metal is melted and sprayed in a plasma stream generated by heating with an electric arc to high temperatures an inert gas, such as argon or nitrogen, optionally containing a minor amount of hydrogen.
- inert gas such as argon or nitrogen
- the spraying parameters such as the volume and temperature of the flame or plasma spraying stream, the spraying distance, the feed rate of particulate metal constituents and the like, are chosen so that the particulate metal components are melted by and in the spray stream and deposited on the metal substrate while still substantially in melted form so as to provide an essentially continuous coating (i.e. one in which the sprayed particles are not discernible) having a foraminous structure.
- spray parameters like those used in the examples give satisfactory coatings.
- the metal substrate during melt spraying is maintained near ambient temperature. This may be achieved by means such as streams of air impinging on the substrate during spraying or allowing the substrate to air cool between spray passes.
- the particulate metal employed e.g., titanium powder
- Particulate metals having different particle sizes should be equally suitable so long as they are readily plasma spray applied.
- the metallic constituency of the particulates may be as above-described for the metals of the substrate, e.g., the titanium might be one of several grades most usually grade 1 titanium. It is also contemplated that mixtures may be applied, e.g., mixtures of metals or of metals with other subsituents, which can include metal oxides, for example a predominant amount of metal with a minor amount of other substituents.
- plasma spray applications may be used in combination with etching of the substrate metal surface, with each treatment most always being applied to different portions of a surface. If etching is used, it is important to aggressively etch the metal surface to provide deep grain boundaries and well exposed, three-dimensional grains. It is preferred that such operation will etch impurities located at such grain boundaries.
- the metal article can be disfigured and can have lost surface planarity.
- disfiguring will be in nicks and gouges of the surface.
- all such surface disfigurement, including nicks, scrapes, and gouges, and burns where metal may actually be melted and resolidify will generally be referred to herein simply as "gouges.”
- gouges may or may not be filled with a metal filling. If the overall surface were to be subsequently etched before recoating, the filled zones can be expected to yield poor etch results.
- gouging of the substrate may be extensive, or the substrate from its heat history and/or chemistry may not achieve desirable results in etching. It may, therefore, be especially desirable to simply plasma spray the entire surface which can overcome these substrate deficiencies. It is also contemplated that it may be useful to combine plasma spray application with etching in some situations.
- gouges and the like may be filled by plasma spray technique. Usually, the areas of the surface which are not disfigured will first be etched, then the planar, etched areas can be masked, and the gouges remaining will be filled and/or surface treated by plasma spray application. That is, plasma spray can be used to fill and reactivate a gouge, or it simply can be used to just reactivate gouges without necessarily restoring surface planarity. By reactivation is meant the plasma spray application to prepare the gouge for subsequent treatment. Hence, the entire surface will have the needed roughness for coating, and if desired it may in the same processing be refurbished to desirable planarity.
- the heat treatment history of the metal can be important.
- a metal such as titanium for etching
- annealing proper annealing of grade 1 titanium will enhance the concentration of the iron impurity at grain boundaries.
- the suitable preparation includes annealing, and the metal is grade 1 titanium
- the titanium can be annealed at a temperature of at least about 500°C. for a time of at least about 15 minutes.
- a more elevated annealing temperature e.g., 600°-800°C. is advantageous.
- etching it will be with a sufficiently active etch solution to develop aggressive grain boundary attack.
- Typical etch solutions are acidic solutions. These can be provided by hydrochloric, sulfuric, perchloric, nitric, oxalic, tartaric, and phosphoric acids as well as mixtures thereof, e.g., aqua regia.
- Other etchants that may be utilized include caustic etchants such as a solution of potassium hydroxide/hydrogen peroxide in combination, or a melt of potassium hydroxide with potassium nitrate.
- the etch solution is advantageously a strong, or concentrated solution, such as an 18-22 weight% solution of hydrochloric acid.
- the solution is advantageously maintained during etching at elevated temperature such as at 80°C. or more for aqueous solutions, and often at or near boiling condition or greater, e.g., under refluxing condition.
- elevated temperature such as at 80°C. or more for aqueous solutions, and often at or near boiling condition or greater, e.g., under refluxing condition.
- the etched metal surface can then be subjected to rinsing and drying steps to prepare the surface for coating.
- the metal surface For the plasma spray applied surface roughness, it is necessary that the metal surface have an average roughness (Ra) of at least about 250 microinches and an average number of surface peaks per inch (Nr) of at least about 40.
- the surface peaks per inch can be typically measured at a lower threshold limit of 300 microinches and an upper threshold limit of 400 microinches.
- a surface having an average roughness of below about 250 microinches will be undesirably smooth, as will a surface having an average number of surface peaks per inch of below about 40, for providing the needed, substantially enhanced, coating adhesion.
- the surface will have an average roughness of on the order of about 400 microinches or more, e.g., ranging up to about 750-1500 microinches, with no low spots of less than about 200 microinches.
- the surface will be free from low spots that are less than about 210 to 220 microinches. It is preferable that the surface have an average roughness of from about 300 to about 500 microinches.
- the surface has an average number of peaks per inch of at least about 60, but which might be on the order of as great as about 130 or more, with an average from about 80 to about 120 being preferred.
- the surface prefferably has an average distance between the maximum peak and the maximum valley (Rm) of at least about 1,000 microinches and to have an average peak height (Rz) of at least about 1,000 microinches. All of such foregoing surface characteristics are as measured by a profilometer. More desirably, the surface for coating will have an Rm value of at least about 1,500 microinches to about 3500 microinches and have a maximum valley characteristic of at least about 1,500 microinches up to about 3500 microinches.
- the surface may then proceed through various operations, including pretreatment before coating.
- the surface may be subjected to a cleaning operation, e.g., a solvent wash.
- a subsequent etching or hydriding or nitriding treatment Prior to coating with an electrochemically active material, it has been proposed to provide an oxide layer by heating the substrate in air or by anodic oxidation of the substrate as described in U.S. Patent No. 3,234,110.
- European patent application No. 0,090,425 proposes to platinum electroplate the substrate to which then an oxide of ruthenium, palladium or iridium is chemideposited.
- electrochemically active coatings that may then be applied to the etched surface of the metal, are those provided from platinum or other platinum group metals or they can be represented by active oxide coatings such as platinum group metal oxides, magnetite , ferrite, cobalt spinel or mixed metal oxide coatings.
- active oxide coatings such as platinum group metal oxides, magnetite , ferrite, cobalt spinel or mixed metal oxide coatings.
- Such coatings have typically been developed for use as anode coatings in the industrial electrochemical industry. They may be water based or solvent based, e.g., using alcohol solvent. Suitable coatings of this type have been generally described in one or more of the U.S. Patent Nos. 3,265,526, 3,632,498, 3,711,385 and 4,528,084.
- the mixed metal oxide coatings can often include at least one oxide of a valve metal with an oxide of a platinum group metal including platinum, palladium, rhodium, iridium and ruthenium or mixtures of themselves and with other metals.
- Further coatings in addition to those enumerated above include manganese dioxide, lead dioxide, platinate coatings such as M x Pt3O4 where M is an alkali metal and X is typically targeted at approximately 0.5, nickel-nickel oxide and nickel plus lanthanide oxides.
- coatings will be applied to the metal by any of those means which are useful for applying a liquid coating composition to a metal substrate. Such methods include dip spin and dip drain techniques, brush application, roller coating and spray application such as electrostatic spray. Moreover spray application and combination techniques, e.g., dip drain with spray application can be utilized. With the above-mentioned coating compositions for providing an electrochemically active coating, a modified dip drain operation can be most serviceable. Following any of the foregoing coating procedures, upon removal from the liquid coating composition, the coated metal surface may simply dip drain or be subjected to other post coating technique such as forced air drying.
- Typical curing conditions for electrocatalytic coatings can include cure temperatures of from about 300°C. up to about 600°C. Curing times may vary from only a few minutes for each coating layer up to an hour or more, e.g., a longer cure time after several coating layers have been applied. However, cure procedures duplicating annealing conditions of elevated temperature plus prolonged exposure to such elevated temperature, are generally avoided for economy of operation.
- the curing technique employed can be any of those that may be used for curing a coating on a metal substrate.
- oven curing including conveyor ovens may be utilized.
- infrared cure techniques can be useful.
- oven curing is used and the cure temperature used for electrocatalytic coatings will be within the range of from about 450°C. to about 550°C. At such temperatures, curing times of only a few minutes, e.g., from about 3 to 10 minutes, will most always be used for each applied coating layer.
- a titanium nut is welded to the back of each sample plate having an approximate 7.5 cm2 sample face and each being unalloyed grade 1 titanium.
- the sample plates were then mounted to a large back plate to provide a mosaic of sample plates. This mounting scheme served to provide a large array of sample plates which could be handled as a unit in ensuing operations.
- the sample plates were grit blasted with aluminum oxide, then rinsed in acetone and dried.
- a coating on the sample plates of titanium powder was produced using a powder having average particle size of 50 - 60 microns.
- the sample plates were coated with this powder using a Metco plasma spray gun equipped with a GH spray nozzle.
- the spraying conditions were: a current of 500 amps; a voltage of 45 - 50 volts; a plasma gas consisting of argon and helium; a titanium feed rate of 3 pounds per hour; a spray bandwidth of 6.7 millimeters (mm); and a spraying distance of 64 mm, with the resulting titanium layer on the titanium sample plates having a thickness of about 150 microns.
- the coated surface of the sample plates were then subjected to surface profilometer measurement using a Hommel model T1000 C instrument manufactured by Hommelwerk GmbH.
- the plate surface profilometer measurements were determined as average values computed from three separate measurements conducted by running the instrument in random orientation across the coated flat face of the plate. This gave average values as measured on three sample plates for surface roughness (Ra) of 448, 490 and 548 microinches, respectively for the three plates, and peaks per inch (Nr) of 76, 63 and 76, respectively for the three plates.
- the peaks per inch were measured within the threshold limits of 300 microinches (lower) and 400 microinches (upper).
- the sample then received a coating of plasma spray applied titanium using the titanium powder and the application procedure as described in Example 1. Under profilometer measurement conducted in the manner of Example 1, the resulting average values for a flat surface of the sample were found to be 650 (Ra) and 69 (Nr).
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Abstract
Description
- The adhesion of coatings applied directly to the surface of a substrate metal is of special concern when the coated metal will be utilized in a rigorous industrial environment. Careful attention is usually paid to surface treatment and pre-treatment operation prior to coating. Achievement particularly of a clean surface is a priority sought in such treatment or pre-treatment operation.
- Representative of a coating applied directly to a base metal is an electrocatalytic coating, often containing a precious metal from the platinum metal group, and applied directly onto a metal such as a valve metal. Within this technical area of electrocatalytic coatings applied to a base metal, the metal may be simply cleaned to give a very smooth surface. U.S. Patent No, 4,797,182. Treatment with fluorine compounds may produce a smooth surface. U.S. Patent No. 3,864,163. Cleaning might include chemical degreasing, electrolytic degreasing or treatment with an oxidizing acid. U.S. Patent 3,864,163.
- Cleaning can be followed by mechanical roughening to prepare a surface for coating. U.S. Patent No, 3,778,307. If the mechanical treatment is sandblasting, such may be followed by etching. U.S. Patent No. 3,878,083. Or such may be followed by flame spray application of a fine-particled mixture of metal powders. U.S. Patent No. 4,849,085.
- Another procedure for anchoring the fresh coating to the substrate, that has found utility in the application of an electrocatalytic coating to a valve metal, is to provide a porous oxide layer which can be formed on the base metal. For example, titanium oxide can be flame or plasma sprayed onto substrate metal before application of electrochemically active substance, as disclosed in U.S. Patent No. 4,140,813. Or the thermally sprayed material may consist of a metal oxide or nitride or so forth, to which electrocatalytically active particles have been pre-applied, as taught in U.S. Patent No. 4,392,927.
- It has however been found difficult to provide long-lived coated metal articles for serving in the most rugged commercial environments, e.g., oxygen evolving anodes for use in the present-day commercial applications utilized in electrogalvanizing, electrotinning, electroforming or electrowinning. Such may be continuous operation. They can involve severe conditions including potential surface damage. It would be most desirable to provide coated metal substrates to serve as electrodes in such operations, exhibiting extended stable operation while preserving excellent coating adhesion. It would also be highly desirable to provide such an electrode not only from fresh metal but also from recoated metal.
- There has now been found a metal surface which provides a locked on coating of excellent coating adhesion. The coated metal substrate can have highly desirable extended lifetime even in most rigorous industrial environments. For the electrocatalytic coatings, the invention can provide for well anchored coatings of uniform planarity, even when utilizing gouged and similarly disfigured substrate metal.
- In one aspect, the invention is directed to a metallic article of a substrate having a metal-containing surface adapted for enhanced coating adhesion, such surface comprising a plasma spray applied valve metal surface on said substrate, which plasma spray applied surface provides a profilometer-measured average surface roughness of at least about 250 microinches and an average surface peaks per inch of at least about 40, basis a profilometer upper threshold limit of 400 microinches and a profilometer lower threshold limit of 300 microinches.
- In another aspect, the invention is directed to the method of preparing a plasma metal surface for enhanced coating adhesion which surface has been gouged and thereby exhibits loss of planarity, which method comprises:
- Plasma spraying the gouges of such surface with a valve metal to establish metal surface planarity, and then plasma spraying the surface to be coated, including the plasma sprayed gouges to provide a surface roughness of enhanced coating adhesion.
- In a still further aspect, the invention is directed to a cell for electrolysis having at least one electrode of a metal article as further defined herein. When the metal articles are electrocatalytically coated and used as oxygen evolving electrodes, even under the rigorous commercial operations including continuous electrogalvanizing, electrotinning, copper foil plating, electroforming or electrowinning, and including sodium sulfate electrolysis such electrodes can have highly desirable service life. Thus the invention is also directed to such metal articles as are utilized as electrodes.
- The metals of the substrate are broadly contemplated to be any coatable metal. For the particular application of an electrocatalytic coating, the substrate metals might be such as nickel or manganese, but will most always be valve metals, including titanium, tantalum, aluminum, zirconium and niobium. Of particular interest for its ruggedness, corrosion resistance and availability is titanium. As well as the normally available elemental metals themselves, the suitable metals of the substrate can include metal alloys and intermetallic mixtures, as well as ceramics and cermets such as contain one or more valve metals. For example, titanium may be alloyed with nickel, cobalt, iron, manganese or copper. More specifically, Grade 5 titanium may include up to 6.75 weight% aluminum and 4.5 weight% vanadium, grade 6 up to 6% aluminum and 3% tin, grade 7 up to 0.25 weight% palladium, grade 10, from 10 to 13 weight% molybdenum plus 4.5 to 7.5 weight% zirconium and so on.
- By use of elemental metals, alloys and intermetallic mixtures, it is most particularly meant the metals in their normally available condition, i.e., having minor amounts of impurities. Thus for the metal of particular interest, i.e., titanium, various grades of the metal are available including those in which other constituents may be alloys or alloys plus impurities. Grades of titanium have been more specifically set forth in the standard specifications for titanium detailed in ASTM B 265-79.
- Regardless of the metal selected and how the metal surface is subsequently processed, the substrate metal advantageously is a cleaned surface. This may be obtained by any of the treatments used to achieve a clean metal surface, but with the provision that unless called for to remove an old coating, and if etching might be employed, as more specifically detailed hereinbelow, mechanical cleaning is typically minimized. Thus the usual cleaning procedures of degreasing, either chemical or electrolytic, or other chemical cleaning operation may be used to advantage.
- Where an old coating is present on the metal surface, such needs to be addressed before recoating. It is preferred for best extended performance when the finished article will be used with an electrocatalytic coating, such as use as an oxygen evolving electrode, to remove the old coating. In the technical area of the invention which pertains to electrochemically active coatings on a valve metal, chemical means for coating removal are well known. Thus a melt of essentially basic material, followed by an initial pickling will suitably reconstitute the metal surface, as taught in U.S. Patent No. 3,573,100. Or a melt of alkali metal hydroxide containing alkali metal hydride, which may be followed by a mineral acid treatment, is useful, as described in U.S. Patent No. 3,706,600. Usual rinsing and drying steps can also form a portion of these operations.
- When a cleaned surface, or prepared and cleaned surface has been obtained, and particularly for later applying an electrocatalytic coating to a valve metal in the practice of the present invention, surface roughness is then obtained. This will be achieved by means which include plasma spray application, usually of particulate valve metal, most especially titanium powder. However, as described hereinbelow, although the metal will be applied in particulate form, the feed metal, i.e., the metal to be applied, may be in different form such as wire form. This should be understood even though for convenience, application will typically be discussed as metal applied in particulate form. In this plasma spraying, the metal is melted and sprayed in a plasma stream generated by heating with an electric arc to high temperatures an inert gas, such as argon or nitrogen, optionally containing a minor amount of hydrogen. It is to be understood by the use herein of the term "plasma spraying" that although plasma spraying is preferred the term is meant to include generally thermal spraying such as magnetohydrodynamic spraying, flame spraying and arc spraying, generally referred to as melt spraying.
- The spraying parameters, such as the volume and temperature of the flame or plasma spraying stream, the spraying distance, the feed rate of particulate metal constituents and the like, are chosen so that the particulate metal components are melted by and in the spray stream and deposited on the metal substrate while still substantially in melted form so as to provide an essentially continuous coating (i.e. one in which the sprayed particles are not discernible) having a foraminous structure. Typically, spray parameters like those used in the examples give satisfactory coatings. Usually, the metal substrate during melt spraying is maintained near ambient temperature. This may be achieved by means such as streams of air impinging on the substrate during spraying or allowing the substrate to air cool between spray passes.
- The particulate metal employed, e.g., titanium powder, has a typical particle size range of 20 - 100 microns, and preferably has all particles within the range of 40 - 80 microns for efficient preparation of surface roughness. Particulate metals having different particle sizes should be equally suitable so long as they are readily plasma spray applied. The metallic constituency of the particulates may be as above-described for the metals of the substrate, e.g., the titanium might be one of several grades most usually grade 1 titanium. It is also contemplated that mixtures may be applied, e.g., mixtures of metals or of metals with other subsituents, which can include metal oxides, for example a predominant amount of metal with a minor amount of other substituents.
- It is also contemplated that such plasma spray applications may be used in combination with etching of the substrate metal surface, with each treatment most always being applied to different portions of a surface. If etching is used, it is important to aggressively etch the metal surface to provide deep grain boundaries and well exposed, three-dimensional grains. It is preferred that such operation will etch impurities located at such grain boundaries.
- Particularly where an old coating has been present and the coated substrate has been in use, e.g., as an anode in electrogalvanizing, the metal article can be disfigured and can have lost surface planarity. Typically, such disfiguring will be in nicks and gouges of the surface. For convenience, all such surface disfigurement, including nicks, scrapes, and gouges, and burns where metal may actually be melted and resolidify, will generally be referred to herein simply as "gouges." These may or may not be filled with a metal filling. If the overall surface were to be subsequently etched before recoating, the filled zones can be expected to yield poor etch results. Also, gouging of the substrate may be extensive, or the substrate from its heat history and/or chemistry may not achieve desirable results in etching. It may, therefore, be especially desirable to simply plasma spray the entire surface which can overcome these substrate deficiencies. It is also contemplated that it may be useful to combine plasma spray application with etching in some situations. Thus, gouges and the like may be filled by plasma spray technique. Usually, the areas of the surface which are not disfigured will first be etched, then the planar, etched areas can be masked, and the gouges remaining will be filled and/or surface treated by plasma spray application. That is, plasma spray can be used to fill and reactivate a gouge, or it simply can be used to just reactivate gouges without necessarily restoring surface planarity. By reactivation is meant the plasma spray application to prepare the gouge for subsequent treatment. Hence, the entire surface will have the needed roughness for coating, and if desired it may in the same processing be refurbished to desirable planarity.
- When etching is utilized the heat treatment history of the metal can be important. For example, to prepare a metal such as titanium for etching, it can be most useful to condition the metal, as by annealing, to diffuse impurities to the grain boundaries. Thus, by way of example, proper annealing of grade 1 titanium will enhance the concentration of the iron impurity at grain boundaries. Where the suitable preparation includes annealing, and the metal is grade 1 titanium, the titanium can be annealed at a temperature of at least about 500°C. for a time of at least about 15 minutes. For efficiency of operation, a more elevated annealing temperature, e.g., 600°-800°C. is advantageous.
- Where etching is employed, it will be with a sufficiently active etch solution to develop aggressive grain boundary attack. Typical etch solutions are acidic solutions. These can be provided by hydrochloric, sulfuric, perchloric, nitric, oxalic, tartaric, and phosphoric acids as well as mixtures thereof, e.g., aqua regia. Other etchants that may be utilized include caustic etchants such as a solution of potassium hydroxide/hydrogen peroxide in combination, or a melt of potassium hydroxide with potassium nitrate. For efficiency of operation, the etch solution is advantageously a strong, or concentrated solution, such as an 18-22 weight% solution of hydrochloric acid. Moreover, the solution is advantageously maintained during etching at elevated temperature such as at 80°C. or more for aqueous solutions, and often at or near boiling condition or greater, e.g., under refluxing condition. Following etching, the etched metal surface can then be subjected to rinsing and drying steps to prepare the surface for coating. A more detailed discussion of the etching and annealing can be found in EP-A-0 407 349, the disclosure of which is incorporated herein by reference.
- For the plasma spray applied surface roughness, it is necessary that the metal surface have an average roughness (Ra) of at least about 250 microinches and an average number of surface peaks per inch (Nr) of at least about 40. The surface peaks per inch can be typically measured at a lower threshold limit of 300 microinches and an upper threshold limit of 400 microinches. A surface having an average roughness of below about 250 microinches will be undesirably smooth, as will a surface having an average number of surface peaks per inch of below about 40, for providing the needed, substantially enhanced, coating adhesion. Advantageously, the surface will have an average roughness of on the order of about 400 microinches or more, e.g., ranging up to about 750-1500 microinches, with no low spots of less than about 200 microinches. Advantageously, for best avoidance of surface smoothness, the surface will be free from low spots that are less than about 210 to 220 microinches. It is preferable that the surface have an average roughness of from about 300 to about 500 microinches. Advantageously, the surface has an average number of peaks per inch of at least about 60, but which might be on the order of as great as about 130 or more, with an average from about 80 to about 120 being preferred. It is further advantageous for the surface to have an average distance between the maximum peak and the maximum valley (Rm) of at least about 1,000 microinches and to have an average peak height (Rz) of at least about 1,000 microinches. All of such foregoing surface characteristics are as measured by a profilometer. More desirably, the surface for coating will have an Rm value of at least about 1,500 microinches to about 3500 microinches and have a maximum valley characteristic of at least about 1,500 microinches up to about 3500 microinches.
- After the substrate has attained the necessary surface roughness, it will be understood that the surface may then proceed through various operations, including pretreatment before coating. For example, the surface may be subjected to a cleaning operation, e.g., a solvent wash. Or it may be subjected to a subsequent etching or hydriding or nitriding treatment. Prior to coating with an electrochemically active material, it has been proposed to provide an oxide layer by heating the substrate in air or by anodic oxidation of the substrate as described in U.S. Patent No. 3,234,110. European patent application No. 0,090,425 proposes to platinum electroplate the substrate to which then an oxide of ruthenium, palladium or iridium is chemideposited. Various proposals have also been made in which an outer layer of electrochemically active material is deposited on a sub-layer which primarily serves as a protective and conductive intermediate. U.K. Patent No. 1,344,540 discloses utilizing and electrodeposited layer of cobalt or lead oxide under a ruthenium-titanium oxide or similar active outer layer. Various tin oxide based underlayers are disclosed in U.S. Patents No, 4,272,354, 3,882,002 and 3,950,240. After providing the necessary surface roughness followed by any pretreatment operation, the coating most contemplated in the present invention is the application of electrochemically active coating.
- As representative of the electrochemically active coatings that may then be applied to the etched surface of the metal, are those provided from platinum or other platinum group metals or they can be represented by active oxide coatings such as platinum group metal oxides, magnetite , ferrite, cobalt spinel or mixed metal oxide coatings. Such coatings have typically been developed for use as anode coatings in the industrial electrochemical industry. They may be water based or solvent based, e.g., using alcohol solvent. Suitable coatings of this type have been generally described in one or more of the U.S. Patent Nos. 3,265,526, 3,632,498, 3,711,385 and 4,528,084. The mixed metal oxide coatings can often include at least one oxide of a valve metal with an oxide of a platinum group metal including platinum, palladium, rhodium, iridium and ruthenium or mixtures of themselves and with other metals. Further coatings in addition to those enumerated above include manganese dioxide, lead dioxide, platinate coatings such as MxPt₃O₄ where M is an alkali metal and X is typically targeted at approximately 0.5, nickel-nickel oxide and nickel plus lanthanide oxides.
- It is contemplated that coatings will be applied to the metal by any of those means which are useful for applying a liquid coating composition to a metal substrate. Such methods include dip spin and dip drain techniques, brush application, roller coating and spray application such as electrostatic spray. Moreover spray application and combination techniques, e.g., dip drain with spray application can be utilized. With the above-mentioned coating compositions for providing an electrochemically active coating, a modified dip drain operation can be most serviceable. Following any of the foregoing coating procedures, upon removal from the liquid coating composition, the coated metal surface may simply dip drain or be subjected to other post coating technique such as forced air drying.
- Typical curing conditions for electrocatalytic coatings can include cure temperatures of from about 300°C. up to about 600°C. Curing times may vary from only a few minutes for each coating layer up to an hour or more, e.g., a longer cure time after several coating layers have been applied. However, cure procedures duplicating annealing conditions of elevated temperature plus prolonged exposure to such elevated temperature, are generally avoided for economy of operation. In general, the curing technique employed can be any of those that may be used for curing a coating on a metal substrate. Thus, oven curing, including conveyor ovens may be utilized. Moreover, infrared cure techniques can be useful. Preferably for most economical curing, oven curing is used and the cure temperature used for electrocatalytic coatings will be within the range of from about 450°C. to about 550°C. At such temperatures, curing times of only a few minutes, e.g., from about 3 to 10 minutes, will most always be used for each applied coating layer.
- The following examples show ways in which the invention has been practiced, as well as showing comparative examples. However, the examples showing ways in which the invention has been practiced should not be construed as limiting the invention.
- A titanium nut is welded to the back of each sample plate having an approximate 7.5 cm² sample face and each being unalloyed grade 1 titanium. The sample plates were then mounted to a large back plate to provide a mosaic of sample plates. This mounting scheme served to provide a large array of sample plates which could be handled as a unit in ensuing operations. The sample plates were grit blasted with aluminum oxide, then rinsed in acetone and dried.
- A coating on the sample plates of titanium powder was produced using a powder having average particle size of 50 - 60 microns. The sample plates were coated with this powder using a Metco plasma spray gun equipped with a GH spray nozzle. The spraying conditions were: a current of 500 amps; a voltage of 45 - 50 volts; a plasma gas consisting of argon and helium; a titanium feed rate of 3 pounds per hour; a spray bandwidth of 6.7 millimeters (mm); and a spraying distance of 64 mm, with the resulting titanium layer on the titanium sample plates having a thickness of about 150 microns.
- The coated surface of the sample plates were then subjected to surface profilometer measurement using a Hommel model T1000 C instrument manufactured by Hommelwerk GmbH. The plate surface profilometer measurements were determined as average values computed from three separate measurements conducted by running the instrument in random orientation across the coated flat face of the plate. This gave average values as measured on three sample plates for surface roughness (Ra) of 448, 490 and 548 microinches, respectively for the three plates, and peaks per inch (Nr) of 76, 63 and 76, respectively for the three plates. The peaks per inch were measured within the threshold limits of 300 microinches (lower) and 400 microinches (upper).
- A sample of titanium which had been previously coated with an electrochemically active coating, was blasted with alumina powder to remove the previous coating. By this abrasive method, it was determined by X-ray fluorescence that the previous coating had been removed. Aster removal of any residue of the abrasive treatment, the resulting sample plate was etched. It was etched for approximately 1 hours by immersion in 20 weight percent hydrochloric acid aqueous solution heated to 95°C. After removal from the hot hydrochloric acid, the plate was again rinsed with deionized water and air dried. Under profilometer measurement conducted in the manner of Example 1, the resulting average values for a flat face surface of the sample were found to be 180 (Ra) and 31 (Nr).
- The sample then received a coating of plasma spray applied titanium using the titanium powder and the application procedure as described in Example 1. Under profilometer measurement conducted in the manner of Example 1, the resulting average values for a flat surface of the sample were found to be 650 (Ra) and 69 (Nr).
Claims (24)
- A metallic article comprising a substrate having a metal-containing surface adapted for enhanced coating adhesion, said surface comprising a melt spray applied valve metal surface on the substrate, which surface is applied by melt spraying valve metal particles having a size within the range from 20 to 100 micrometers and has a profilometer-measured average surface roughness of at least about 250 microinches (about 635 micrometers) and an average surface peaks per inch of at least about 40 (about 15.15 peaks per cm), basis a profilometer upper threshold limit of 400 microinches (about 1016 micrometers) and a profilometer lower threshold limit of 300 microinches (about 762 micrometers).
- The article of claim 1, wherein the substrate comprises a valve metal as one or more of a metal, alloy, intermetallic mixture, ceramic or cermet.
- The article of claim 1 or 2, wherein the melt-sprayed metal of said surface is selected from the metals, alloys, and intermetallic mixtures of titanium, tantalum, niobium, aluminium, zirconium, manganese and nickel.
- The article of claim 3, wherein said metal surface has a profilometer-measured average roughness of at least about 300 microinches (about 762 micrometers) with no low spots of less than about 210 microinches (about 533 micrometers).
- The article of any preceding claim, wherein said surface has a profilometer-measured average surface peaks per inch of at least about 60 (about 23.6 peaks per cm), basis an upper threshold limit of 400 microinches (about 1016 micrometers) and a lower threshold limit of 300 microinches (about 762 micrometers).
- The article of any preceding claim, wherein said surface has profilometer-measured average distance between the maximum peak and the maximum valley of at least about 1000 microinches (about 2540 micrometers).
- The article of claim 6, wherein said surface has profilometer-measured average distance between the maximum peak and the maximum valley of from about 1500 microinches (about 3810 micrometers) to about 3500 microinches (about 8890 micrometers).
- The method of any preceding claim, wherein said surface has a profilometer-measured average peaks height of at least about 1000 microinches (about 2450 micrometers).
- The article of claim 8, wherein said surface has a profilometer-measured average peaks height of from at least about 1500 microinches (about 3810 micrometers) up to about 3500 microinches (about 8890 micrometers).
- The article of any preceding claim, wherein said surface is coated.
- The article of claim 10, wherein said coated surface has an electrochemically active surface coating containing a platinum group metal, or a metal oxide or their mixtures, in particular a mixed crystal material of at least one oxide of a valve metal and at least one oxide of a platinum group metal.
- The article of claim 10, wherein said electrochemically active surface coating contains at least one oxide selected from the platinum group metal oxides, magnetite, ferrite, and cobalt oxide spinel, manganese dioxide, lead dioxide, tin oxide, platinate substituent, nickel-nickel oxide and nickel plus lanthanide oxides.
- The article of any preceding claim, which is an electrode for electrochemical processes, especially an oxygen-evolving anode.
- The article of claim 13, which is an anode in anodizing, electroplating or electrowinning cell.
- The article of claim 13, which is an anode in electrogalvanizing, electrotinning, sodium sulfate electrolysis or copper foil plating.
- A method of producing the article of any one of claims 1 to 15, comprising melt spraying valve metal particles having a size within the range from 20 to 100 micrometers, preferably by plasma spraying.
- The method of preparing a planar metal surface for enhanced coating adhesion, which surface has been gouged and thereby exhibits loss of planarity, which method comprises :a) melt spraying the gouges of said surface with a valve metal, preferably by plasma spraying, to establish metal surface planarity, and thenb) melt spraying the surface to be coated, including the melt sprayed gouges, preferably with the same valve metal as before and preferably by plasma spraying, to provide a surface roughness of enhanced coating adhesion.
- The method of claim 17, wherein said gouges are first partially filled with weld material and then melt sprayed with valve metal.
- The method of claim 17 or 18, wherein said gouges are first milled to provide milled gouges for melt spray applied metal.
- The method of preparing a surface of a coated metal in planar shape for recoating, which surface has been gouged in use and exhibits loss of planarity, which method comprises :a) subjecting said coated metal surface to a melt containing molten material for removing said coating, preferably by dipping the coated metal surface in said melt;b) separating said metal surface from said melt, cooling same and removing melt residue therefrom;c) etching intergranularly the surface at an elevated temperature and with a strong acid or caustic etchant;d) washing said etched surface exposing said gouges; ande) melt spraying the gouges of said surface with a valve metal, preferably by plasma spraying, to establish metal surface planarity and provide surface roughness; andf) whereby said surface has surface planarity plus surface roughness for enhanced coating adhesion and said surface roughness is established by both intergranular etching and plasma spraying.
- The method of claim 20, wherein said surface separated from said coating-removal melt is subjected to elevated temperature annealing for a time sufficient to provide an at least substantially continuous intergranular network of impurities, including impurities at the surface of said metal.
- The method of claim 20 or 21, wherein said gouges are first partially filled with weld material and then melt sprayed with valve metal, preferably by plasma spraying.
- The method of claim 22, wherein said gouges are first milled to provide milled gouges for melt-spray applied valve metal.
- A cell for the electrolysis of a dissolved species contained in a bath of said cell and having an anode immersed in said bath, which cell has an anode as defined in claim 14.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63391490A | 1990-12-26 | 1990-12-26 | |
US633914 | 1990-12-26 |
Publications (3)
Publication Number | Publication Date |
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EP0493326A2 true EP0493326A2 (en) | 1992-07-01 |
EP0493326A3 EP0493326A3 (en) | 1993-03-17 |
EP0493326B1 EP0493326B1 (en) | 1997-06-25 |
Family
ID=24541661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91810992A Expired - Lifetime EP0493326B1 (en) | 1990-12-26 | 1991-12-20 | Substrate of improved melt sprayed surface morphology |
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) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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AU657248B2 (en) * | 1992-06-25 | 1995-03-02 | Eltech Systems Corporation | Electrodes of improved service life |
WO1997017478A1 (en) * | 1995-11-08 | 1997-05-15 | Fissler Gmbh | Process for producing a non-stick coating and objects provided with such a coating |
US8632836B2 (en) | 2007-07-09 | 2014-01-21 | Astra Tech Ab | Nanosurface |
CN104073842A (en) * | 2011-10-13 | 2014-10-01 | 金川集团有限公司 | Negative plate used for electrodepositing electrolyzing nickel |
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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 |
CA2627605A1 (en) * | 2005-09-20 | 2007-03-29 | Kudu Industries Inc. | 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 |
ITMI20102354A1 (en) * | 2010-12-22 | 2012-06-23 | Industrie De Nora Spa | ELECTRODE FOR ELECTROLYTIC CELL |
EP2862960B1 (en) | 2012-06-18 | 2020-03-04 | Asahi Kasei Kabushiki Kaisha | Bipolar alkaline water electrolysis unit |
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 |
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- 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 AT AT91810992T patent/ATE154834T1/en not_active IP Right Cessation
- 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 AU AU89954/91A patent/AU643350B2/en not_active Ceased
- 1991-12-20 DE DE69126656T patent/DE69126656T2/en not_active Expired - Lifetime
- 1991-12-20 DK DK91810992.7T patent/DK0493326T3/en active
- 1991-12-26 JP JP3344634A patent/JP2825383B2/en not_active Expired - Lifetime
- 1991-12-26 KR KR1019910024456A patent/KR100235378B1/en not_active IP Right Cessation
-
1997
- 1997-09-10 GR GR970402323T patent/GR3024677T3/en unknown
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Cited By (6)
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---|---|---|---|---|
AU657248B2 (en) * | 1992-06-25 | 1995-03-02 | Eltech Systems Corporation | Electrodes of improved service life |
EP0576402B1 (en) * | 1992-06-25 | 1997-03-05 | Eltech Systems Corporation | Electrodes of improved service life |
WO1997017478A1 (en) * | 1995-11-08 | 1997-05-15 | Fissler Gmbh | Process for producing a non-stick coating and objects provided with such a coating |
US8632836B2 (en) | 2007-07-09 | 2014-01-21 | Astra Tech Ab | Nanosurface |
US9642708B2 (en) | 2007-07-09 | 2017-05-09 | Astra Tech Ab | Nanosurface |
CN104073842A (en) * | 2011-10-13 | 2014-10-01 | 金川集团有限公司 | Negative plate used for electrodepositing electrolyzing nickel |
Also Published As
Publication number | Publication date |
---|---|
KR100235378B1 (en) | 1999-12-15 |
MX9102511A (en) | 1992-06-01 |
JPH04301062A (en) | 1992-10-23 |
DE69126656D1 (en) | 1997-07-31 |
EP0493326A3 (en) | 1993-03-17 |
GR3024677T3 (en) | 1997-12-31 |
DK0493326T3 (en) | 1997-12-29 |
AU643350B2 (en) | 1993-11-11 |
CA2056943A1 (en) | 1992-06-27 |
AU8995491A (en) | 1992-07-02 |
KR920011628A (en) | 1992-07-24 |
ATE154834T1 (en) | 1997-07-15 |
JP2825383B2 (en) | 1998-11-18 |
DE69126656T2 (en) | 1998-01-02 |
TW197475B (en) | 1993-01-01 |
EP0493326B1 (en) | 1997-06-25 |
ES2104684T3 (en) | 1997-10-16 |
CA2056943C (en) | 1997-11-11 |
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