US3505178A - Process of electroplating an article by sequentially passing the same and a platinum coated tungsten anode through a series of different electroplating baths - Google Patents
Process of electroplating an article by sequentially passing the same and a platinum coated tungsten anode through a series of different electroplating baths Download PDFInfo
- Publication number
- US3505178A US3505178A US637938A US3505178DA US3505178A US 3505178 A US3505178 A US 3505178A US 637938 A US637938 A US 637938A US 3505178D A US3505178D A US 3505178DA US 3505178 A US3505178 A US 3505178A
- Authority
- US
- United States
- Prior art keywords
- electroplating
- platinum
- plating
- anodes
- baths
- 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.)
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title description 42
- 229910052697 platinum Inorganic materials 0.000 title description 21
- 229910052721 tungsten Inorganic materials 0.000 title description 16
- 239000010937 tungsten Substances 0.000 title description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title description 15
- 238000009713 electroplating Methods 0.000 title description 14
- 238000000034 method Methods 0.000 title description 14
- 238000007747 plating Methods 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000011651 chromium Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 6
- -1 fluoride ions Chemical class 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 229910018487 Ni—Cr Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XRBURMNBUVEAKD-UHFFFAOYSA-N chromium copper nickel Chemical compound [Cr].[Ni].[Cu] XRBURMNBUVEAKD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting 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
- 239000010959 steel Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Definitions
- This invention relates to a method for electroplating copper, chromium and/or nickel from electrolyte solutions in processes in which the electroplating anodes are carried through a pre-treatment bath comprising an acidic etchant solution containing fluoride ions.
- this invention concerns methods of electroplating from such electrolytes employing platinum on tungsten anodes.
- Platinum-coated titanium anodes are known in the art. Such electrodes have been employed as insoluble anodes in the electroplating of nickel and chromium. It has been found that while these anodes are relatively stable toward dislodgment of the platinum coating when employed in conventional plating baths, the anode suifers from corrosion and platinum dislodgment when carried through pre-treatment immersion baths containing free fluorides.
- plated metal in the automotive industry especially for body appearance is well known. Where strength is required, as in chrome-plated bumpers, the support is generally heavy steel.
- Other plated parts with more intricate shapes are generally made from castings of relatively low melting metals or alloys. For example, zinc die castings are extensively plated with a Cu-Ni-Cr plating cycle for door handles, grill work and other metallic parts.
- Each plating bath gener ally has main electrodes, which are ordinarily expendable anodes for the copper and nickel plating steps, and nonexpendable anodes for the Cr plating.
- main electrodes which are ordinarily expendable anodes for the copper and nickel plating steps, and nonexpendable anodes for the Cr plating.
- additional anodes are positioned in the bath for the purpose of controlling the rate of deposition of the plating metal at corners or deep-set recesses of the work, and these are normally designated deep-throw anodes.
- Such anodes are especially useful in nickel and chromium plating because of the low throwing power of conventional nickel and chromium plating baths and, advantageously, would be of the non-expendable type.
- Such solutions may contain hydrogen fluoride, a compound capable of producing fluoride ions in solution, e.g. an acid, or alkali metal or ammonium salt of F, HF2 BF4 SiF and the like.
- Such treatment activates the support surface for improved adhesion of the plate. It would therefore be of further advantage to provide an electroplating anode capable of passing high current density in a plating bath and substantially inert to fluoridecontaining etchant baths.
- non-expendable deepthrow anodes suitable for such plating procedures are usually attacked by acidic fluoride-containing solutions.
- non-expendable anodes of tungsten having platinum coatings thereon are employed in electroplating processes to deposit electroplates of copper, nickel and/or chromium where immersion of the rack in an acidic fluoride containing etchant solution precedes the electrodeposition.
- the anode which is used in the practice of the present inven tion consists of a tungsten base of suitable shape for the work to be performed, partly or completely coated with a conducting layer of platinum.
- Such anodes can be prepared by electroplating platinum on tungsten by means of conventional platinum plating solutions, e.g. P salt platinum baths as disclosed in US. Patents No. 1,779,436 and No. 1,779,457.
- the platinum coating may cover all or a portion of the anode sutficient to carry the electric current applied during use as an anode.
- the electroplated platinum coating will not ordinarily be imporous and need not be of substantial thickness, a coating of microinches platinum Ibeing usually suificient for use as an anode. While platinum is preferred as a coating, other platinum group metals such as rhodium and iridium as well as alloys thereof with platinum, are also suitable.
- EXAMPLE I A coupon of commercially pure tungsten was coated with 100 microinches platinum by electrodeposition from a P salt platinum bath. The coating was fired in an inert atmosphere at a temperature of 800C. for one hour.
- the platinized tungsten coupon so prepared was immersed in 52% by volume hydrofluoric acid for 19 hours. No attack was visible on either the tungsten or the platinum coating.
- a similar coupon was employed as anode in a commercial chromium-plating bath (M & T Cr chromium plating bath). Electrolysis was carried out at 1.5 amperes per square inch for five hours. No attack was evident on the coating or the tungsten substrate.
- EXAMPLE II Three coupons were prepared by the procedure of Example I, one of platinized-tantalum, one of platinized tungsten and one of platinized molybdenum. Each of the coupons was immersed in a 52% by volume HF solution. The platinized tantalum coupon showed immediate gasing, and was removed within three minutes of immersion; attack was severe. The platinized-tungsten and platinized molybdenum were removed after 66 hours. Neither of these coupons showed any evidence of attack.
- valve metals which are employed as substrate for platinized electrodes are not all equivalent, and where pre-treatment in solutions containing free fluoride is required, platinized tungsten is an outstandingly useful electrode.
- Such electrodes can be employed as the main anodes for the electrodeposition process, or as auxiliary deep-throw anodes, and may be used in both nickel and chromium plating baths, thus obviating any need for anode replacement in plating processes which employ a nickel-chromium plating cycle.
Description
United States Patent PROCESS OF ELECTROPLATING AN ARTICLE BY SEQUENTIALLY PASSING THE SAME AND A PLATINUM COATED TUNGSTEN ANODE THROUGH A SERIES OF DIFFER- ENT ELECTROPLATING BATHS James E. May, Dorchester, Mass., and Alfred J. Haley,
Jr., Westfield, N.J., assignors to Engelhard Industries,
Inc., Newark, N.J., a corporation of Delaware No Drawing. Filed May 12, 1967, Ser. No. 637,938
Int. Cl. C23b 5/06, 5/72, 5/62 US. Cl. 20432 1 Claim ABSTRACT OF THE DISCLOSURE A method is disclosed for the electroplating of metal objects in copper-nickel-chromium plating cycles, wherin the electroplating steps are preceded by an acidic etching solution containing fluoride ions, by means of a platinum coated tungsten anode.
This invention relates to a method for electroplating copper, chromium and/or nickel from electrolyte solutions in processes in which the electroplating anodes are carried through a pre-treatment bath comprising an acidic etchant solution containing fluoride ions. In particular, this invention concerns methods of electroplating from such electrolytes employing platinum on tungsten anodes.
Platinum-coated titanium anodes are known in the art. Such electrodes have been employed as insoluble anodes in the electroplating of nickel and chromium. It has been found that while these anodes are relatively stable toward dislodgment of the platinum coating when employed in conventional plating baths, the anode suifers from corrosion and platinum dislodgment when carried through pre-treatment immersion baths containing free fluorides.
The extensive usage of plated metal in the automotive industry especially for body appearance is well known. Where strength is required, as in chrome-plated bumpers, the support is generally heavy steel. Other plated parts with more intricate shapes are generally made from castings of relatively low melting metals or alloys. For example, zinc die castings are extensively plated with a Cu-Ni-Cr plating cycle for door handles, grill work and other metallic parts.
In the automotive industry, the Cu-Ni-Cr cycle of plating is carried out automatically. Each plating bath gener ally has main electrodes, which are ordinarily expendable anodes for the copper and nickel plating steps, and nonexpendable anodes for the Cr plating. Generally, in the plating of complex shapes, additional anodes are positioned in the bath for the purpose of controlling the rate of deposition of the plating metal at corners or deep-set recesses of the work, and these are normally designated deep-throw anodes. Such anodes are especially useful in nickel and chromium plating because of the low throwing power of conventional nickel and chromium plating baths and, advantageously, would be of the non-expendable type.
Conventional zinc die-cast plating processes employ deep-throw nickel anodes, which must be replaced in ordinary nickel-chromium plating procedures by non-expendable anodes for the chromium plating steps of the plating cycle. It is seen therefore that non-expendable deep-throw anodes which could remain in place throughout the copper, nickel and chromium plating cycle for plating of die-cast metal shapes would be especially advantageous.
When metallic parts, such as zinc or lead-containing die-cast structural shapes are to be plated in a nickelchromium plating cycle, it is recognized that by far the most difficult step is to clean the surface and it has been found particularly advantageous to first treat the part with an acidic etching solution containing fluoride ions. No electrolysis is performed in this pro-treatment step,
Such solutions may contain hydrogen fluoride, a compound capable of producing fluoride ions in solution, e.g. an acid, or alkali metal or ammonium salt of F, HF2 BF4 SiF and the like. Such treatment activates the support surface for improved adhesion of the plate. It would therefore be of further advantage to provide an electroplating anode capable of passing high current density in a plating bath and substantially inert to fluoridecontaining etchant baths. However, non-expendable deepthrow anodes suitable for such plating procedures are usually attacked by acidic fluoride-containing solutions.
In accordance with the present invention, non-expendable anodes of tungsten having platinum coatings thereon are employed in electroplating processes to deposit electroplates of copper, nickel and/or chromium where immersion of the rack in an acidic fluoride containing etchant solution precedes the electrodeposition. The anode which is used in the practice of the present inven tion, consists of a tungsten base of suitable shape for the work to be performed, partly or completely coated with a conducting layer of platinum. Such anodes can be prepared by electroplating platinum on tungsten by means of conventional platinum plating solutions, e.g. P salt platinum baths as disclosed in US. Patents No. 1,779,436 and No. 1,779,457. In general, the platinum coating may cover all or a portion of the anode sutficient to carry the electric current applied during use as an anode. The electroplated platinum coating will not ordinarily be imporous and need not be of substantial thickness, a coating of microinches platinum Ibeing usually suificient for use as an anode. While platinum is preferred as a coating, other platinum group metals such as rhodium and iridium as well as alloys thereof with platinum, are also suitable.
EXAMPLE I A coupon of commercially pure tungsten was coated with 100 microinches platinum by electrodeposition from a P salt platinum bath. The coating was fired in an inert atmosphere at a temperature of 800C. for one hour.
The platinized tungsten coupon so prepared was immersed in 52% by volume hydrofluoric acid for 19 hours. No attack was visible on either the tungsten or the platinum coating.
A similar coupon was employed as anode in a commercial chromium-plating bath (M & T Cr chromium plating bath). Electrolysis was carried out at 1.5 amperes per square inch for five hours. No attack was evident on the coating or the tungsten substrate.
EXAMPLE II (A) Three coupons were prepared by the procedure of Example I, one of platinized-tantalum, one of platinized tungsten and one of platinized molybdenum. Each of the coupons was immersed in a 52% by volume HF solution. The platinized tantalum coupon showed immediate gasing, and was removed within three minutes of immersion; attack was severe. The platinized-tungsten and platinized molybdenum were removed after 66 hours. Neither of these coupons showed any evidence of attack.
(B) A similar test of three coupons was conducted by immersing each in a solution of a commercially available fluoride-containing etchant (Actisalt-l, Northwest Chemical Co.) containing 4 oz./ gallon of salt for a period of 66 hours. At the end of this time, the coupons were examined visually with the following results:
Platinized tantalum-slight attack Platinized tungsten-no change Platinized molybdenum-no change Platinized titanium-moderate corrosion -Platinized molybdenum-severe corrosion Platinized tungstenno change Platinized tantalumno change From the above tests, it is apparent that platinized tungsten resists attack in highly-concentrated HF solution, in etchant salts containing fluoride conventionally employed in pre-treatment of metal objects to be subjected to nickel plating, and to anodic attack in conventional nickel and chromium plating baths. It will be seen therefore that the so-called valve metals, which are employed as substrate for platinized electrodes are not all equivalent, and where pre-treatment in solutions containing free fluoride is required, platinized tungsten is an outstandingly useful electrode. Such electrodes can be employed as the main anodes for the electrodeposition process, or as auxiliary deep-throw anodes, and may be used in both nickel and chromium plating baths, thus obviating any need for anode replacement in plating processes which employ a nickel-chromium plating cycle.
What is claimed is:
1. In a process for electroplating zinc or lead-containing die castings wherein the casting and associated anodes are immersed in an acidic etchant containing fluoride ions and subsequently and consecutively immersed in nickel plating and chrome plating baths for electrodeposition of nickel and chromium electrodeposits on the castings, the improvement of employing platinum-coated tungsten as the anode.
References Cited UNITED STATES PATENTS 1,835,679 12/1931 Van Derau 20441XR 1,970,804 8/ 1934 Kerk.
2,128,550 8/1938 Ford 20441XR 2,979,553 4/1961 McCallum et al. 20429O 3,287,250 11/1966 Broun et a1. 204-290 3,336,658 8/1967 Husni 29492 3,410,785 11/1968 Clough et al 20429O 3,412,000 11/1968 Bedi 204147 JOHN H. MACK, Primary Examiner W. VAN SISE, Assistant Examiner US. Cl. X.R. 204--41, 290
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US63793867A | 1967-05-12 | 1967-05-12 |
Publications (1)
Publication Number | Publication Date |
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US3505178A true US3505178A (en) | 1970-04-07 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US637938A Expired - Lifetime US3505178A (en) | 1967-05-12 | 1967-05-12 | Process of electroplating an article by sequentially passing the same and a platinum coated tungsten anode through a series of different electroplating baths |
Country Status (1)
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US (1) | US3505178A (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1835679A (en) * | 1929-01-05 | 1931-12-08 | Westinghouse Electric & Mfg Co | Chromium plated article |
US1970804A (en) * | 1932-12-24 | 1934-08-21 | Paul C Kerk | Electrode for electrolytic baths |
US2128550A (en) * | 1933-02-06 | 1938-08-30 | Gen Motors Corp | Anticorrosion process for zinc base castings |
US2979553A (en) * | 1958-01-03 | 1961-04-11 | Remington Arms Co Inc | Current generator cell |
US3287250A (en) * | 1962-05-28 | 1966-11-22 | Pittsburgh Plate Glass Co | Alkali-chlorine cell containing improved anode |
US3336658A (en) * | 1963-12-06 | 1967-08-22 | Rca Corp | Superconductive articles |
US3410785A (en) * | 1965-08-24 | 1968-11-12 | Nat Res Corp | Vacuum metallized electrode |
US3412000A (en) * | 1965-04-14 | 1968-11-19 | M & T Chemicals Inc | Cathodic protection of titanium surfaces |
-
1967
- 1967-05-12 US US637938A patent/US3505178A/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1835679A (en) * | 1929-01-05 | 1931-12-08 | Westinghouse Electric & Mfg Co | Chromium plated article |
US1970804A (en) * | 1932-12-24 | 1934-08-21 | Paul C Kerk | Electrode for electrolytic baths |
US2128550A (en) * | 1933-02-06 | 1938-08-30 | Gen Motors Corp | Anticorrosion process for zinc base castings |
US2979553A (en) * | 1958-01-03 | 1961-04-11 | Remington Arms Co Inc | Current generator cell |
US3287250A (en) * | 1962-05-28 | 1966-11-22 | Pittsburgh Plate Glass Co | Alkali-chlorine cell containing improved anode |
US3336658A (en) * | 1963-12-06 | 1967-08-22 | Rca Corp | Superconductive articles |
US3412000A (en) * | 1965-04-14 | 1968-11-19 | M & T Chemicals Inc | Cathodic protection of titanium surfaces |
US3410785A (en) * | 1965-08-24 | 1968-11-12 | Nat Res Corp | Vacuum metallized electrode |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ENGELHARD CORPORATION 70 WOOD AVENUE SOUTH, METRO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:PHIBRO CORPORATION, A CORP. OF DE;REEL/FRAME:003968/0801 Effective date: 19810518 |