US3671408A - Rhodium-platinum plating bath and process - Google Patents

Rhodium-platinum plating bath and process Download PDF

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Publication number
US3671408A
US3671408A US146808A US3671408DA US3671408A US 3671408 A US3671408 A US 3671408A US 146808 A US146808 A US 146808A US 3671408D A US3671408D A US 3671408DA US 3671408 A US3671408 A US 3671408A
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United States
Prior art keywords
rhodium
bath
platinum
metal
electroplating
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Expired - Lifetime
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US146808A
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English (en)
Inventor
Albert Michael Martini
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OMI International Corp
Sel Rex Corp
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Sel Rex Corp
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Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to OMI INTERNATIONAL CORPORATION reassignment OMI INTERNATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
Assigned to MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF reassignment MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL CORPORATION, A CORP OF DE
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/567Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals

Definitions

  • the electrolyte comprises an aqueous solution of rhodium sulfate, platinum as P salt and sulfamic acid.
  • Electrodeposited rhodium is used for a decorative coating and as a contact base metal because of its extreme hardness and resistence to corrosion and to wear. Rhodium plating is particularly useful as a protective coating for silverware, hollow ware, jewelry and for electronic products. Such deposits, however, tend to be brittle, especially thick deposits.
  • Electrodeposited platinum has not been as popular as rhodium in the jewelry and decorative filed because its color is darker than rhodium or silver and it tends to darken further with time. There would be a great interest in the above areas for obtaining bright low stress deposits of rhodium, platinum or mutual alloys of the two.
  • rhodium sulfate, platinum P salt, and sulfamic acid are generally mixed with sufficient water to obtain the following approximate concentrations:
  • Rhodium metal as the sulfate
  • Platinum metal as platinum P salt
  • the rhodium metal concentration ranges from about 0.5 to 12 g/l, most preferably from about 2 to 10 g/l.
  • the platinum metal varies from about 0.07 to 12 g/l, most preferably from about 0.1 to 10 g/l.
  • the sulfamic acid concentration preferably varies from 30 g/l to saturation concentration, most preferably from 50 to 100 g/l.
  • a high rhodium bath is used for electrodepositing a predominantly rhodium containing alloy.
  • the rhodium metal concentration generally ranges from about 1 to 12 g/l, preferably from about 2 to 7 g/l; the platinum metal concentration varies from about 0.04 to 1.2 g/l, preferably from about 0.1 to 0.7 g/l; and the sulfamic acid concentration varies from about 30 g]! to saturation concentration, preferably 50 to 100 g/l.
  • the rhodium concentrations for the high rhodium bath can be further broken down according to the thickness of the deposit desired.
  • the rhodium content of the bath be 1 to 2 g/l; for deposits of 2 to 10 microinches, the rhodium content preferably is 2 to g/l; and for deposits greater than microinches, the rhodium content preferably is 2 to 10 g/l.
  • the platinum content for each range of thickness varies proportionately with the rhodium content.
  • a high platinum bath is used for electrodepositing a predominantly platinum containing alloy.
  • the platinum metal concentration varies from about 2 to 24 g/l, preferably from about 5 to 12 g/l; the rhodium metal concentration varies from about 0.10 to 5 gll, preferably from about 0.2 to 2 g/l; and the sulfamic acid concentration varies from about 30 to saturation, preferably from about 50 to g/l.
  • the limits of current density can usually be improved by the addition of concentrated sulfuric acid generally up to about 100 ml/l of solution, preferably from 1 to 50 ml/l of solution.
  • the plating solution of this invention can be used to coat any substrate that is capable of receiving an electrodeposit, particularly such basis metals as copper, brass, nickel, mild steel, silver and the like. Because the acid bath of this invention might cause dissolution of the basis metal thereby contaminating the bath, it is preferred that the basis metal be protected, eg. by flash coating with palladium, palladium-gold, or preferably gold, so as to inhibit attack on the basis metal. In the case where the basis metal contains iron, it is preferred that the basis metal first be preplated with, for example, nickel, copper, or silver, prior to flash coating.
  • the rhodiumplatinum alloy may be deposited from the plating bath, at a temperature of about 60 to 180 F., by passing a current at a current density of about 5 to 40 ASP through the bath to a cathode immersed therein.
  • the current density is about 10 to 30 ASP and the temperature about 80 to F.
  • the lower temperatures are generally used for flash deposits and the higher temperatures for heavier deposits and for high platinum deposits.
  • the deposit obtained using the high platinum bath contains from about 90 to 99 percent platinum, preferably from about 93 to 98 percent by weight.
  • the high rhodium bath yields a low stress, predominantly rhodium containing deposit which is mirror bright, ductile, and contains from about 90 to 99.5 percent rhodium, preferably from about 93 to 99 percent rhodium, most preferably from about 96 to 98.5 percent rhodium by weight, and from about 0.5 to 10 percent platinum, preferably from about 1.0 to 7 percent platinum, most preferably from about 1.5 to 4.0 percent platinum by weight.
  • the deposits obtained by the process of this invention range from flash coatings, eg. 2 microinches, up to thick coatings of 200 microinches or more. Preferably this process is used to obtain low stress deposits of 50 to microinches.
  • lead metal is added per liter of bath, preferably from 2 to 6 mg/liter.
  • the lead is added as a water soluble salt, preferably as lead nitrate.
  • the high rhodium bath is particularly useful for the plating of coins, jewelry, hollow water, tableware, and the like, giving a mirror bright finish which greatly adds to their appearance.
  • the high rhodium bath is especially useful for plating silver articles, preferably those containing greater than 90 weight percent silver, in that the deposit inhibits tarnishing of the silver, probably because of the non-porous nature of the deposit.
  • the article In plating silver articles with the high rhodium bath, it is preferred that the article first be given a flash coating of gold.
  • EXAMPLE 1 2gms (as the sulfate) 0.05 (as platinum P salt) SOgmt.
  • Test panel is plated to 100 microinches, with agitation, and analysis shows that deposit contains 2 to 5 percent Pt. and is low stress.
  • Test panels are plated mirror bright (15ASF) with a finish approaching the color of a highly buffed silver piece. 0.5 to 5 minutes. Thickness: Flash to microinches.
  • Brass watch bezels are plated at 118 to 122 F. and 20 ASP for 20 to 42 minutes.
  • Mirror bright, silver colored deposits are obtained having thicknesses of 100 to 200 microinches.
  • Test panel of nickel plated brass with gold flash is plated at 1 10 to 115 F. and ASF, with agitation for 10 minutes. Deposit is 50 to 70 microinches, mirror bright and low stress, and has a silver color.
  • a test panel of nickel plated brass with gold strike is plated at to F. and 20ASF for 2 minutes without agitation.
  • a 2 microinch mirror bright deposit is obtained having a silver color.
  • a test panel of nickel plated brass with gold strike is plated at to F. and 20 ASP for 17 minutes with agitation. A 100 microinch semi-mirror bright deposit is obtained.
  • An electroplating bath for depositing rhodium-platinum alloy therefrom comprising an aqueous solution of:
  • Rhodium metal as the sulfate
  • Platinum metal as P salt
  • the bath of claim 1 comprising an aqueous solution of:
  • Rhodium metal as the sulfate
  • Platinum metal as P salt
  • the bath of claim 2 additionally containing up to about 100 ml/l concentrated sulfuric acid per liter of solution.
  • An electroplating bath for depositing a predominantly rhodium containing alloy comprising an aqueous solution of:
  • Rhodium metal (as the sulfate) 1 to l2g/l
  • Platinum metal (as P salt) 0.04 to 1.2g/l
  • the bath of claim 4 comprising an aqueous solution of:
  • Rhodium metal as the sulfate 2 to 73/1
  • Platinum metal as P salt 0.1 to 0.7g/l
  • the bath of claim 6 additionally containing up to about 100 ml/l of concentrated sulfuric acid per liter of solution.
  • the bath of claim 5 additionally containing up to about 100 ml/] of concentrated sulfuric acid per liter of solution.
  • a process of electroplating rhodium-platinum alloy comprising electrodepositing the rhodium and platinum upon a basis metal from the aqueous bath of claim 1.
  • a process for electroplating a predominantly rhodium containing alloy comprising electrodepositing rhodium and platinum upon a basis metal from the bath of claim 4.
  • a process for electroplating a predominantly rhodium containing alloy comprising electrodepositing rhodium and platinum upon a basis metal from the bath of claim 5.
  • a process for electroplating a predominantly rhodium containing alloy comprising electrodepositing rhodium and platinum upon a basis metal from the bath of claim 8.
  • a process for electroplating a predominantly rhodium containing alloy comprising electrodepositing rhodium and 5 platium upon a basis metal from the bath of claim 4.

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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)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
US146808A 1971-05-25 1971-05-25 Rhodium-platinum plating bath and process Expired - Lifetime US3671408A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US14680871A 1971-05-25 1971-05-25

Publications (1)

Publication Number Publication Date
US3671408A true US3671408A (en) 1972-06-20

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US146808A Expired - Lifetime US3671408A (en) 1971-05-25 1971-05-25 Rhodium-platinum plating bath and process

Country Status (9)

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US (1) US3671408A (enrdf_load_stackoverflow)
BR (1) BR7203327D0 (enrdf_load_stackoverflow)
CA (1) CA1027892A (enrdf_load_stackoverflow)
CH (1) CH541627A (enrdf_load_stackoverflow)
DE (1) DE2226699A1 (enrdf_load_stackoverflow)
FR (1) FR2140231A1 (enrdf_load_stackoverflow)
GB (1) GB1383850A (enrdf_load_stackoverflow)
IT (1) IT958011B (enrdf_load_stackoverflow)
NL (1) NL7206694A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2211539A1 (enrdf_load_stackoverflow) * 1972-12-22 1974-07-19 Western Electric Co
US4285784A (en) * 1980-07-10 1981-08-25 The United States Of America As Represented By The Secretary Of The Interior Process of electroplating a platinum-rhodium alloy coating
US6306277B1 (en) 2000-01-14 2001-10-23 Honeywell International Inc. Platinum electrolyte for use in electrolytic plating
US20080261066A1 (en) * 2007-04-20 2008-10-23 Ibm Corporation (Yorktown) Fabricating a contact rhodium structure by electroplating and electroplating composition
DE102008050135A1 (de) 2008-10-04 2010-04-08 Umicore Galvanotechnik Gmbh Verfahren zur Abscheidung von Platin-Rhodiumschichten mit verbesserter Helligkeit
CN103397358A (zh) * 2013-08-01 2013-11-20 江苏协鑫软控设备科技发展有限公司 用于铂铑合金热电偶修复的电镀液及修复工艺
CN108130566A (zh) * 2018-01-31 2018-06-08 西北有色金属研究院 用于镍基高温合金表面电镀铂层的电镀液及其电镀方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1431548A (en) * 1972-09-21 1976-04-07 Engelhard Ind Ltd Electrodeposition of plantinum
DE3100997C2 (de) * 1981-01-15 1986-08-14 Degussa Ag, 6000 Frankfurt Bad zum galvanischen Abscheiden von Rhodiumüberzügen
US4673472A (en) * 1986-02-28 1987-06-16 Technic Inc. Method and electroplating solution for deposition of palladium or alloys thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2984604A (en) * 1958-08-06 1961-05-16 Sel Rex Corp Platinum plating composition and process
US3515651A (en) * 1966-02-07 1970-06-02 Katsuhiro Ohkubo Plating solutions for rhodium and rhodium alloy platings having low internal stress
US3528895A (en) * 1967-07-10 1970-09-15 Sel Rex Corp Plating low stress bright rhodium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2984604A (en) * 1958-08-06 1961-05-16 Sel Rex Corp Platinum plating composition and process
US3515651A (en) * 1966-02-07 1970-06-02 Katsuhiro Ohkubo Plating solutions for rhodium and rhodium alloy platings having low internal stress
US3528895A (en) * 1967-07-10 1970-09-15 Sel Rex Corp Plating low stress bright rhodium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Abner Brenner, Electrodeposition of Alloys, Vol. II, pp. 544 545, (1963). *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2211539A1 (enrdf_load_stackoverflow) * 1972-12-22 1974-07-19 Western Electric Co
US4285784A (en) * 1980-07-10 1981-08-25 The United States Of America As Represented By The Secretary Of The Interior Process of electroplating a platinum-rhodium alloy coating
US6306277B1 (en) 2000-01-14 2001-10-23 Honeywell International Inc. Platinum electrolyte for use in electrolytic plating
US6521113B2 (en) 2000-01-14 2003-02-18 Honeywell International Inc. Method of improving the oxidation resistance of a platinum modified aluminide diffusion coating
US8372744B2 (en) 2007-04-20 2013-02-12 International Business Machines Corporation Fabricating a contact rhodium structure by electroplating and electroplating composition
US20080261066A1 (en) * 2007-04-20 2008-10-23 Ibm Corporation (Yorktown) Fabricating a contact rhodium structure by electroplating and electroplating composition
US8941240B2 (en) 2007-04-20 2015-01-27 International Business Machines Corporation Fabricating a contact rhodium structure by electroplating and electroplating composition
DE102008050135A1 (de) 2008-10-04 2010-04-08 Umicore Galvanotechnik Gmbh Verfahren zur Abscheidung von Platin-Rhodiumschichten mit verbesserter Helligkeit
WO2010037495A1 (en) * 2008-10-04 2010-04-08 Umicore Galvanotechnik Gmbh Process for the deposition of platinum-rhodium layers having improved whiteness
US20110308959A1 (en) * 2008-10-04 2011-12-22 Umicore Galvanotechnik Gmbh Process for the deposition of platinum-rhodium layers having improved whiteness
CN102171387B (zh) * 2008-10-04 2012-12-26 尤米科尔电镀技术有限公司 具有改善的白度的铂-铑层的沉积方法
CN103397358A (zh) * 2013-08-01 2013-11-20 江苏协鑫软控设备科技发展有限公司 用于铂铑合金热电偶修复的电镀液及修复工艺
CN103397358B (zh) * 2013-08-01 2016-01-20 江苏协鑫软控设备科技发展有限公司 用于铂铑合金热电偶修复的电镀液及修复工艺
CN108130566A (zh) * 2018-01-31 2018-06-08 西北有色金属研究院 用于镍基高温合金表面电镀铂层的电镀液及其电镀方法
CN108130566B (zh) * 2018-01-31 2019-08-27 西北有色金属研究院 用于镍基高温合金表面电镀铂层的电镀液及其电镀方法

Also Published As

Publication number Publication date
GB1383850A (en) 1974-02-12
NL7206694A (enrdf_load_stackoverflow) 1972-11-28
FR2140231A1 (enrdf_load_stackoverflow) 1973-01-12
CA1027892A (en) 1978-03-14
BR7203327D0 (pt) 1973-05-10
IT958011B (it) 1973-10-20
CH541627A (fr) 1973-09-15
DE2226699A1 (de) 1972-12-28

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AS Assignment

Owner name: HOOKER CHEMICALS & PLASTICS CORP.

Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885

Effective date: 19801222

AS Assignment

Owner name: OCCIDENTAL CHEMICAL CORPORATION

Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054

Effective date: 19820330

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827

Effective date: 19830915

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Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY

Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733

Effective date: 19830930