EP0384679B1 - Dépôt électrolytique d'alliages d'or - Google Patents

Dépôt électrolytique d'alliages d'or Download PDF

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Publication number
EP0384679B1
EP0384679B1 EP90301749A EP90301749A EP0384679B1 EP 0384679 B1 EP0384679 B1 EP 0384679B1 EP 90301749 A EP90301749 A EP 90301749A EP 90301749 A EP90301749 A EP 90301749A EP 0384679 B1 EP0384679 B1 EP 0384679B1
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EP
European Patent Office
Prior art keywords
bath
gold
copper
cyanide
aqueous bath
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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 - Lifetime
Application number
EP90301749A
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German (de)
English (en)
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EP0384679A1 (fr
Inventor
Rebecca Victoria Green
Peter Wilkinson
Sally Ann Peacey
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BASF Catalysts LLC
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Engelhard Corp
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Publication date
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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 a bath for the electrolytic deposition of a gold-copper alloy, to a method of electroplating articles using such a bath and to electroplated articles obtained by that method.
  • DE-A-2,221,159 discloses the use of electrolytic baths which contain cyanide complexes of gold and copper, cadmium, and a chelating agent, in the presence of free cyanide, and/or a polyoxyalkylene compound, which baths may also contain a soluble selenium or tellurium salt and a buffer salt such as a carbonate or phosphate.
  • US-A-4,687,557 discloses a bath for the electrolytic deposition of a gold-copper-cadmium-zinc alloy, which bath contains cyanide complexes of gold, copper, cadmium and zinc, together with at least one complexing agent and a surface-active agent.
  • These baths may also contain, as an inorganic brightener, a soluble salt containing an element selected from selenium, tellurium, vanadium, arsenic, antimony, thallium, bismuth, titanium, germanium, zirconium, tantalum and niobium.
  • Such brighteners examples of which include sodium selenite and potassium vanadate, are used at low concentrations, in particular 0.01 to 100 mg/l.
  • GB-A-2,151,661 it has been proposed in GB-A-2,151,661 to deposit a yellow to pink-coloured gold-copper-zinc alloy of low carat value from a bath containing at least 2 g/l gold, at least 10 g/l copper and at least 5 g/l zinc in the form of an alkali metal-zinc chelate.
  • concentration of chelate-formers is above 20 g/l, the bath having a pH value within the range 9 to 12 and also containing sodium ions at a concentration greater than 20 g/l and below the solubility limit thereof.
  • US-A-4,617,096 teaches that light yellow, glossy and ductile gold-indium alloys which have a good resistance to gradual corrosion by silver sulfide are obtained from electrolytic (galvanic) baths containing 1 to 20 g/l of gold in the form of alkali metal or ammonium tetracyanoaurate (III), 0.5-50 g/l of indium in the form of a water-soluble indium salt, a buffer or conducting salt and 0.5 to 10 mg/l of selenium and/or tellurium.
  • electrolytic (galvanic) baths containing 1 to 20 g/l of gold in the form of alkali metal or ammonium tetracyanoaurate (III), 0.5-50 g/l of indium in the form of a water-soluble indium salt, a buffer or conducting salt and 0.5 to 10 mg/l of selenium and/or tellurium.
  • Japanese patent application JP62-164889 discloses an electrolytic bath containing 7-16 g/l gold, 2-4 g/l silver and 10-50 g/l copper (each of these metals being in the form of an alkali metal cyanide), 10-100 g/l alkali metal cyanide and, as a brightener, 0.0001-5 g/l tellurium in the form of a water-soluble compound thereof.
  • European patent application EP-A-0 304 315 discloses a bath for the electrolytic deposition of a gold-copper-zinc alloy, which bath contains gold, copper and zinc, each in the form of a cyanide complex thereof, at least one surface-active agent and a water-soluble tellurium salt and/or a water-soluble bismuth salt.
  • the said bath may also comprise a non-cyanide organic complex of zinc, a conductive salt, a depolarizing agent and an alkali metal (or ammonium) cyanide.
  • the present invention provides an aqueous bath for the electrolytic deposition of a gold-copper alloy, which bath contains (a) gold in the form of a cyanide compound, (b) copper in the form of a cyanide compound, (c) tellurium in the form of a water-soluble compound and optionally (d) bismuth in the form of a water-soluble compound, the bath containing less than 0.1g/l, in total, of any other metal in an electrolytically depositable form.
  • the present invention also provides a method of coating a substrate with a gold-copper alloy, wherein the said substrate and an electrode are immersed in a bath according to this invention and an electric current is passed through said bath between the substrate and electrode.
  • the present invention also provides an article having at least one surface that has been coated with a gold-copper alloy by means of such a method.
  • the bath according to the present invention contains gold preferably in the form of a cyanide complex.
  • Preferred complexes are the alkali metal (eg. sodium or potassium) and the ammonium gold cyanides, eg. KAu(CN)2.
  • the gold is present in an amount of from 0.5 to 20 g/l, more preferably from 3.0 to 6.0 g/l.
  • the present baths also contain copper and this may be in the form of a cyanide complex, preferred complexes being the alkali metal (eg. sodium or potassium) and the ammonium copper cyanides, eg. K2Cu(CN)3. Copper oxide, CuO, copper carbonate, CuCO3, or copper cyanide, Cu(CN)2, may, for example, be employed as the source of copper although these may require the presence of sufficient cyanide to solubilize them. Copper cyanide is the preferred source of copper.
  • the copper is present in the bath in an amount of from 0.1 to 30 g/l, more preferably from 10.0 to 20.0 g/l.
  • a further component of the baths according to the present invention is tellurium, in the form of a soluble salt thereof.
  • Suitable salts include the alkali metal, ammonium or amine salts with tellurium-containing anions, eg. sodium tellurite or potassium tellurite.
  • the expression "soluble salt” also extends to complex salts with carboxylic acids, amino acids, aminocarboxylic acids and the like.
  • the tellurium is present in an amount of from 1 to 2,000 mg/l, preferably from 1 to 100 mg/l when the tellurium is in the tetravalent form or from 200 to 2,000 mg/l when the tellurium is in a hexavalent form. It is particularly preferred that the tellurium should be in the tetravalent form and present in an amount of from 5 to 28 ppm (mg/l).
  • the tellurium may be replaced, in part, by bismuth in the form of a water-soluble salt thereof.
  • bismuth has been found to impart corrosion resistance to the gold-copper alloys it has also resulted in alloys of poor (i.e. dull and brownish) appearance. For that reason it is preferred to employ tellurium in the substantial absence of bismuth.
  • tellurium and bismuth if present
  • tellurium may be co-deposited with the gold and copper and, although the Applicant does not wish to be bound or limited by any hypothesis herein, it is believed that this contributes to the corrosion resistance of the alloy deposit despite the substantial absence of zinc or cadmium. This effect could not be predicted from the known use of tellurium or bismuth as a brightener in certain alloys. Nevertheless, the amount of any co-deposited tellurium (and bismuth if present) is very small and the deposited coating therefore is essentially a gold-copper alloy.
  • the baths of the present invention are essentially free of metals (other than gold, copper, bismuth and tellurium) which are in electrolytically depositable form.
  • the bath contains less than 0.1 g/l, preferably less than 0.01 g/l, of total electrolytically depositable metal other than gold, copper, bismuth and tellurium. It is particularly preferred that there should be no deliberate addition to the bath of such other electrolytically depositable metal, eg. cadmium, zinc or silver, although, of course, it is possible that traces of such metals may be introduced as impurities in the main components of the bath, or may dissolve out of the substrate or workpiece to be coated.
  • a bath according to the present invention to contain more than a trace amount of a metal other than gold, copper, bismuth or tellurium, provided that it is in such a form that there is no significant deposition of the metal under the normal conditions of use of the bath.
  • a metal other than gold, copper, bismuth or tellurium for example, it has been found that zinc can be held in solution in the bath by means of a sufficiently strong chelating agent, eg. nitrilotriacetic acid (NTA).
  • NTA nitrilotriacetic acid
  • the baths according to the present invention also contain free cyanide salt selected from alkali metal and ammonium cyanides, amongst which potassium cyanide is particularly preferred.
  • free cyanide salt selected from alkali metal and ammonium cyanides, amongst which potassium cyanide is particularly preferred.
  • such cyanide salt is preferably present in a concentration of up to 20 g/l, more preferably from 5 to 15 g/l.
  • the level of free cyanide is governed by the copper concentration: the higher the copper level the higher should be the level of free cyanide.
  • cyanide ions constitute a powerful complexing agent.
  • free cyanide will generally convert simple cyanide salts, e.g. copper cyanide, into complex salts and may also serve to prevent unwanted deposition of foreign metals (e.g. small amounts of zinc and, possibly, tin or lead which may have entered into solution from a brass substrate).
  • the baths of this invention preferably contain a surface-active or wetting agent. It is possible to employ, singly or in combinations, commercially available products selected from nonionic, anionic, cationic and amphoteric surfactants. In particular, amidopropyldimethylamino oxides of fatty acids, dimethylamino oxides of saturated fatty acids, dimethylalkylamino oxides and bis(2-hydroxyethyl) alkylamino oxides, and the like, may be advantageously employed.
  • ampholytic ion an amidoaminopropionate derivative in the form of the ampholytic ion (zwitterion) having the following formula where R is a C8 to C20 alkyl group and R' is a hydrogen atom or a -CH2COOH residue.
  • R is a C8 to C20 alkyl group
  • R' is a hydrogen atom or a -CH2COOH residue.
  • amphopropionates by way of examples there may be mentioned the cocoamphopropionate and cocoamphocarboxypropionate, which are marketed under the trademark "Miranol”.
  • the surface-active agent is preferably used in an amount of from 0.1 to 20 ml/l, more preferably from 0.5 to 10 ml/l, typically 2 ml/l.
  • a conducting salt may be added, for example sodium, potassium or ammonium salts of carboxylic, hydroxycarboxylic, amino or aminocarboxylic acids, such as acetic, formic, succinic, tartaric, citric, hydroxyacetic, glycolic, malonic, maleic, mandelic, gluconic or heptonic acid.
  • a particularly preferred conducting salt is sodium potassium tartrate (Rochelle salt).
  • the conducting salt if used, is preferably present in an amount of up to 100 g/l, more preferably from 50 to 70 g/l, and typically 60 g/l.
  • the chelating agent NTA may be included in the bath: in addition to, or instead of, NTA any of the other conventional chelating agents such as EDTA may also come into consideration.
  • any of the other conventional chelating agents such as EDTA may also come into consideration.
  • the use of a chelating agent to hold foreign metals in solution is often not necessary since the baths commonly contain free cyanide which, as mentioned above, can prove effective for such a purpose.
  • any of the components of the bath discussed above can, of course, be constituted by a mixture of compounds of the appropriate description. It is, of course, desirable that each component should, in the amount used, be completely soluble or solubilized in the aqueous medium of the bath.
  • the pH of the bath is preferably from 7 to 12, more preferably from 9.5 to 10.5.
  • the baths according to the present invention may be used in a conventional manner for the deposition of the gold-containing alloy onto the appropriate surfaces ofarticles to be plated.
  • the bath will normally be operated at a temperature between 50° and 75°C, especially at a temperature of from 55 to 65°C.
  • the current density will usually be from 0.5 to 2.5 A/dm2, preferably from 0.6 to 1.1 A/dm2.
  • the anode(s) will be of platinum or platinized titanium.
  • a depolarising agent it is possible to dispense with the use of a depolarising agent, although the use of such an agent (as described in EP-A-0 304 315) may be advisable when using anodes of stainless steel or the like and/or when using high current densities.
  • the pink alloys that can be obtained in the practice of this invention are suitable as decorative coating on spectacle frames.
  • the present invention is illustrated in and by the following specific examples.
  • small polished brass panels were used as the substrates (cathodes) onto which the gold-containing alloy was electrolytically deposited, using a platinum anode.
  • the corrosion resistance of the resultant alloy deposit or coating was measured by various tests, including the following.
  • the nitric acid test was carried out by placing one drop of cold 50% v/v HNO3 on the back of the test panel. To pass this test, there shall be no attack on the deposit after 30 seconds have elapsed.
  • the copper chloride test is carried out by placing one drop of saturated copper chloride solution on the back of the test panel. To pass this test, there shall be no attack on the deposit after 30 seconds have elapsed.
  • An aqueous bath was prepared in accordance with the following formulation: Gold (added as potassium gold cyanide) 3 g/l Copper (added as copper cyanide) 14 g/l Potassium cyanide 25 g/l Sodium potassium tartrate 60 g/l Tellurium (added as sodium tellurite) 20 mg/l Cu 84 (surfactant) 2 ml/l
  • a gold-copper alloy was deposited onto test panels under the following operating conditions: pH 10.5; current density 0.8 A/dm2; temperature 60°C. A 16.8 carat deposit was obtained that was pale pink and fully bright in appearance. The corrosion resistance in the nitric acid test and the copper chloride test was deemed to be a borderline pass.
  • Example 1 The procedures of Example 1 were followed except that the concentration of gold (added as potassium gold cyanide) was 5 g/l. A 21.8 carat deposit was obtained which was fully bright in appearance but of a paler pink colour than the deposit obtained in Example 1. The deposit passed both the nitric acid test and the copper chloride test for corrosion resistance.
  • Example 1 The procedures of Example 1 were followed except that the concentration of the gold (added as potassium gold cyanide) was 7 g/l. A 23.0 carat deposit of alloy was obtained, which was gold in colour. The deposit passed both the nitric acid test and the copper chloride test for corrosion resistance.
  • a bath of the following formulation was prepared: Gold (added as potassium gold cyanide) 7 g/l Copper (added as copper cyanide) 20 g/l Potassium cyanide 30 g/l Sodium potassium tartrate 60 g/l Zinc carbonate 9.5 g/l Nitrilotriacetic acid 20 g/l Cu 84 (wetting agent) 2 ml/l Tellurium (added as sodium tellurite) 15 mg/l
  • the copper cyanide formed a complex with (and was hence solublized by) cyanide from the KCN, thereby reducing the free cyanide content in the bath to 2.5 g/l. Alloy was electrolytically deposited on test panels using a bath of the above formulation under the following operating conditions: pH 10.5; current density 0.8 A/dm2; bath temperature 60°C.
  • Example 4 The procedures of Example 4 were repeated except that the amount of zinc carbonate was increased to 19 g/l and the amount of NTA was increased to 40 g/l. These two ingredients were reacted in water to form a Zn-NTA complex which was then added to the bath, giving a concentration of zinc (Zn) of 5 g/l. The resultant bath had a pH of 10.0.
  • Example 4 The procedures of Example 4 were repeated, except that the content of free cyanide was increased from 2.5 to 16.5 g/l.
  • An aqueous bath was prepared in accordance with the following formulation: Gold (added as potassium gold cyanide) 5 g/l Copper (added as copper cyanide) 21 g/l Potassium cyanide 35 g/l Sodium potassium tartrate 60 g/l Tellurium (added as sodium tellurite) 20 mg/l Cu 84 (surfactant) 2 ml/l
  • a gold-copper alloy was deposited onto test panels under the following operating conditions: pH 10.0; current density 0.8 A/dm2; temperature 60°C.
  • a gold-copper alloy deposit of 19.8 carat was obtained.
  • the deposit was fully bright and pale pink in appearance and passed the copper chloride test for corrosion resistance.
  • the alloy deposit also showed corrosion resistance in the nitric acid test, the conventional sweat test and the Leeds and Clark test.
  • aqueous bath disclosed in any of the preceding Examples may be modified by the inclusion of saccharin in an amount of 2 g/l.
  • saccharin has been found to reduce slightly the internal stress of the deposits obtained, to improve the appearance of the deposits and to widen slightly the bright plating range; it is especially useful in electroforming. It is envisaged that this additive will commonly be used in an amount of from 0.5 to 5 g/l.

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (19)

  1. Bain aqueux pour le dépôt électrolytique d'un alliage d'or et de cuivre, ce bain contenant (a) de l'or sous la forme d'un composé dérivé de cyanure, (b) du cuivre sous la forme d'un composé dérivé de cyanure, (c) du tellure sous la forme d'un composé soluble dans l'eau, et éventuellement (d) du bismuth sous la forme d'un composé soluble dans l'eau, le bain contenant moins de 0,1 g/litre au total, d'un autre métal quelconque sous forme déposable par électrolyse.
  2. Bain aqueux selon la revendication 1, caractérisé en ce que l'or est présent dans le bain sous la forme d'un complexe dérivé de cyanure, de préférence, un cyanure de métal alcalin ou d'or et d'ammonium.
  3. Bain aqueux selon la revendication 1 ou 2, caractérisé en ce que l'or est présent selon une concentration de 0,5 à 20 g/litre.
  4. Bain aqueux selon la revendication 1, 2 ou 3, caractérisé en ce que le cuivre est présent dans le bain sous la forme d'un complexe dérivé de cyanure, de préférence un cyanure de métal alcalin, ou de cuivre et d'ammonium.
  5. Bain aqueux selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le cuivre est présent selon une concentration de 0,1 à 30 g/litre.
  6. Bain aqueux selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le tellure est introduit dans le bain sous la forme d'un tellurite de métal alcalin, d'ammonium, ou dérivé d'amine.
  7. Bain aqueux selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le tellure est présent selon une concentration de 1 à 2.000 mg/litre.
  8. Bain aqueux selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il contient également un agent tensioactif.
  9. Bain aqueux selon la revendication 8, caractérisé en ce que l'agent tensioactif est présent selon une concentration de 0,1 à 20 ml/litre.
  10. Bain aqueux selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il contient également un sel cyanure libre choisi parmi les cyanures de métal alcalin et d'ammonium.
  11. Bain aqueux selon la revendication 10, caractérisé en ce que le sel cyanure libre est présent dans le bain selon une concentration allant jusqu'à 20 g/litre.
  12. Bain aqueux selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'il contient un sel conducteur choisi parmi les sels dérivés de métal alcalin et d'ammonium d'acides carboxyliques, hydroxycarboxyliques, aminés ou aminocarboxyliques, à une concentration allant jusqu'à 100 g/litre.
  13. Bain aqueux selon la revendication 12, caractérisé en ce que le sel conducteur est le tartrate de sodium et de potassium.
  14. Bain aqueux selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'il contient du zinc suffisamment fortement chélaté ou complexé pour empêcher son dépôt électrolytique.
  15. Bain aqueux selon l'une quelconque des revendications 1 à 14, caractérisé en ce que le bain contient moins de 0,01 g/litre au total, d'un métal déposable par électrolyse autre que l'or, le cuivre, le tellure ou le bismuth.
  16. Bain aqueux selon l'une quelconque des revendications 1 à 15, caractérisé en ce que le bismuth est absent ou à peu près absent.
  17. Procédé de revêtement d'un substrat avec un alliage d'or et de cuivre, selon lequel le substrat et une électrode sont immergés dans un bain, et on fait passer un courant électrique à travers ce bain entre le substrat et l'électrode, caractérisé en ce que le bain contient (a) de l'or sous la forme d'un composé dérivé de cyanure, (b) du cuivre sous la forme d'un composé dérivé de cyanure, (c) du tellure sous la forme d'un composé soluble dans l'eau et éventuellement (d) du bismuth sous la forme d'un composé soluble dans l'eau, le bain contenant moins de 0,1 g/litre au total d'un quelconque autre métal sous forme déposable par électrolyse.
  18. Procédé selon la revendication 17, caractérisé en ce que le bain est tel que cela est défini dans les revendications 2 à 16.
  19. Article comportant au moins une surface qui a été revêtue avec un alliage d'or et de cuivre selon un procédé tel que défini dans la revendication 17 ou 18.
EP90301749A 1989-02-20 1990-02-19 Dépôt électrolytique d'alliages d'or Expired - Lifetime EP0384679B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898903818A GB8903818D0 (en) 1989-02-20 1989-02-20 Electrolytic deposition of gold-containing alloys
GB8903818 1989-02-20

Publications (2)

Publication Number Publication Date
EP0384679A1 EP0384679A1 (fr) 1990-08-29
EP0384679B1 true EP0384679B1 (fr) 1994-08-17

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EP90301749A Expired - Lifetime EP0384679B1 (fr) 1989-02-20 1990-02-19 Dépôt électrolytique d'alliages d'or

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EP (1) EP0384679B1 (fr)
AT (1) ATE110124T1 (fr)
DE (1) DE69011549T2 (fr)
GB (1) GB8903818D0 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011056318B3 (de) * 2011-12-13 2013-04-18 Doduco Gmbh Elektrolytisches Bad zum Abscheiden einer Goldkupferlegierung

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3170924A1 (fr) 2007-04-19 2017-05-24 Enthone, Inc. Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre
CH710184B1 (fr) 2007-09-21 2016-03-31 Aliprandini Laboratoires G Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques.
EP2312021B1 (fr) 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques
IT201900001769A1 (it) * 2019-02-07 2020-08-07 Italfimet Srl Lega d'oro rosa, procedimento di realizzazione ed uso.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3319772A1 (de) * 1983-05-27 1984-11-29 Schering AG, 1000 Berlin und 4709 Bergkamen Bad fuer die galvanische abscheidung von goldlegierungen
DE3505473C1 (de) * 1985-02-16 1986-06-05 Degussa Ag, 6000 Frankfurt Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsueberzuegen
CH662583A5 (fr) * 1985-03-01 1987-10-15 Heinz Emmenegger Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011056318B3 (de) * 2011-12-13 2013-04-18 Doduco Gmbh Elektrolytisches Bad zum Abscheiden einer Goldkupferlegierung
EP2604727A1 (fr) 2011-12-13 2013-06-19 DODUCO GmbH Bain électrolytique pour la séparation d'un alliage or-cuivre

Also Published As

Publication number Publication date
GB8903818D0 (en) 1989-04-05
ATE110124T1 (de) 1994-09-15
DE69011549D1 (de) 1994-09-22
EP0384679A1 (fr) 1990-08-29
DE69011549T2 (de) 1995-04-06

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