US3213004A - Surface preparation of platinum group metals for electrodeposition - Google Patents
Surface preparation of platinum group metals for electrodeposition Download PDFInfo
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- US3213004A US3213004A US94137A US9413761A US3213004A US 3213004 A US3213004 A US 3213004A US 94137 A US94137 A US 94137A US 9413761 A US9413761 A US 9413761A US 3213004 A US3213004 A US 3213004A
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- platinum
- lead dioxide
- coating
- anodic
- platinum surface
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- 229910052751 metal Inorganic materials 0.000 title description 12
- 239000002184 metal Substances 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 4
- 238000004070 electrodeposition Methods 0.000 title description 3
- -1 platinum group metals Chemical class 0.000 title description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 66
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 42
- 229910052697 platinum Inorganic materials 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000000758 substrate Substances 0.000 description 10
- 238000007747 plating Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 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
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Definitions
- an article made of platinum or having a platinum surface will serve as a base for a tightly adhering, blister-free electro-deposited coating if it is subject to a periodic reverse current treatment in a weak oxidizing acid electrolyte.
- the periodic reverse treatment the several cycles are of equal length and the last half cycle must be anodic if a subsequent anodic deposition is to be achieved.
- an electrode made of titanium base or substrate, flashcoated with a platinum group metal and having an outer lead dioxide surface is useful in electrolytic per-oxidation reactions such as the production of sodium perchlorate.
- electrolytic per-oxidation reactions such as the production of sodium perchlorate.
- such electrodes suffered from peeling and blistering of the lead dioxide coating. I have found that the poor adhesion between the lead dioxide and platinum can be overcome by using the periodic reverse current procedure of this invention.
- the platinum surface can be provided by the solid metal as such or the platinum can be only a surface coating on a substrate applied by fiashcoating, cladding or in any other suitable manner. If a substrate other than platinum is employed, the nature of the substrate is controlled by the use to which the final article is to be put. For example, when the article is to be employed as an anode in a chlorate or perchlorate cell one desirably uses titanium or tantalum for such common metals and alloys as copper, nickel, brass, and steel will corrode if exposed in the cell. Irrespective of the substrate, the periodic reverse current activation procedure is the same.
- the plating of the various platinum group metals on a metal or alloy substrate is well known in the art and forms no part of this invention.
- the periodic reverse current cycling activates the platinum surface in the following manner.
- hydrogen is evolved on the platinum surface. This exerts a cleaning action by gas scrubbing and reducing any obnoxious oxide contamination on the surface or which is embedded in the base.
- further cleaning by oxygen gas scrubbing occurs.
- any organic surface contamination is destroyed by the oxidation.
- the combination of the adsorbed hydrogen with the nascent oxygen diminishes the deleterious effect of hydrogen absorption.
- a uniform oxygen-containing layer forms over the anode which is only a few molecular layers thick. This cycling must be repeated several times, depending on the state of the surface.
- articles that were platinum surfaced and then were allowed to dry out for some time before the deposition of lead dioxide coating require approximately 5 minutes cycling, at approximately seconds per half cycle, just prior to their transfer to the lead dioxide plating cell.
- the last half cycle being anodic,
- the platinum surface experiences no further change in adsorbed gas content in the plating cell where it continues as an anode.
- Example 1 A titanium sheet of 4" x 8" x dimensions was cleaned with caustic, rinsed and washed with hot hydrofluoric acid. The sheet was then anodized after removal of a major portion of the oxide film by immersion in 10% HF at room temperature for several seconds. The anodizing was effected by placing the plate in a 2% nitric acid solution at room temperature and raising the voltage from zero to about four volts whereupon a pale yellow anodic film formed on the plate. The sheet was then platinized using a known composition and technique as described in Metal Finishing Guidebook, pages 359-362 (1957, Finishing Publications, Inc.).
- the temperature was maintained between and C. throughout the electrolysis.
- the anodic current density was 10 amps/ft
- the electrodeposition proceeded at the approximate rate of 0.0015 inch per hour.
- the adherence of the electrodeposited lead dioxide was excellent, as tested by repeated bending and hammering of the sheets.
- Example 2 A titanium sheet, 4" x 8" x ,5 was flashcoated with 0.005 mil thickness of rhodium and was activated as in Example 1. After rinsing the sheet was transferred to a lead plumbate plating solution of the following composi tion:
- Example 3 A titanium sheet of 4" x 8" x dimensions was flashcoated with 0.01 mil thickness of palladium using a bath of the following composition and under the conditions indicated:
- the opposite electrode is the opposite electrode.
- the invention has been disclosed as employed for producing a lead dioxide coated electrode suitable for use in an electrolytic per-oxidation cell for production of sodium chlorate the invention is not limited to the use of lead dioxide.
- coatings of other useful and generally inert oxides can be applied using known procedures, these oxides including manganese dioxide and magnetite.
- the invention is not limited to oxide coatings and one can apply any other material to the platinum surface. The anodizing of the platinum surface prepares it for the subsequent inferred deposition of any other coating which may desirably be applied to the platinum surface.
- the improvement which comprises, making the platinum surface an electrode in an electrolyte comprising a solution of an oxidizing acid, exposing said platinum surface while in said electrolyte to periodically reversed current at a current density of from to 80 a.s.f., the last half-cycle of said periodically reversed current being anodic to anodize said platinum surface, and then electrolytically depositing an anodic coating of lead dioxide upon said anodized surface.
- the improvement which comprises, making the platinum surface an electrode in an electrolyte comprising a solution of an oxidizing acid, exposing said platinum surface while in said electrolyte to periodically reversed current at a current density of from 10 to a.s.f., the last half-cycle of said periodically reversed current being anodic to anodize said platinum surface, thereafter making the anodized surface an electrode in a second plating bath from which a coating of another material can be electrodeposited on said surface, and passing direct current through said second bath to anodically deposit a tightly adhering coating of said material on said surface.
- the improvement which comprises, making the platinum surface an electrode in an electrolyte comprising a solution of an oxidizing acid, exposing said platinum surface while in said electrolyte to periodically reversed current at a current density of from 10 to 80 a.s.f. for a period per cycle of approximately 30 seconds, the last half-cycle of said periodically reversed current being anodic to anodize said platinum surface, thereafter making the anodized surface an electrode in a second plating bath from which a coating of lead dioxide can be plated on said surface, and passing direct current through said second bath to anodically deposit a tightly adhering coating of said lead dioxide on said surface.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
United States Patent 3,213,004 SURFACE PREPARATION OF PLATINUM GROUP METALS FOR ELECTRODEPOSITION Francis J. Schmidt, Philadelphia, Pa., assignor to American Potash & Chemical Corporation, a corporation of Delaware No Drawing. Filed Mar. 8, 1961, Ser. No. 94,137 3 Claims. (Cl. 204-29) This invention relates in general to the preparation of the surface of a metal of the platinum group to make it suitable as a base for electroplating and, in particular, to the preparation of a platinum group metal surfaced substrate as a base for the subsequent anodic deposition of an inert coating such as alpha or beta lead dioxide. For the sake of brevity platinum will be used in a generic sense in the following and in the claims and it is to be understood to include all members of the platinum group, namely, Ru, Rh, Pd, Os, Ir, Pt.
It has been found that an article made of platinum or having a platinum surface will serve as a base for a tightly adhering, blister-free electro-deposited coating if it is subject to a periodic reverse current treatment in a weak oxidizing acid electrolyte. During the periodic reverse treatment the several cycles are of equal length and the last half cycle must be anodic if a subsequent anodic deposition is to be achieved.
As illustrative of the utility of the invention, an electrode made of titanium base or substrate, flashcoated with a platinum group metal and having an outer lead dioxide surface is useful in electrolytic per-oxidation reactions such as the production of sodium perchlorate. As made heretofore, such electrodes suffered from peeling and blistering of the lead dioxide coating. I have found that the poor adhesion between the lead dioxide and platinum can be overcome by using the periodic reverse current procedure of this invention.
The platinum surface can be provided by the solid metal as such or the platinum can be only a surface coating on a substrate applied by fiashcoating, cladding or in any other suitable manner. If a substrate other than platinum is employed, the nature of the substrate is controlled by the use to which the final article is to be put. For example, when the article is to be employed as an anode in a chlorate or perchlorate cell one desirably uses titanium or tantalum for such common metals and alloys as copper, nickel, brass, and steel will corrode if exposed in the cell. Irrespective of the substrate, the periodic reverse current activation procedure is the same. The plating of the various platinum group metals on a metal or alloy substrate is well known in the art and forms no part of this invention.
The periodic reverse current cycling activates the platinum surface in the following manner. During the cathodic half cycles, hydrogen is evolved on the platinum surface. This exerts a cleaning action by gas scrubbing and reducing any obnoxious oxide contamination on the surface or which is embedded in the base. Also during the anodic half cycles further cleaning by oxygen gas scrubbing occurs. In addition, any organic surface contamination is destroyed by the oxidation. The combination of the adsorbed hydrogen with the nascent oxygen diminishes the deleterious effect of hydrogen absorption. Finally, a uniform oxygen-containing layer forms over the anode which is only a few molecular layers thick. This cycling must be repeated several times, depending on the state of the surface. Thus articles that were platinum surfaced and then were allowed to dry out for some time before the deposition of lead dioxide coating require approximately 5 minutes cycling, at approximately seconds per half cycle, just prior to their transfer to the lead dioxide plating cell. The last half cycle being anodic,
Wee
the platinum surface experiences no further change in adsorbed gas content in the plating cell where it continues as an anode.
Example 1 A titanium sheet of 4" x 8" x dimensions was cleaned with caustic, rinsed and washed with hot hydrofluoric acid. The sheet was then anodized after removal of a major portion of the oxide film by immersion in 10% HF at room temperature for several seconds. The anodizing was effected by placing the plate in a 2% nitric acid solution at room temperature and raising the voltage from zero to about four volts whereupon a pale yellow anodic film formed on the plate. The sheet was then platinized using a known composition and technique as described in Metal Finishing Guidebook, pages 359-362 (1957, Finishing Publications, Inc.).
G./l. Lead nitrate 200 Copper nitrate 10 Nitric acid to give a pH of 2.0.
The temperature was maintained between and C. throughout the electrolysis. The anodic current density was 10 amps/ft The electrodeposition proceeded at the approximate rate of 0.0015 inch per hour. The adherence of the electrodeposited lead dioxide was excellent, as tested by repeated bending and hammering of the sheets.
Example 2 A titanium sheet, 4" x 8" x ,5 was flashcoated with 0.005 mil thickness of rhodium and was activated as in Example 1. After rinsing the sheet was transferred to a lead plumbate plating solution of the following composi tion:
G./1. Sodium hydroxide 50 Lead oxide 50 Zinc acetate 2 The temperature was maintained at 60 C. The anodic current density was 10 amps/ft. and the solution was vi orously agitated throughout the electrolysis.
A tightly adhering deposit of lead dioxide was obtained, fragments of which clung tenaciously to the substrate even after shattering the deposit by heavy blows with a hammer.
Example 3 A titanium sheet of 4" x 8" x dimensions was flashcoated with 0.01 mil thickness of palladium using a bath of the following composition and under the conditions indicated:
Sodium palladium chloride g./l 10 Sodium nitrate g./l 10 Sodium chloride g./l.. 50 pH 4-5 Temperature C- 50 Cathodic current density amps/ft?" 10 The resulting article was then activated and thereafter coated with lead dioxide as in Example 1. The adherence of the electrodeposited lead dioxide was excellent and resisted bending and hammering.
The opposite electrode.
3 Examples 46 Three metal substrates were each coated with plates of ruthenium, osmium and iridium using baths and procedures which are well known. Following the plating with the respective members of the platinum group, each of the metal substrates was anodized and a plating of lead dioxide applied as in Example 1. The electrodeposited lead dioxide coating was quite smooth, uniform and tenacious in each instance.
While the invention has been disclosed as employed for producing a lead dioxide coated electrode suitable for use in an electrolytic per-oxidation cell for production of sodium chlorate the invention is not limited to the use of lead dioxide. Thus, coatings of other useful and generally inert oxides can be applied using known procedures, these oxides including manganese dioxide and magnetite. The invention is not limited to oxide coatings and one can apply any other material to the platinum surface. The anodizing of the platinum surface prepares it for the subsequent inferred deposition of any other coating which may desirably be applied to the platinum surface.
I claim:
1. In the method for electrolytically depositing a coating of lead dioxide on a platinum surface the improvement which comprises, making the platinum surface an electrode in an electrolyte comprising a solution of an oxidizing acid, exposing said platinum surface while in said electrolyte to periodically reversed current at a current density of from to 80 a.s.f., the last half-cycle of said periodically reversed current being anodic to anodize said platinum surface, and then electrolytically depositing an anodic coating of lead dioxide upon said anodized surface.
2. In the method for producing an electro-deposited coating on a platinum surface the improvement which comprises, making the platinum surface an electrode in an electrolyte comprising a solution of an oxidizing acid, exposing said platinum surface while in said electrolyte to periodically reversed current at a current density of from 10 to a.s.f., the last half-cycle of said periodically reversed current being anodic to anodize said platinum surface, thereafter making the anodized surface an electrode in a second plating bath from which a coating of another material can be electrodeposited on said surface, and passing direct current through said second bath to anodically deposit a tightly adhering coating of said material on said surface.
3. In the method for electrolytically depositing a coating of lead dioxide on a platinum surface the improvement which comprises, making the platinum surface an electrode in an electrolyte comprising a solution of an oxidizing acid, exposing said platinum surface while in said electrolyte to periodically reversed current at a current density of from 10 to 80 a.s.f. for a period per cycle of approximately 30 seconds, the last half-cycle of said periodically reversed current being anodic to anodize said platinum surface, thereafter making the anodized surface an electrode in a second plating bath from which a coating of lead dioxide can be plated on said surface, and passing direct current through said second bath to anodically deposit a tightly adhering coating of said lead dioxide on said surface.
References Cited by the Examiner UNITED STATES PATENTS 1,897,902 2/33 Harsanyi 20414l 2,546,150 3/51 Brenner et al. 20429 2,872,405 2/59 Miller et al. I 2,888,387 5/59 Wasserman 204-33 2,926,125 2/60 Currah et al 20429 2,945,791 7/60 Gibson 204290 FOREIGN PATENTS 836,078 1/58 Great Britain. 586,846 11/59 Canada.
JOHN H. MACK, Primary Examiner.
JOHN R. SPECK, MURRAY TILLMAN, Examiners.
Claims (1)
1. IN THE METHOD FOR ELECTROLYTICALLY DEPOSITING A COATING OF LEAD DIOXIDE ON A PLATINUM SURFACE THE IMPROVEMENT WHICH COMPRISES, MAKING THE PLATINUM SURFACE AN ELECTRODE IN AN ELECROLYTE COMPRISING A SOLUTION OF AN OXIDIZING ACID, EXPOSING SAID PLATINUM SURFACE WHILE IN SAID ELECTROLYTE TO PERIODICALY REVERSED CURRENT AT A CURRENT DENSITY OF FROM 10 TO 80 A.S.F., THE LAST HALF-CYCLE OF SAID PERIODICALLY REVERSED CURRENT BEING ANODIC TO ANODIZE AID PLATINUM SURFACE, AND THEN ELECTROLYTICALLY DEPOSITING AN ANODIC COATING OF LEAD DIOXIDE UPON SAID ANODIZED SURFACE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94137A US3213004A (en) | 1961-03-08 | 1961-03-08 | Surface preparation of platinum group metals for electrodeposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94137A US3213004A (en) | 1961-03-08 | 1961-03-08 | Surface preparation of platinum group metals for electrodeposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3213004A true US3213004A (en) | 1965-10-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US94137A Expired - Lifetime US3213004A (en) | 1961-03-08 | 1961-03-08 | Surface preparation of platinum group metals for electrodeposition |
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| Country | Link |
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| US (1) | US3213004A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454472A (en) * | 1962-09-05 | 1969-07-08 | Ionics | Stable anode and method for making the same |
| US3622487A (en) * | 1968-09-09 | 1971-11-23 | Dynasciences Corp | Apparatus for measuring nitrogen oxide concentrations |
| US3622488A (en) * | 1968-09-09 | 1971-11-23 | Dynasciences Corp | Apparatus for measuring sulfur dioxide concentrations |
| US3668085A (en) * | 1968-08-24 | 1972-06-06 | Isomura Sangyo Kaisha Ltd | Method of electrolytically coating lead dioxide on the surface of various materials |
| US3864163A (en) * | 1970-09-25 | 1975-02-04 | Chemnor Corp | Method of making an electrode having a coating containing a platinum metal oxide thereon |
| USRE28820E (en) * | 1965-05-12 | 1976-05-18 | Chemnor Corporation | Method of making an electrode having a coating containing a platinum metal oxide thereon |
| US4038170A (en) * | 1976-03-01 | 1977-07-26 | Rhees Raymond C | Anode containing lead dioxide deposit and process of production |
| US4051000A (en) * | 1974-11-04 | 1977-09-27 | The International Nickel Company, Inc. | Non-contaminating anode suitable for electrowinning applications |
| US4052271A (en) * | 1965-05-12 | 1977-10-04 | Diamond Shamrock Technologies, S.A. | Method of making an electrode having a coating containing a platinum metal oxide thereon |
| US4173497A (en) * | 1977-08-26 | 1979-11-06 | Ametek, Inc. | Amorphous lead dioxide photovoltaic generator |
| US4309315A (en) * | 1978-12-27 | 1982-01-05 | Nissan Motor Company, Ltd. | Surface-activated functional materials and a method of producing the same |
| US4612094A (en) * | 1985-08-05 | 1986-09-16 | The Dow Chemical Company | Electrical conditioning of a platinum electrode useful in measurement in hypochlorite |
| US5249446A (en) * | 1991-07-19 | 1993-10-05 | Aluminum Company Of America | Process for making an aluminum alloy finstock lubricated by a water-microemulsifiable composition |
| NL1019733C2 (en) * | 2002-01-11 | 2003-07-15 | Univ Delft Tech | Method for manufacturing electrodes. |
| US20220042964A1 (en) * | 2019-04-29 | 2022-02-10 | Shenzhen Angel Drinking Water Industrial Group Corporation | Water hardness detection probe, sensor, detection method and water softener |
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| CA586846A (en) * | 1959-11-10 | C. Miller Henry | Electrode, its preparation and use | |
| US1897902A (en) * | 1927-03-14 | 1933-02-14 | Harsanyi Eugene | Method of coating radiant bodies |
| US2546150A (en) * | 1946-11-08 | 1951-03-27 | Brenner Abner | Method for securing adhesion of electroplated coatings to a metal base |
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| US2926125A (en) * | 1956-03-17 | 1960-02-23 | Canadian Ind | Coating articles of magnesium or magnesium base alloys |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454472A (en) * | 1962-09-05 | 1969-07-08 | Ionics | Stable anode and method for making the same |
| US4052271A (en) * | 1965-05-12 | 1977-10-04 | Diamond Shamrock Technologies, S.A. | Method of making an electrode having a coating containing a platinum metal oxide thereon |
| USRE28820E (en) * | 1965-05-12 | 1976-05-18 | Chemnor Corporation | Method of making an electrode having a coating containing a platinum metal oxide thereon |
| US3668085A (en) * | 1968-08-24 | 1972-06-06 | Isomura Sangyo Kaisha Ltd | Method of electrolytically coating lead dioxide on the surface of various materials |
| US3622487A (en) * | 1968-09-09 | 1971-11-23 | Dynasciences Corp | Apparatus for measuring nitrogen oxide concentrations |
| US3622488A (en) * | 1968-09-09 | 1971-11-23 | Dynasciences Corp | Apparatus for measuring sulfur dioxide concentrations |
| US3864163A (en) * | 1970-09-25 | 1975-02-04 | Chemnor Corp | Method of making an electrode having a coating containing a platinum metal oxide thereon |
| US4051000A (en) * | 1974-11-04 | 1977-09-27 | The International Nickel Company, Inc. | Non-contaminating anode suitable for electrowinning applications |
| US4038170A (en) * | 1976-03-01 | 1977-07-26 | Rhees Raymond C | Anode containing lead dioxide deposit and process of production |
| US4173497A (en) * | 1977-08-26 | 1979-11-06 | Ametek, Inc. | Amorphous lead dioxide photovoltaic generator |
| US4309315A (en) * | 1978-12-27 | 1982-01-05 | Nissan Motor Company, Ltd. | Surface-activated functional materials and a method of producing the same |
| US4612094A (en) * | 1985-08-05 | 1986-09-16 | The Dow Chemical Company | Electrical conditioning of a platinum electrode useful in measurement in hypochlorite |
| US5249446A (en) * | 1991-07-19 | 1993-10-05 | Aluminum Company Of America | Process for making an aluminum alloy finstock lubricated by a water-microemulsifiable composition |
| NL1019733C2 (en) * | 2002-01-11 | 2003-07-15 | Univ Delft Tech | Method for manufacturing electrodes. |
| WO2003057946A1 (en) * | 2002-01-11 | 2003-07-17 | Technische Universiteit Delft | A method for the manufacture of electrodes |
| US20220042964A1 (en) * | 2019-04-29 | 2022-02-10 | Shenzhen Angel Drinking Water Industrial Group Corporation | Water hardness detection probe, sensor, detection method and water softener |
| US11927584B2 (en) * | 2019-04-29 | 2024-03-12 | Shenzhen Angel Drinking Water Industrial Group Corporation | Water hardness detection probe, sensor, detection method and water softener |
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