EP0140832B1 - Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads - Google Patents

Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads Download PDF

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Publication number
EP0140832B1
EP0140832B1 EP19840810428 EP84810428A EP0140832B1 EP 0140832 B1 EP0140832 B1 EP 0140832B1 EP 19840810428 EP19840810428 EP 19840810428 EP 84810428 A EP84810428 A EP 84810428A EP 0140832 B1 EP0140832 B1 EP 0140832B1
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EP
European Patent Office
Prior art keywords
cyanide
zinc
copper
gold
cadmium
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
EP19840810428
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English (en)
French (fr)
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EP0140832A3 (en
EP0140832A2 (de
Inventor
Heinz Emmenegger
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.)
H E Finishing SA
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H E Finishing SA
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Publication date
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Publication of EP0140832A2 publication Critical patent/EP0140832A2/de
Publication of EP0140832A3 publication Critical patent/EP0140832A3/fr
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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 present invention relates to an electrolysis bath allowing the deposition of a gold-copper-cadmium-zinc alloy and to its use in electroplating.
  • the present invention aims to provide a bath allowing the deposition of a gold-copper-cadmium-zinc alloy from the cyanide complexes of these four metals and providing brilliant deposits ranging from pink to yellow.
  • the object of the present invention is the galvanic bath defined in claim 1 and the galvanic process using this bath according to claim 6.
  • Such a bath must contain the metals of the alloy deposited, preferably within the limits of the following concentrations: from 1 to 20 g / I of gold, from 6 to 70 g / I of copper, from 0.1 to 5 g / I of cadmium and from 1 to 50 g / I of zinc.
  • These various metals must be introduced into the bath in the form of soluble salts, more precisely in the form of cyanide complexes, but without an excess of potassium or sodium cyanide, that is to say without free cyanide according to the definition given in the US Patent 2660554, according to which the free cyanide is the portion of cyanide of alkali metal theoretically not combined with the other metals present in the form of complex salts.
  • the bath must preferably contain from 1 to 50 g / 1 of copper cyanide CuCN or zinc cyanide Zn (CN) 2 which, during the preparation of the bath or during electrolysis, make it possible to avoid the formation of free cyanide by hydrolysis.
  • the deposition bath of the gold-copper-cadmium-zinc alloy which is the subject of the present invention it is no longer copper, but zinc which plays the main role in the balance of different ions present, allowing to obtain the desired deposit.
  • the cyanide complex of zinc can play the role held by free cyanide in baths of gold-copper-cadmium alloy.
  • the cyanide groups linked to zinc or cadmium can, under certain conditions, be released into the bath according to the balance which governs the concentrations of the different ions.
  • the concentration of total cyanide (bound to zinc and cadmium) must be of the order of one to four times the value of the zinc concentration, this zinc cyanide concentration being controlled by the amount of copper cyanide or zinc cyanide involved in the preparation of the bath.
  • composition of the gold-copper-cadmium-zinc alloy bath allows in the practice of electrolysis a much greater margin of concentration of the various constituents than the bath bath formulations.
  • gold-copper-cadmium alloy known so far.
  • a bath containing 4 g / l of gold, 0.8 g / l of cadmium, 35 g / l of copper and 10 g / l of zinc has a total cyanide content of 30 to 40 g / l, which which gives a ratio of 1/1 of the total copper / cyanide concentrations. It provides good deposits.
  • the bath of gold-copper-cadmium-zinc alloy which is the subject of the present invention allows the deposition of a correct alloy from the point of view of the titer and the texture, at a speed greater than that allowed by conventional baths, ie 1 ⁇ m per minute, while a speed of 0.5 ⁇ m per minute is generally considered to be relatively high.
  • methyl phosphonic acids whose molecule contains one or more nitrogen atoms which can be used are for example amino-tri- (methylene-phosphonic), 1-hydroxy-ethylidene 1.1 diphosphonic, ethylene-diamine tetra- (methylene -phosphinic), hexamethylene-diamine-tetra (methylene-phosphonic) or methylene-triamine-penta- (methylene-phosphonic).
  • R represents an alkylene group in which the number of carbon atoms is campris between 1 and 4, or again nitri-10-triacetic acids (NTA) or oxycarbonyl-ethyl-amino-diacetic.
  • NTA nitri-10-triacetic acids
  • All these acids are preferably used in the form of soluble salts, that is to say in the form of potassium, sodium, ammonium or amine salts. To be effective, all of these compounds must be able to complex cadmium ions in a solution free of free potassium or sodium cyanides.
  • amido-propyl-dimethyl-aminooxides of saturated fatty acids of general formula dimethylamino-oxides of saturated fatty acids, of general formula dimethyl-alkyl-amino-oxides, of general formula and bis- (2 hydroxyethyl) -alkyl-amino-oxides, of general formula where n always represents a number between 11 and 20.
  • the fatty acid or alkyl groups can also be ethoxylated.
  • phosphorus-containing esters of ethylene oxide chains linked to an aliphatic chain of general formula monoester, or diester.
  • n represents a number between 8 and 18
  • x represents a number between 6 and 15
  • M represents a sodium or potassium ion.
  • concentrations of these various organic adducts can vary within a relatively large range, from 20 to 200 g / l for the complexing agents and from 0.1 to 50 ml / l for the surfactants.
  • the electrolytic bath which is the subject of the present invention is preferably used at a pH of 9 to 11, with a current density of 0.6 to 2.5 A / dm 2 and at a temperature of 50 ° to 75 ° C.
  • Zinc (as zinc cyanide Zn (CN) 2 and double zinc cyanide and potassium K 2 Zn (CN) 4 )] 10 g / 1
  • wetting agent (amid propyl-dimethyl-amino-oxide of fatty acids from 11 to 17 carbons) 9% solution 2 ml / l
  • the mixture of zinc cyanide and double cyanide of zinc and potassium was composed so that the total cyanide content, determined by a solution of silver nitrate 0.1 N, in the presence of NaOH and KI, gives a value of 30 g / I of KCN linked to zinc.
  • zinc in this bath composition, only in the form of double cyanide of zinc and potassium, we would find 40 g / I of total KCN, ie four times the concentration of zinc.
  • a steel plate 5 cm long and 2 cm wide was subjected to electrolysis, in this bath, at a current density of 0.75 A / dm 2 at the temperature of 60 ° C.
  • the deposit obtained is uniform and bright, pale yellow in color and the title of the deposited alloy is 18 carats.

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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)

Claims (6)

1. Galvanisches Bad für die elektrolytische Ablagerung einer Gold-Kupfer-Cadmium-Zink-Legierung, dadurch gekennzeichnet, dass es einen Goldcyanid-Komplex, einen Kupfercyanid-Komplex, einen Cadmiumcyanid-Komplex, ein organisches Komplexierungsmittel, welches fähig ist, die Cadmiumionen in Abwesenheit von freiem Cyanid zu komplexieren, ein oberflächenaktives Mittel und eine Mischunq von Zinkcyanid oder Kupfercyanid und einem Zink- und Kaliumcyanid-Doppelsalz enthält, in solcher Weise zusammengesetzt ist, dass die Konzentration des gesamten Cyanides, welches an Zink gebunden ist, gleich eins- bis viermal derjenigen des Zinks beträgt.
2. Bad gemäss Anspruch 1, dadurch gekennzeichnet, dass das organische Komplexierungsmittel ein alkalisches Salz einer Säure ist, dessen Molekül ein oder mehrere gebundene Stickstoffatome aufweist, die an eine oder mehrere Methylen-phosphon-Gruppen gebunden sind.
3. Galvanisches Bad gemäss Anspruch 1, dadurch gekennzeichnet, dass das organische Komplexierungsmittel ein Natrium-, Kalium-, Ammonium- oder Aminsalz von Hydroxy-ethyl-iminodiessigsäure, Nitrilo-triessigsäure oder Oxy-carbonyl-ethyl amino-diessigsäure ist.
4. Galvanisches Bad gemäss Anspruch 1, dadurch gekennzeichnet, dass das oberflächenaktive Mittel in Form von Amidopropyl-dimethyl-amino-oxiden oder Dimethyl-amino-oxiden von gesättigten Fettsäuren, von Dimethyl-alkyl-amino-oxiden oder bis-(2-Hydroxy-ethyl)-alkyl-amino-oxiden, in deren Molekül die Alkylgruppe 10 bis 18 Kohlenstoffatome aufweist, vorliegt.
5. Galvanisches Bad nach den Ansprüchen 1 - 4, dadurch gekennzeichnet, dass es 1 bis 20 g/I Gold, 6 bis 70 g/I Kupfer, 0,1 bis 5,0 g/I Cadmium, 1 - 50 g/I Zink, 1 bis 200 g/I Cyanide, die an Zink gebunden sind, 20 bis 200 g/1 Komplexiermittel und 0,1 bis 50 g/I oberflächenaktives Mittel enthält.
6. Galvanisches Verfahren zur Beschichtung mit einer Gold-Kupfer-Cadmium-Zink-Legierung, welche 50 bis 92 % Gold, bezogen auf das Gewicht der Legierung enthält, dadurch gekennzeichnet, dass man das galvanische Bad gemäss einen der Ansprüche 1 - 5 verwendet.
EP19840810428 1983-09-01 1984-08-30 Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads Expired EP0140832B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH4812/83 1983-09-01
CH481283 1983-09-01

Publications (3)

Publication Number Publication Date
EP0140832A2 EP0140832A2 (de) 1985-05-08
EP0140832A3 EP0140832A3 (en) 1985-06-12
EP0140832B1 true EP0140832B1 (de) 1988-01-13

Family

ID=4282973

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840810428 Expired EP0140832B1 (de) 1983-09-01 1984-08-30 Galvanisches Bad für das elekrolytische Absetzen einer Goldlegierung und galvanisches Verfahren für die Verwendung dieses Bads

Country Status (2)

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EP (1) EP0140832B1 (de)
DE (1) DE3468704D1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH662583A5 (fr) * 1985-03-01 1987-10-15 Heinz Emmenegger Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc.
AU7320996A (en) 1995-11-03 1997-05-29 Enthone-Omi Inc Electroplating processes compositions and deposits

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4012294A (en) * 1972-08-10 1977-03-15 Oxy Metal Industries Corporation Gold sulfite baths containing organophosphorous compounds
DE3020765A1 (de) * 1980-05-31 1981-12-10 Degussa Ag, 6000 Frankfurt Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten

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EP0140832A3 (en) 1985-06-12
DE3468704D1 (en) 1988-02-18
EP0140832A2 (de) 1985-05-08

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