EP0126921B1 - Bain de dépôt galvanique d'alliages d'or - Google Patents

Bain de dépôt galvanique d'alliages d'or Download PDF

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Publication number
EP0126921B1
EP0126921B1 EP84103995A EP84103995A EP0126921B1 EP 0126921 B1 EP0126921 B1 EP 0126921B1 EP 84103995 A EP84103995 A EP 84103995A EP 84103995 A EP84103995 A EP 84103995A EP 0126921 B1 EP0126921 B1 EP 0126921B1
Authority
EP
European Patent Office
Prior art keywords
acid
bismuth
aqueous bath
alkali
liter
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.)
Expired
Application number
EP84103995A
Other languages
German (de)
English (en)
Other versions
EP0126921A2 (fr
EP0126921A3 (en
Inventor
Manfred Dr. Dettke
Rudolf Klein
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.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Schering AG
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 Schering AG filed Critical Schering AG
Publication of EP0126921A2 publication Critical patent/EP0126921A2/fr
Publication of EP0126921A3 publication Critical patent/EP0126921A3/de
Application granted granted Critical
Publication of EP0126921B1 publication Critical patent/EP0126921B1/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 aqueous bath for the galvanic deposition of uniform rose to violet-colored gold-copper bismuth alloys, exclusively containing an alkali metal or ammonium cyanoaurate-I, alkali copper cyanide, alkali metal cyanide, a bismuth compound and optionally organic wetting and glossing agents.
  • Bismuth-containing baths are already known, from which two- or three-substance alloys can be galvanically deposited.
  • Bismuth trifluoride or bismuth triperchlorate or alkali bismuth mutates are generally used as bismuth compounds, of which the former can only be used in the acidic range and the latter only in the strongly alkaline range, since these compounds are sparingly soluble in the pH range from 6 to 13.
  • Baths of this composition are of no technical importance, since they are unstable and deposit coatings with only a low gloss.
  • FR 2 353 656 also describes additional mixtures for baths for the electrolytic deposition of gold or gold alloys, which are intended to modify the galvanic properties of the baths and thereby improve the electrolytically deposited deposits of gold or gold alloys.
  • Organic water-soluble nitro compounds and water-soluble compounds of arsenic, antimony, bismuth, thallium and selenium are proposed as such additives.
  • the object of the present invention is to provide a stable bismuth-containing gold alloy bath, which enables the deposition of shiny ternary gold alloys with a high bismuth content.
  • the bismuth compound being a water-soluble complex compound of bismuth with ethylenediaminetetramethylphosphonic acid, 2,3-dihydroxypropylphosphonic acid, 1-hydroxyrelihiphiphonic acid, nitrilotriacetic acid, 4-oxyphenylmalonic acid, 1,2-diaminocyclohexanoic acid, dantaminocyclohexane Contains sugar acid, d-manno sugar acid, mucic acid, 1,2,3,4-tetrahydroxy-butane-1,1,4-tricarboxylic acid, 3,4,5-trihydroxybenzoic acid or ethylenediaminetetra-isopropyl alcohol.
  • the bathroom according to the invention is outstandingly suitable for the deposition of shiny rose-colored to violet-colored ternary gold alloys on decorative objects, such as jewelry, watches and glasses, which is not possible with the known bathrooms of similar composition.
  • the bismuth can be incorporated in the alloys with extraordinarily high contents of up to 30 percent by weight, which opens up further areas of application.
  • the bathroom according to the invention is surprisingly also suitable for finishing electronic components, such as plug-in connections, since the precipitates deposited thereby are particularly hard and have good electrical conductivity and excellent abrasion resistance.
  • the soluble complex compounds of bismuth can be prepared before their use according to the invention, for example by reacting the complexing agents with bismuth hydroxide or bismuth nitrate in aqueous solution in a molar ratio of 1 mol bismuth to 1 to 4 mol complexing agent at room temperature.
  • bismuth hydroxide or bismuth nitrate and complexing agent directly to the bath solution.
  • An aqueous solution is used as the bath, which contains exclusively alkali metal or ammonium dicyanoaurate-I, alkali copper cyanide, alkali metal cyanide, the water-soluble complex compound of bismuth and, if appropriate, organic wetting and brightening agents.
  • the preferred concentrations are:
  • Sodium and potassium salts are advantageously used as the alkali salt.
  • the bath can contain customary non-ionic, cationic or anionic wetting agents. These substances can also act as brighteners, in concentrations of 0.01 to 20 g / liter.
  • the pH can be from 6 to 13 and, if desired, is adjusted by adding alkali metal hydroxide.
  • the bath is expediently operated at temperatures of 20 to 70 ° C., current densities of 0.1 to 3 A / dm 2 preferably being used.
  • the pH of 11.5 is adjusted with potassium hydroxide.
  • a rose-colored coating with a fineness of 750/000 is deposited at an average current density of 0.4 A / dm 2 .
  • the coatings have a hardness of HK 420.
  • Precipitation with a purity of 850/000 is separated from this electrolyte.
  • the coatings have an unexpectedly high resistance to corrosion and behave excellently in the wear test.

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)
  • Cosmetics (AREA)

Claims (4)

1. Bain aqueux destiné au dépôt galvanique d'alliages orcuivre-bismuth homogènes de couleur rose à violette, contenant exclusivement un dicyanoaurate-1 d'ammonium ou alcalin, cyanure de cuivre alcalin, cyanure alcalin, un composé du bismuth ainsi que, le cas échéant, des agents mouillants et produits brillanteurs, ledit bain contenant comme composé du bismuth une combinaison complexe soluble à l'eau du bismuth et de l'acide diaminetétraméthylphosphonique, de l'acide 2,3-dihydroxypropylphosphonique, de l'acide 1-hydroxyéthane-diphosphonique, de l'acide nitrilotriacétique, de l'acide 4-oxyphénylmalo- nique, de l'acide 1,2-diaminecyclohexane-tétra- acétique, de l'acide d-saccharique, de l'acide d-mannosaccharique, de l'acide mucique, de l'acide 1,2,3,4-tétrahydroxy-butane-1,1,4-tricarbonique, de l'acide 3,4,5-trihydroxybenzoique ou de l'alcool éthylènediaminetétraisopropylique.
2. Bain aqueux selon revendication 1, caractérisé en ce qu'il contient le complexe composé du bismuth à des concentrations comprises entre 10 mg/litre et 100 mg/litre, l'idéal étant compris entre 5 et 20 g/litre.
3. Bain aqueux selon revendication 1, caractérisé en ce que le rapport molaire du complexe composé du bismuth aux agents complexants est de 1 : 1 à 1 : 4.
4. Bain aqueux selon revendication 1, ledit bain étant caractérisé en ce que sa valeur pH est de 6 à 13.
EP84103995A 1983-05-27 1984-04-10 Bain de dépôt galvanique d'alliages d'or Expired EP0126921B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3319772 1983-05-27
DE19833319772 DE3319772A1 (de) 1983-05-27 1983-05-27 Bad fuer die galvanische abscheidung von goldlegierungen

Publications (3)

Publication Number Publication Date
EP0126921A2 EP0126921A2 (fr) 1984-12-05
EP0126921A3 EP0126921A3 (en) 1985-01-30
EP0126921B1 true EP0126921B1 (fr) 1989-01-18

Family

ID=6200354

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84103995A Expired EP0126921B1 (fr) 1983-05-27 1984-04-10 Bain de dépôt galvanique d'alliages d'or

Country Status (8)

Country Link
US (1) US4517060A (fr)
EP (1) EP0126921B1 (fr)
JP (1) JPS59232289A (fr)
AT (1) AT383148B (fr)
DE (2) DE3319772A1 (fr)
ES (1) ES8502741A1 (fr)
HK (1) HK74389A (fr)
IE (1) IE56353B1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10110743A1 (de) * 2001-02-28 2002-09-05 Wieland Dental & Technik Gmbh Bad zur galvanischen Abscheidung von Gold und Goldlegierungen sowie dessen Verwendung

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8903818D0 (en) * 1989-02-20 1989-04-05 Engelhard Corp Electrolytic deposition of gold-containing alloys
DE3905705A1 (de) * 1989-02-24 1990-08-30 Degussa Bad zur galvanischen abscheidung von feingoldueberzuegen
GB2309032A (en) * 1996-01-11 1997-07-16 Procter & Gamble Bismuth salts and complexes with nitrogen-free organic diphosphonic acids
SG127854A1 (en) 2005-06-02 2006-12-29 Rohm & Haas Elect Mat Improved gold electrolytes
US20090104463A1 (en) 2006-06-02 2009-04-23 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH494284A (fr) * 1968-11-28 1970-07-31 Sel Rex Corp Procédé pour le dépôt électrolytique d'un alliage d'or avec au moins un autre métal commun et bain aqueux de placage pour la mise en oeuvre de ce procédé
FR2053770A5 (en) * 1969-07-17 1971-04-16 Radiotechnique Compelec Electrolytic deposition of gold-bismuth - alloys
CH615464A5 (en) * 1976-06-01 1980-01-31 Systemes Traitements Surfaces Special compositions and particular additives for gold electrolysis baths and their use
US4199416A (en) * 1977-05-03 1980-04-22 Johnson, Matthey & Co., Limited Composition for the electroplating of gold
JPS5951058B2 (ja) * 1977-07-20 1984-12-12 松下電器産業株式会社 磁気記録再生装置
FR2405312A1 (fr) * 1977-10-10 1979-05-04 Oxy Metal Industries Corp Bains electrolytiques pour le depot d'alliages d'or
JPS609117B2 (ja) * 1980-06-19 1985-03-07 セイコーエプソン株式会社 金合金メッキ浴

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10110743A1 (de) * 2001-02-28 2002-09-05 Wieland Dental & Technik Gmbh Bad zur galvanischen Abscheidung von Gold und Goldlegierungen sowie dessen Verwendung

Also Published As

Publication number Publication date
ES532837A0 (es) 1985-02-01
IE56353B1 (en) 1991-07-03
DE3319772A1 (de) 1984-11-29
DE3319772C2 (fr) 1991-05-16
DE3476225D1 (en) 1989-02-23
EP0126921A2 (fr) 1984-12-05
AT383148B (de) 1987-05-25
JPH0565598B2 (fr) 1993-09-20
JPS59232289A (ja) 1984-12-27
IE841268L (en) 1984-11-27
EP0126921A3 (en) 1985-01-30
ATA168784A (de) 1986-10-15
US4517060A (en) 1985-05-14
HK74389A (en) 1989-09-22
ES8502741A1 (es) 1985-02-01

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