EP0119424A1 - Procédé pour le dépôt des couches en alliage or-argent brillantes de bas carat - Google Patents

Procédé pour le dépôt des couches en alliage or-argent brillantes de bas carat Download PDF

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Publication number
EP0119424A1
EP0119424A1 EP84101158A EP84101158A EP0119424A1 EP 0119424 A1 EP0119424 A1 EP 0119424A1 EP 84101158 A EP84101158 A EP 84101158A EP 84101158 A EP84101158 A EP 84101158A EP 0119424 A1 EP0119424 A1 EP 0119424A1
Authority
EP
European Patent Office
Prior art keywords
gold
silver
carat
tellurium
cyanide
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
Application number
EP84101158A
Other languages
German (de)
English (en)
Other versions
EP0119424B1 (fr
Inventor
Bernd Dr. Dipl.-Chem. Dorbath
Rainer Dr. Dipl.-Chem. Schlodder
Norbert Giesecke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to AT84101158T priority Critical patent/ATE27007T1/de
Publication of EP0119424A1 publication Critical patent/EP0119424A1/fr
Application granted granted Critical
Publication of EP0119424B1 publication Critical patent/EP0119424B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the invention relates to an electrolytic bath for depositing low-carat, shiny gold-silver alloy coatings, consisting of an aqueous solution of 0.5-25 g / 1 gold in the form of alkali gold cyanide, 0.25-15 g / 1 silver in the form of Alkali silver cyanide and 10 - 200 g / 1 alkali cyanide.
  • organic substances and / or foreign metals, which are not separated, to the electrolyte shiny coatings can be deposited.
  • organic brighteners are e.g. B. triphenylmethane dyes (DD-PS 98 698), condensation Products from polyalkyleneimines and alkylene polyamines (DE-PS 27 13 507).
  • DD-PS 98 698 triphenylmethane dyes
  • DE-PS 27 13 507 condensation Products from polyalkyleneimines and alkylene polyamines
  • CH-PS 629 260 a water-soluble indium compound is described together with an organic aliphatic amine as a gloss additive, in US Pat. No.
  • the gold content in the coating largely depends on the Au / Ag ratio in the bath and on the selected operating parameters for the deposition, in particular on the current density and the bath temperature. These dependencies are disadvantageous for a practical bathroom operation for the deposition of low-carat gold-silver alloys with a constant carat content.
  • an object of the present invention to provide an electrolytic bath for depositing low-carat, shiny gold-silver alloy coatings, consisting of an aqueous solution of 0.5 to 25 g / 1 gold in the form of alkali gold cyanide, 0.25-15 g / 1 silver in the form of alkali silver cyanide and 10 to 200 g / 1 alkali cyanide, from which consistently low-carat layers largely independent of the operating parameters, such as current density and Bath temperature, and the gold-silver ratio in the bath can be deposited in layers over 25 ⁇ m glossy and as ductile as possible.
  • the bath additionally contains 0.005 to 5 g / 1 tellurium in the form of a water-soluble tellurium compound.
  • the electrolyte preferably contains 0.001 to 1 g / 1 tellurium in the form of a water-soluble tellurium compound, it being possible for the tellurium to be present in the oxidation stage II, IV or VI.
  • tellurium-containing bath additives are tellurium dioxide (Te02), tellurium trioxide (Te03), telluric acid and its derivatives, such as tellurite and higher-condensed molecular complexes, telluric acid and its derivatives, tellurium-halogen compounds and tellurides.
  • a 12-carat, shiny gold-silver alloy deposit is achieved that is accurate to one carat.
  • Practical deviations from other working parameters, such as temperature, pH, gold, silver and KCN content, from the specified bath operating values hardly change the composition and quality of the deposited alloys.
  • a gold-silver alloy cryptokarätigen a bath temperature of 40 0 C and a pH of 11.5, the bath temperature to i 5 ° C may be at a current density of approximately 0.9 A / dm 2 during the deposition, or change the pH between 10.5 and 12.5 without the composition of the deposited 12-carat alloy fluctuating by more than ⁇ 1 carat.
  • these baths allow low-carat, shiny gold-silver alloy layers with layer thicknesses over 100 ⁇ m to be produced in a single deposition process without intermediate treatment. Also the approx. 100 ⁇ m thick, low-carat gold-silver alloy layers still show an excellent gloss and a strikingly constant alloy composition over the entire layer thickness.
  • Such gold-silver alloy baths are therefore also suitable for the galvanoplastic production of 12-14 carat gold-silver moldings.
  • a known electrolyte which contains gold, silver and free potassium cyanide dissolved in an aqueous solution, and a tellurium-containing compound is added to it, which is either soluble in water or reacts with water to form a soluble compound.
  • the bath is preferably prepared with potassium salts, but sodium salts or ammonium salts can also be used, or other reaction products of AuCN and AgCN with alkali cyanides. Baths containing 5 to 10 g / 1 gold in the form of potassium gold cyanide, 1 to 6 g / 1 silver in the form of potassium silver cyanide and 50 to 150 g / 1 potassium cyanide have proven successful.
  • wetting agents such as B. partially esterified forms of phosphoric acid
  • the quality of the coatings can be improved.
  • Such wetting agents are preferably used in the concentration range from 0.5 to 5 ml / l.
  • the bath is maintained at an alkaline pH, preferably between 10.5 and 12.5. Suitable bath temperatures are between 25 ° C and 70 ° C. The higher the bath temperature, the higher the current density required for the deposition of qualitatively perfect low-carat Au / Ag alloys.
  • a gold-silver alloy of 12 carat ⁇ 1 carat is obtained at a bath temperature of 40 ° C in a current density range of 0.6 to 1.2 A / dm 2 .
  • the same alloy composition is obtained in a current density range of 2.2 to 3.0 A / dm 2 .

Landscapes

  • 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)
  • Physical Vapour Deposition (AREA)
  • Electrolytic Production Of Metals (AREA)
EP84101158A 1983-03-16 1984-02-04 Procédé pour le dépôt des couches en alliage or-argent brillantes de bas carat Expired EP0119424B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84101158T ATE27007T1 (de) 1983-03-16 1984-02-04 Verfahren zum abscheiden von niederkaraetigen, glaenzenden gold-silber-legierungsueberzuegen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3309397 1983-03-16
DE19833309397 DE3309397A1 (de) 1983-03-16 1983-03-16 Elektrolytisches bad zum abscheiden von niederkaraetigen, glaenzenden gold-silber-legierungsueberzuegen

Publications (2)

Publication Number Publication Date
EP0119424A1 true EP0119424A1 (fr) 1984-09-26
EP0119424B1 EP0119424B1 (fr) 1987-05-06

Family

ID=6193635

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84101158A Expired EP0119424B1 (fr) 1983-03-16 1984-02-04 Procédé pour le dépôt des couches en alliage or-argent brillantes de bas carat

Country Status (7)

Country Link
US (1) US4487664A (fr)
EP (1) EP0119424B1 (fr)
JP (1) JPS59179794A (fr)
AT (1) ATE27007T1 (fr)
BR (1) BR8401131A (fr)
DE (2) DE3309397A1 (fr)
HK (1) HK102891A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198998A1 (fr) * 1985-02-16 1986-10-29 Degussa Aktiengesellschaft Bain de dépôt galvanique d'un revêtement d'un alliage d'or-indium
US7465385B2 (en) 2005-06-02 2008-12-16 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
US8142637B2 (en) 2005-06-02 2012-03-27 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007537358A (ja) * 2004-05-11 2007-12-20 テクニック・インコーポレイテッド 金−スズ共晶合金のための電気めっき用溶液
US9290311B2 (en) 2012-03-22 2016-03-22 Saint-Gobain Ceramics & Plastics, Inc. Sealed containment tube
EP2828222B1 (fr) 2012-03-22 2019-05-01 Saint-Gobain Ceramics & Plastics Inc. Structures de tube de longueur étendue
PL2828221T3 (pl) 2012-03-22 2020-11-16 Saint-Gobain Ceramics & Plastics Inc. Wyroby ceramiczne połączone przez spiekanie
ITFI20120103A1 (it) 2012-06-01 2013-12-02 Bluclad Srl Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE750185C (de) * 1939-07-08 1944-12-27 Baeder zur elektrolytischen Abscheidung von glaenzenden Metallniederschlaegen
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL277803A (fr) * 1961-05-01
JPS4410363Y1 (fr) * 1966-12-08 1969-04-25
GB1283024A (en) * 1970-01-22 1972-07-26 B J S Electro Plating Company Electro-depositing silver alloys
US3864222A (en) * 1973-03-26 1975-02-04 Technic Baths for Electrodeposition of Gold and Gold Alloys and Method Therefore
US4121982A (en) * 1978-02-03 1978-10-24 American Chemical & Refining Company Incorporated Gold alloy plating bath and method
CH629260A5 (en) * 1978-02-22 1982-04-15 Systemes Traitements Surfaces Process for gold-silver electrolytic deposition, bath for its use and alloy thus obtained

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE750185C (de) * 1939-07-08 1944-12-27 Baeder zur elektrolytischen Abscheidung von glaenzenden Metallniederschlaegen
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 73, Nr. 14, 5. Oktober 1970, Seite 444, Nr. 72575w, Columbus, Ohio, USA & JP-B-45 012963 (SUMITOMO METAL MINING CO., LTD.) 11.05.1970 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0198998A1 (fr) * 1985-02-16 1986-10-29 Degussa Aktiengesellschaft Bain de dépôt galvanique d'un revêtement d'un alliage d'or-indium
US7465385B2 (en) 2005-06-02 2008-12-16 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
US8142637B2 (en) 2005-06-02 2012-03-27 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Also Published As

Publication number Publication date
US4487664A (en) 1984-12-11
JPH0571673B2 (fr) 1993-10-07
JPS59179794A (ja) 1984-10-12
ATE27007T1 (de) 1987-05-15
EP0119424B1 (fr) 1987-05-06
BR8401131A (pt) 1984-10-23
DE3463528D1 (en) 1987-06-11
DE3309397A1 (de) 1984-09-20
HK102891A (en) 1991-12-27

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