EP2312021B1 - Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals - Google Patents

Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals Download PDF

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Publication number
EP2312021B1
EP2312021B1 EP09173198.4A EP09173198A EP2312021B1 EP 2312021 B1 EP2312021 B1 EP 2312021B1 EP 09173198 A EP09173198 A EP 09173198A EP 2312021 B1 EP2312021 B1 EP 2312021B1
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EP
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Prior art keywords
bath
copper
gold
cyanide
silver
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Application number
EP09173198.4A
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German (de)
French (fr)
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EP2312021A1 (en
Inventor
Christophe Henzirohs
Guido Plankert
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Swatch Group Research and Development SA
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Swatch Group Research and Development SA
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Priority to EP09173198.4A priority Critical patent/EP2312021B1/en
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to KR1020100100585A priority patent/KR101297476B1/en
Priority to CN201010552012.7A priority patent/CN102041527B/en
Priority to US12/905,788 priority patent/US20110089040A1/en
Priority to JP2010232903A priority patent/JP5563421B2/en
Publication of EP2312021A1 publication Critical patent/EP2312021A1/en
Priority to HK11111618.6A priority patent/HK1157415A1/en
Priority to US14/452,364 priority patent/US9567684B2/en
Priority to US15/898,330 priority patent/US20180171499A1/en
Application granted granted Critical
Publication of EP2312021B1 publication Critical patent/EP2312021B1/en
Priority to US16/847,699 priority patent/US20200240030A1/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • 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
    • 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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • the invention relates to electrolytic deposition in the form of a thick layer gold alloy as well as its manufacturing process.
  • the deposits obtained by these known methods have cadmium contents of between 1 and 10%.
  • Cadmium facilitates the deposition of thick layers, that is to say between 1 and 800 microns and makes it possible to obtain an alloy of yellow color by reducing the quantity of copper contained in the alloy; however cadmium is extremely toxic and banned in some countries.
  • the object of the present invention is to overcome all or part of the drawbacks mentioned above, a manufacturing process allowing the deposition in a thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.
  • the invention relates to a process for the galvanoplastic deposition of a gold alloy on an electrode immersed in a bath comprising metal gold in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, free cyanide, the alloying metals being copper in the form of double cyanide of copper and potassium, and silver in cyanide form, characterized in that the bath respects a percentage by weight proportion of 9.08% of gold, of 90.85% of copper and of 0.07% of silver making it possible to deposit on the electrode a gold alloy of the shiny mirror yellow type, said bath being free of cadmium.
  • the invention relates to an electrolytic deposition of a gold alloy of shade 3N which, surprisingly, comprises main compounds Au-Cu-Ag whose proportions are not known to obtain shade 3N, that is to say - say bright yellow.
  • a gold alloy free of toxic metals or metalloids, in particular free of cadmium, of 3N yellow tint, with a thickness of 200 microns, of excellent gloss and having a very high resistance to wear and tarnishing.
  • the electrolysis is preferably followed by a heat treatment at a temperature between 200 and 450 degrees Celsius for 1 to 30 minutes in order to obtain a deposit of optimal quality.
  • the bath according to the invention makes it possible to obtain a deposit substantially in a proportion of 75% gold, 21% copper and 4% silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion from the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% gold, 12.5% copper and 12.5% silver.
  • the bath can also contain a brightener.
  • a brightener This is preferably a derivative of butynediol, a pyridinio-propanesulfonate or a mixture of the two, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.
  • the electrolytic bath contained in a polypropylene or PVC tank with heat-insulating coating.
  • the bath is heated by quartz, PTFE, porcelain or stabilized stainless steel immersion heaters. Good cathodic agitation and circulation of the electrolyte must be maintained.
  • the anodes are made of platinum titanium, stainless steel, ruthenium, iridium or alloys of the latter two.
  • the bath can contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantities.
  • the wetting agent can be of any type capable of wetting in an alkaline cyanide medium.

Description

Domaine de l'inventionField of the invention

L'invention se rapporte à dépôt électrolytique sous forme d'un alliage d'or en couche épaisse ainsi que son procédé de fabrication.The invention relates to electrolytic deposition in the form of a thick layer gold alloy as well as its manufacturing process.

Arrière plan de l'inventionBackground of the invention

Dans le domaine décoratif du placage, on connaît des procédés pour la production de dépôts électrolytiques d'or, de couleur jaune, dont le titre est supérieur ou égal à 9 carats, ductile à une épaisseur de 10 microns, et de grande résistance au ternissement. Ces dépôts sont obtenus par une électrolyse dans un bain galvanique alcalin contenant, en plus de l'or et du cuivre, du cadmium à raison de 0,1 à 3 g.l-1. De tels dépôts sont, par exemple, décrits dans le document GB 1,400,492 .In the decorative field of plating, processes are known for the production of electrolytic deposits of gold, of yellow color, the title of which is greater than or equal to 9 carats, ductile to a thickness of 10 microns, and of great resistance to tarnishing. . These deposits are obtained by electrolysis in an alkaline galvanic bath containing, in addition to gold and copper, cadmium at a rate of 0.1 to 3 gl -1 . Such deposits are, for example, described in the document GB 1,400,492 .

Les dépôts obtenus par ces procédés connus présentent cependant des teneurs en cadmium comprises entre 1 et 10 %. Le cadmium facilite le dépôt de couches épaisses, c'est-à-dire entre 1 et 800 microns et permet d'obtenir un alliage de couleur jaune en diminuant la quantité de cuivre contenue dans l'alliage; toutefois le cadmium est extrêmement toxique et interdit dans certains pays.The deposits obtained by these known methods, however, have cadmium contents of between 1 and 10%. Cadmium facilitates the deposition of thick layers, that is to say between 1 and 800 microns and makes it possible to obtain an alloy of yellow color by reducing the quantity of copper contained in the alloy; however cadmium is extremely toxic and banned in some countries.

On connaît aussi des alliages d'or de 18 carats sans cadmium, contenant du cuivre et du zinc. Cependant, ces dépôts sont de teinte trop rose (titre trop riche en cuivre). Enfin, ces dépôts ont une mauvaise résistance à la corrosion ce qui implique un ternissement rapide. De tels dépôts sont, par exemple, décrits dans le document EP 0416342 A1 .Also known are 18-carat gold alloys without cadmium, containing copper and zinc. However, these deposits are too pink in color (title too rich in copper). Finally, these deposits have poor corrosion resistance which implies rapid tarnishing. Such deposits are, for example, described in the document EP 0416342 A1 .

Résumé de l'inventionSummary of the invention

Le but de la présente invention est de pallier tout ou partie les inconvénients cités précédemment un procédé de fabrication permettant le dépôt en couche épaisse d'un alliage d'or de couleur jaune n'ayant ni de zinc ni de cadmium comme constituants principaux.The object of the present invention is to overcome all or part of the drawbacks mentioned above, a manufacturing process allowing the deposition in a thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.

A cet effet, l'invention se rapporte à un procédé de dépôt galvanoplastique d'un alliage d'or sur une électrode plongée dans un bain comportant de l'or métal sous forme d'aurocyanure alcalin, des composés organométalliques, un mouillant, un complexant, du cyanure libre, les métaux d'alliage étant du cuivre sous forme de cyanure double de cuivre et potassium, et de l'argent sous forme cyanure caractérisé en ce que le bain respecte une proportion en pourcentage en poids de 9,08 % d'or, de 90,85 % de cuivre et de 0,07 % d'argent permettant de déposer sur l'électrode un alliage d'or du type jaune miroir brillant ledit bain étant exempt de cadmium.To this end, the invention relates to a process for the galvanoplastic deposition of a gold alloy on an electrode immersed in a bath comprising metal gold in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, free cyanide, the alloying metals being copper in the form of double cyanide of copper and potassium, and silver in cyanide form, characterized in that the bath respects a percentage by weight proportion of 9.08% of gold, of 90.85% of copper and of 0.07% of silver making it possible to deposit on the electrode a gold alloy of the shiny mirror yellow type, said bath being free of cadmium.

Conformément à d'autres caractéristiques avantageuses de l'invention :

  • le bain comporte de 1 à 10 g.l-1 d'or métal sous forme d'aurocyanure alcalin ;
  • le bain comporte de 30 à 80 g.l-1 de cuivre métal sous forme de cyanure double alcalin ;
  • le bain comporte de 10 mg.l-1 à 1 g.l-1 d'argent métal sous forme complexé ;
  • le mouillant comporte une concentration comprise entre 0,05 et 10 ml.l-1 ;
  • le mouillant est choisi parmi les types polyoxyalcoilenique, étherphosphate, lauryl sulfate, diaméthydodécylamine-N-oxide, diméthyldodécyl ammonium propane sulfonate ;
  • le bain comporte une amine de concentration comprise entre 0,01 et 5 ml.l-1 ;
  • le bain comporte un dépolarisant de concentration comprise entre 0,1 mg.l-1 à 20 mg.l-1 ;
  • le bain comporte des sels conducteurs du type phosphates, carbonates, citrates, sulfates, tartrates, gluconates et/ou phosphonates ;
  • la température du bain est maintenue entre 50 et 80°C ;
  • le pH du bain est maintenu entre 8 et 12 ;
  • le procédé est réalisé à une densité de courant comprise entre 0,05 et 1,5 A.dm-2 ;
  • le bain respecte une proportion de 9,08 % d'or, de 90,85 % de cuivre et de 0,07 % d'argent.
In accordance with other advantageous features of the invention:
  • the bath comprises from 1 to 10 gl -1 of metal gold in the form of alkaline aurocyanide;
  • the bath comprises from 30 to 80 gl -1 of copper metal in the form of double alkaline cyanide;
  • the bath comprises from 10 mg.l -1 to 1 gl -1 of metal silver in complexed form;
  • the wetting agent has a concentration of between 0.05 and 10 ml.l -1 ;
  • the wetting agent is chosen from polyoxyalcoilenic, etherphosphate, lauryl sulfate, diamethydodecylamine-N-oxide, dimethyldodecyl ammonium propane sulfonate types;
  • the bath comprises an amine of concentration between 0.01 and 5 ml.l -1 ;
  • the bath comprises a depolarizer with a concentration of between 0.1 mg.l -1 to 20 mg.l -1 ;
  • the bath contains conductive salts of the phosphates, carbonates, citrates, sulfates, tartrates, gluconates and / or phosphonates type;
  • the bath temperature is maintained between 50 and 80 ° C;
  • the pH of the bath is maintained between 8 and 12;
  • the process is carried out at a current density of between 0.05 and 1.5 A.dm -2 ;
  • the bath respects a proportion of 9.08% gold, 90.85% copper and 0.07% silver.

Description détaillée des modes de réalisation préférésDetailed description of preferred embodiments

L'invention concerne un dépôt électrolytique d'un alliage d'or de teinte 3N qui, de manière surprenante, comporte des composés principaux Au-Cu-Ag dont les proportions ne sont pas connues pour obtenir la teinte 3N, c'est-à-dire jaune brillant.The invention relates to an electrolytic deposition of a gold alloy of shade 3N which, surprisingly, comprises main compounds Au-Cu-Ag whose proportions are not known to obtain shade 3N, that is to say - say bright yellow.

Dans un exemple de dépôt ci-dessus, on a un alliage d'or, exempt de métaux ou métalloïdes toxiques, en particulier exempt de cadmium, de teinte 3N jaune, d'une épaisseur de 200 microns, de brillance excellente et ayant une très grande résistance à l'usure et au ternissement.In an example of deposit above, there is a gold alloy, free of toxic metals or metalloids, in particular free of cadmium, of 3N yellow tint, with a thickness of 200 microns, of excellent gloss and having a very high resistance to wear and tarnishing.

Ce dépôt est obtenu par une électrolyse dans un bain électrolytique du type :

  • Au : 5,5 g.l-1
  • Cu : 55 g.l-1
  • Ag : 40 mg.l-1
  • KCN : 26 g.l-1
  • pH : 10,5
  • Température : 65°C
  • Densité de Courant : 0,3 A.dm-2
  • Mouillant : 0,05 ml.l-1 NN-Diméthyldodecyl N-Oxide
  • Iminodiacétique : 20 g.l-1
  • Ethylènediamine : 0.5 ml.l-1
  • Gallium, sélénium ou tellure : 10 mg.l-1
This deposit is obtained by electrolysis in an electrolytic bath of the type:
  • Au: 5.5 gl -1
  • Cu: 55 gl -1
  • Ag: 40 mg.l -1
  • KCN: 26 gl -1
  • pH: 10.5
  • Temperature: 65 ° C
  • Current Density: 0.3 A.dm -2
  • Wetting agent: 0.05 ml.l -1 NN-Dimethyldodecyl N-Oxide
  • Iminodiacetic: 20 gl -1
  • Ethylenediamine: 0.5 ml.l -1
  • Gallium, selenium or tellurium: 10 mg.l -1

L'électrolyse est de préférence suivie d'un traitement thermique à une température comprise entre 200 et 450 degrés Celsius pendant 1 à 30 minutes afin d'obtenir un dépôt de qualité optimale.The electrolysis is preferably followed by a heat treatment at a temperature between 200 and 450 degrees Celsius for 1 to 30 minutes in order to obtain a deposit of optimal quality.

Ces conditions permettent d'obtenir un rendement cathodique de 98 mg.A.min-1 avec une vitesse de déposition d'environ 10 µm par heure dans le cas de l'exemple.These conditions make it possible to obtain a cathodic yield of 98 mg.A.min -1 with a deposition rate of approximately 10 μm per hour in the case of the example.

Ainsi, de manière étonnante, le bain selon l'invention permet d'obtenir un dépôt sensiblement selon une proportion de 75 % d'or, de 21 % de cuivre et de 4 % d'argent correspondant à un dépôt de teinte 3N à 18 carats qui est une proportion très différente des dépôts électrolytiques habituels pour cette teinte qui sont plutôt des dépôts selon sensiblement 75 % d'or, 12,5 % de cuivre et 12,5 % d'argent.Thus, surprisingly, the bath according to the invention makes it possible to obtain a deposit substantially in a proportion of 75% gold, 21% copper and 4% silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion from the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% gold, 12.5% copper and 12.5% silver.

Le bain peut contenir en outre un brillanteur. Celui-ci est, de préférence, un dérivé du butynediol, un pyridinio-propanesulfonate ou un mélange des deux, un sel d'étain, de l'huile de castor sulfonées, du méthylimidozole, de l'acide dithiocarboxylique tels que du thiourée, de l'acide thiobarbiturique, de l'imidazolidinthione ou de l'acide thiomalique.The bath can also contain a brightener. This is preferably a derivative of butynediol, a pyridinio-propanesulfonate or a mixture of the two, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.

Dans ces exemples, le bain électrolytique, contenu dans une cuve en polypropylène ou en PVC avec revêtement calorifuge. Le chauffage du bain est réalisé grâce à des thermo-plongeurs en quartz, en PTFE, en porcelaine ou en acier inoxydable stabilisé. Une bonne agitation cathodique ainsi qu'une circulation de l'électrolyte doit être maintenue. Les anodes sont en titane platiné, en acier inoxydable, en ruthénium, en iridium ou alliages de ces deux derniers.In these examples, the electrolytic bath, contained in a polypropylene or PVC tank with heat-insulating coating. The bath is heated by quartz, PTFE, porcelain or stabilized stainless steel immersion heaters. Good cathodic agitation and circulation of the electrolyte must be maintained. The anodes are made of platinum titanium, stainless steel, ruthenium, iridium or alloys of the latter two.

Bien entendu, la présente invention ne se limite pas à l'exemple illustré mais est susceptible de diverses variantes et modifications qui apparaîtront à l'homme de l'art. En particulier, le bain peut contenir les métaux suivants Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi en quantité négligeable.Of course, the present invention is not limited to the example illustrated but is capable of various variants and modifications which will appear to those skilled in the art. In particular, the bath can contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantities.

De plus, le mouillant peut être de tout type susceptible de mouiller en milieu cyanuré alcalin.In addition, the wetting agent can be of any type capable of wetting in an alkaline cyanide medium.

Claims (12)

  1. Method for the galvanoplastic deposition of a gold alloy on an electrode dipped into a bath including gold metal in alkaline aurocyanide form, organometallic compounds, a wetting agent, a sequestering agent and free cyanide, the alloy metals being copper, in double copper and potassium cyanide form, and silver, in cyanide form, characterized in that the bath respects a proportion of 9.08 wt% gold, 90.85 wt% copper and 0.07 wt% silver allowing a mirror-bright yellow gold alloy to be deposited on the electrode, said bath not containing cadmium.
  2. Method according to claim 1, characterized in that the bath includes 1 to 10 g.l-1 of gold metal in alkaline aurocyanide form.
  3. Method according to the claim 1 or 2, characterized in that the bath includes from 30 to 80 g.l-1 of copper metal in double alkaline cyanide form.
  4. Method according to any of the preceding claims, characterized in that the bath includes from 10 mg.l-1 to 1 g.l-1 of silver metal in complex form.
  5. Method according to any of the preceding claims, characterized in that the wetting agent includes a concentration of between 0.05 and 10 ml.l-1.
  6. Method according to claim 1 or 5, characterized in that the wetting agent is chosen from among poly-oxy-alkylenic, ether phosphate, lauryl sulphate, dimethyldodecylamine-N-oxide, dimethyl(dodecyl) ammonium propane sulfonate types.
  7. Method according to any of the preceding claims, characterized in that the bath includes a concentration of amine of between 0.01 and 5 ml.l-1.
  8. Method according to any of the preceding claims, characterized in that the bath includes a concentration of depolariser of between 0.1 mg.l-1 to 20 mg.l-1.
  9. Method according to any of the preceding claims, characterized in that the bath includes phosphate, carbonate, citrate, sulphate, tartrate, gluconate and/or phosphonate type conductive salts.
  10. Method according to any of the preceding claims, characterized in that the temperature of the bath is kept between 50 and 80°C.
  11. Method according to any of the preceding claims, characterized in that the pH of the bath is kept between 8 and 12.
  12. Method according to any of the preceding claims, characterized in that the method is performed at a current density of between 0.05 and 1.5 A.dm-2.
EP09173198.4A 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals Active EP2312021B1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP09173198.4A EP2312021B1 (en) 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
CN201010552012.7A CN102041527B (en) 2009-10-15 2010-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
US12/905,788 US20110089040A1 (en) 2009-10-15 2010-10-15 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
JP2010232903A JP5563421B2 (en) 2009-10-15 2010-10-15 Method for obtaining yellow gold alloy deposits by electroplating without using toxic metals
KR1020100100585A KR101297476B1 (en) 2009-10-15 2010-10-15 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals
HK11111618.6A HK1157415A1 (en) 2009-10-15 2011-10-27 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals
US14/452,364 US9567684B2 (en) 2009-10-15 2014-08-05 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US15/898,330 US20180171499A1 (en) 2009-10-15 2018-02-16 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US16/847,699 US20200240030A1 (en) 2009-10-15 2020-04-14 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP09173198.4A EP2312021B1 (en) 2009-10-15 2009-10-15 Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals

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EP2312021A1 EP2312021A1 (en) 2011-04-20
EP2312021B1 true EP2312021B1 (en) 2020-03-18

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EP (1) EP2312021B1 (en)
JP (1) JP5563421B2 (en)
KR (1) KR101297476B1 (en)
CN (1) CN102041527B (en)
HK (1) HK1157415A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2505691B1 (en) * 2011-03-31 2014-03-12 The Swatch Group Research and Development Ltd. Process for obtaining a gold alloy deposit of 18 carat 3N
WO2018066007A1 (en) * 2016-10-06 2018-04-12 Valmet Plating S.R.L. A galvanic and thermal process to obtain the coloration of metals, in particular precious metals
CN107299364A (en) * 2017-06-07 2017-10-27 常州富思通管道有限公司 A kind of zinc-plating brightener and preparation method thereof

Family Cites Families (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2127676A (en) * 1938-04-21 1938-08-23 Claude H Coleman Process of tempering gold and silver alloys
US2141157A (en) * 1938-08-23 1938-12-20 Metals & Controls Corp Alloy
US2229463A (en) * 1939-10-21 1941-01-21 Handy & Harman Alloy
US2596454A (en) * 1949-09-10 1952-05-13 Metals & Controls Corp Gold alloys
US2660554A (en) * 1950-11-10 1953-11-24 Barnet D Ostrow Bright gold and gold alloy plating baths
CH286123A (en) * 1952-05-08 1952-10-15 Spreter Victor Bath for the galvanic deposition of gold alloys.
US2976180A (en) * 1957-12-17 1961-03-21 Hughes Aircraft Co Method of silver plating by chemical reduction
FR1259407A (en) 1960-03-10 1961-04-28 Maison Murat Electrolytic bath for thick deposit of gold-copper alloy
DE1460993A1 (en) 1965-07-23 1970-07-23 Kieninger & Obergfell Electrical program control device, preferably for electrical household appliances, especially washing machines and dishwashers
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process
GB1156186A (en) 1966-09-26 1969-06-25 Sel Rex Corp Gold Plating
BE743946A (en) 1969-01-07 1970-05-28
US3642589A (en) * 1969-09-29 1972-02-15 Fred I Nobel Gold alloy electroplating baths
US3666640A (en) * 1971-04-23 1972-05-30 Sel Rex Corp Gold plating bath and process
DE2121150C3 (en) 1971-04-24 1980-08-21 Schering Ag, 1000 Berlin Und 4619 Bergkamen Process for the electrodeposition of gold alloys
CH529843A (en) 1971-07-09 1972-10-31 Oxy Metal Finishing Europ S A Bath for the electrolytic deposition of gold alloys and its use in electroplating
FR2181455B1 (en) * 1972-04-25 1974-08-30 Parker Ste Continentale
DE2244434C3 (en) * 1972-09-06 1982-02-25 Schering Ag, 1000 Berlin Und 4619 Bergkamen Aqueous bath for the galvanic deposition of gold and gold alloys
US3834879A (en) * 1973-05-11 1974-09-10 J Chin Plated coins
JPS6014115B2 (en) * 1977-07-05 1985-04-11 オクシ メタル インダストリ−ズ コ−ポレ−シヨン Shiny low karat silver-gold electrodeposition
CH621367A5 (en) 1977-07-08 1981-01-30 Systemes Traitements Surfaces Electrolytic bath for plating gold-copper-cadmium alloys and its use in galvanoplasty
JPS5433834A (en) * 1977-08-22 1979-03-12 Citizen Watch Co Ltd Golddcopper alloy plating solution
CH622829A5 (en) * 1977-08-29 1981-04-30 Systemes Traitements Surfaces
FR2405312A1 (en) 1977-10-10 1979-05-04 Oxy Metal Industries Corp Bath for electrodeposition of gold-zinc alloys - contains alkali sulphite, gold-sulphite complex, zinc salt, complex or chelate, complexing or chelating agent and metal
US4168214A (en) * 1978-06-14 1979-09-18 American Chemical And Refining Company, Inc. Gold electroplating bath and method of making the same
DE3020765A1 (en) * 1980-05-31 1981-12-10 Degussa Ag, 6000 Frankfurt ALKALINE BATH FOR GALVANIC DEPOSITION OF LOW-CARAINE PINK TO YELLOW-COLORED GOLD ALLOY LAYERS
GB8334226D0 (en) * 1983-12-22 1984-02-01 Learonal Uk Ltd Electrodeposition of gold alloys
US4626324A (en) 1984-04-30 1986-12-02 Allied Corporation Baths for the electrolytic deposition of nickel-indium alloys on printed circuit boards
CH662583A5 (en) * 1985-03-01 1987-10-15 Heinz Emmenegger GALVANIC BATH FOR THE ELECTROLYTIC DEPOSITION OF GOLD-COPPER-CADMIUM-ZINC ALLOYS.
JPS62164890A (en) * 1986-01-16 1987-07-21 Seiko Instr & Electronics Ltd Gold-silver-copper alloy plating solution
JPS62164889A (en) * 1986-01-16 1987-07-21 Seiko Instr & Electronics Ltd Gold-silver-copper alloy plating solution
JPH067210B2 (en) * 1986-08-12 1994-01-26 沖電気工業株式会社 Plug-in optical connector
ATE86313T1 (en) * 1987-08-21 1993-03-15 Engelhard Ltd BATH FOR ELECTROPLATING A GOLD-COPPER-ZINC ALLOY.
JPH01247570A (en) 1988-03-29 1989-10-03 Furukawa Electric Co Ltd:The Formation of film of multicomponent substance by beam sputtering
GB8903818D0 (en) 1989-02-20 1989-04-05 Engelhard Corp Electrolytic deposition of gold-containing alloys
DE3929569C1 (en) * 1989-09-06 1991-04-18 Degussa Ag, 6000 Frankfurt, De
US5045411A (en) * 1990-01-10 1991-09-03 P.M. Refining, Inc. Alloy compositions
GB2242200B (en) * 1990-02-20 1993-11-17 Omi International Plating compositions and processes
CH680927A5 (en) 1990-10-08 1992-12-15 Metaux Precieux Sa
US5085744A (en) * 1990-11-06 1992-02-04 Learonal, Inc. Electroplated gold-copper-zinc alloys
US5244593A (en) * 1992-01-10 1993-09-14 The Procter & Gamble Company Colorless detergent compositions with enhanced stability
US5256275A (en) * 1992-04-15 1993-10-26 Learonal, Inc. Electroplated gold-copper-silver alloys
JPH067210A (en) * 1992-06-29 1994-01-18 Mitsubishi Materials Corp Method for manufacturing metallic article having inclined pattern
US5340529A (en) * 1993-07-01 1994-08-23 Dewitt Troy C Gold jewelry alloy
CA2235408A1 (en) * 1995-11-03 1997-05-15 Enthone-Omi, Inc. Electroplating processes compositions and deposits
JP2832344B2 (en) * 1996-05-21 1998-12-09 大蔵省造幣局長 Manufacturing method of plated body
DE19629658C2 (en) 1996-07-23 1999-01-14 Degussa Cyanide-free galvanic bath for the deposition of gold and gold alloys
US6814850B1 (en) * 1999-06-17 2004-11-09 Umicore Galvanotechnik Gmbh Acid bath for electrodeposition of glossy gold and gold alloy layers and a gloss additive for same
JP4023138B2 (en) * 2001-02-07 2007-12-19 日立金属株式会社 Compound containing iron-based rare earth alloy powder and iron-based rare earth alloy powder, and permanent magnet using the same
FR2828889B1 (en) * 2001-08-24 2004-05-07 Engelhard Clal Sas ELECTROLYTIC BATH FOR THE ELECTROCHEMICAL DEPOSITION OF GOLD AND ITS ALLOYS
KR100442519B1 (en) * 2002-04-09 2004-07-30 삼성전기주식회사 Alloy Plating Solution for Surface Treatment of Modular PCB
EP1548525B2 (en) * 2003-12-23 2017-08-16 Rolex Sa Ceramic element for watch case and method of manufacturing the same
JP4566667B2 (en) * 2004-01-16 2010-10-20 キヤノン株式会社 Plating solution, method of manufacturing structure using plating solution, and apparatus using plating solution
JP2005214903A (en) 2004-01-30 2005-08-11 Kawaguchiko Seimitsu Co Ltd Method of manufacturing dial with index, and dial with index manufactured using the same
SG127854A1 (en) * 2005-06-02 2006-12-29 Rohm & Haas Elect Mat Improved gold electrolytes
EP3170924A1 (en) * 2007-04-19 2017-05-24 Enthone, Inc. Electrolyte and method for electrolytic deposition of gold-copper alloys
CH710184B1 (en) * 2007-09-21 2016-03-31 Aliprandini Laboratoires G Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids.
CN105308198B (en) * 2013-09-10 2018-04-13 苹果公司 Crystal billon with improved hardness

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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HK1157415A1 (en) 2012-06-29
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JP5563421B2 (en) 2014-07-30
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US20200240030A1 (en) 2020-07-30
US9567684B2 (en) 2017-02-14
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US20150027898A1 (en) 2015-01-29
KR101297476B1 (en) 2013-08-16

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