EP2505691B1 - Process for obtaining a gold alloy deposit of 18 carat 3N - Google Patents

Process for obtaining a gold alloy deposit of 18 carat 3N Download PDF

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Publication number
EP2505691B1
EP2505691B1 EP11160669.5A EP11160669A EP2505691B1 EP 2505691 B1 EP2505691 B1 EP 2505691B1 EP 11160669 A EP11160669 A EP 11160669A EP 2505691 B1 EP2505691 B1 EP 2505691B1
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Prior art keywords
bath
gold
copper
silver
metal
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EP11160669.5A
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German (de)
French (fr)
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EP2505691A1 (en
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Christophe Henzirohs
Guido Plankert
Thomas Froelicher
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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 EP11160669.5A priority Critical patent/EP2505691B1/en
Priority to US13/427,558 priority patent/US10053789B2/en
Priority to CN201210113840.XA priority patent/CN102732920B/en
Priority to JP2012083556A priority patent/JP5627629B2/en
Publication of EP2505691A1 publication Critical patent/EP2505691A1/en
Priority to HK13104533.1A priority patent/HK1177235A1/en
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Publication of EP2505691B1 publication Critical patent/EP2505691B1/en
Priority to US16/038,662 priority patent/US10793961B2/en
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    • 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 electrolytic deposition in the form of a gold alloy in a thick layer, as well as to its method of manufacture.
  • 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 a yellow-colored alloy by decreasing the quantity of copper contained in the alloy, however the cadmium is extremely toxic and banned in some countries.
  • the document EP 1 728 898 discloses a bath for the electroplating of 18K gold alloys in 2N or 3N colors using a gold-copper-silver alloy. To obtain the 3N color, the document EP 1 728 898 discloses a deposit of 75% gold, 12.5% copper and 12.5% silver.
  • the object of the present invention is to overcome all or part of the aforementioned drawbacks by proposing a manufacturing method for the thick-layer deposition of a 3N yellow gold 18-carat gold alloy having neither zinc nor nickel. cadmium as major constituents.
  • the invention relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal, organometallic compounds, a wetting agent, a complexing agent, free cyanide, the alloying metals are copper metal and silver metal making it possible to deposit on the electrode a golden alloy of the brilliant mirror yellow type, characterized in that the bath has a mass proportion of about 21.53% gold, 78.31% copper and 0.16% silver.
  • the bath even with a very high concentration of copper makes it possible, according to the invention, to obtain a deposit substantially in a proportion of 75% of gold, 19% of copper and 6% of silver. corresponding to a deposit of 18 carats of yellow tint 3N and not pink 5N.
  • the invention also relates to an electrolytic deposit in the form of a gold alloy obtained from a process according to one of the preceding claims whose thickness is between 1 and 800 ⁇ m and which comprises copper characterized in that it comprises silver as the third main compound in a mass proportion of 75% gold, 19% copper and 6% silver to obtain a brilliant shade 3N.
  • the invention relates to an electrolytic deposition of a 3N gold alloy which, surprisingly, comprises principal compounds in order of importance which are Au-Cu-Ag and whose proportions are not known to obtain the 3N color, that is to say bright yellow.
  • gold alloy free of toxic metals or metalloids, in particular free of cadmium and zinc, 3N yellow, 200 ⁇ m thick, excellent gloss and having a very high resistance to wear and tarnishing.
  • the bath has a mass proportion of about 21.53% gold, 78.31% copper and 0.16% silver between these three main materials.
  • the electrolysis is preferably followed by a heat treatment at a temperature between 200 and 450 degrees Celsius for 1 to 30 minutes to obtain an optimal quality deposit.
  • the bath according to the invention makes it possible to obtain a deposit substantially in a proportion of 75% of gold, 19% of copper and 6% of silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion of the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% of gold, 12.5% of copper and 12.5% of silver.
  • the bath may further contain a brightener.
  • a brightener This is preferably a butynediol derivative, a pyridinio-propanesulfonate or a mixture of both, 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. Bath heating is achieved by thermo-plungers in quartz, PTFE, porcelain or stabilized stainless steel. Good cathodic stirring as well as a flow of the electrolyte must be maintained.
  • the anodes are platinized titanium, stainless steel, ruthenium, iridium or alloys of the latter two.
  • the bath may contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantity.
  • the wetting agent may 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 gold alloy in a thick layer, as well as to its method of manufacture.

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.1-1.In the decorative field of plating processes are known for the production of electrolytic deposits of gold, yellow color, whose title is greater than or equal to 9 carats, ductile to a thickness of 10 microns, and high 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 g.1 -1 .

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 µm 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 a yellow-colored alloy by decreasing the quantity of copper contained in the alloy, however the 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.Also known are cadmium-free 18-carat gold alloys containing copper and zinc. However, these deposits are too pink (title too rich in copper). Finally, these deposits have a poor resistance to corrosion which implies a rapid tarnishing.

Le document EP 1 728 898 divulgue un bain pour le dépôt galvanique d'alliages d'or 18 carats selon des teintes 2N ou 3N à l'aide d'un alliage or-cuivre-argent. Pour l'obtention de la teinte 3N, le document EP 1 728 898 divulgue un dépôt selon une proportion de 75 % d'or, de 12,5 % de cuivre et de 12,5 % d'argent.The document EP 1 728 898 discloses a bath for the electroplating of 18K gold alloys in 2N or 3N colors using a gold-copper-silver alloy. To obtain the 3N color, the document EP 1 728 898 discloses a deposit of 75% gold, 12.5% copper and 12.5% silver.

Résumé de l'inventionSummary of the invention

Le but de la présente invention est de pallier tout ou partie les inconvénients cités précédemment en proposant un procédé de fabrication permettant le dépôt en couche épaisse d'un alliage d'or de 18 carats de couleur jaune 3N 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 aforementioned drawbacks by proposing a manufacturing method for the thick-layer deposition of a 3N yellow gold 18-carat gold alloy having neither zinc nor nickel. cadmium as major 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, des composés organométalliques, un mouillant, un complexant, du cyanure libre, les métaux d'alliage sont du cuivre métal et de l'argent métal permettant de déposer sur l'électrode un alliage d'or du type jaune miroir brillant caractérisé en ce que le bain respecte une proportion en masse d'environ 21,53% d'or, 78,31 % de cuivre et 0,16% d'argent.To this end, the invention relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal, organometallic compounds, a wetting agent, a complexing agent, free cyanide, the alloying metals are copper metal and silver metal making it possible to deposit on the electrode a golden alloy of the brilliant mirror yellow type, characterized in that the bath has a mass proportion of about 21.53% gold, 78.31% copper and 0.16% silver.

Ainsi, de manière étonnante, le bain même à très forte concentration de cuivre permet, selon l'invention, d'obtenir un dépôt sensiblement selon une proportion de 75% d'or, de 19% de cuivre et de 6% d'argent correspondant à un dépôt à 18 carats de teinte jaune 3N et non pas rose 5N.Thus, surprisingly, the bath even with a very high concentration of copper makes it possible, according to the invention, to obtain a deposit substantially in a proportion of 75% of gold, 19% of copper and 6% of silver. corresponding to a deposit of 18 carats of yellow tint 3N and not pink 5N.

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

  • le bain comporte de 1 à 10 g.l-1 d'or métal sous forme de cyanure double d'or et de potassium ;
  • le bain comporte de 10 à 60 g.l-1 de cuivre métal sous forme d'iodure de cuivre ;
  • le bain comporte de 10 mg.l-1 à 1 g.l-1 d'argent métal sous forme de cyanure double d'argent et de potassium ;
  • le bain comporte de 3 à 35 g.l-1 de cyanure ;
  • 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 et 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 90°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.
According to other advantageous features of the invention:
  • the bath comprises from 1 to 10 gl -1 of gold metal in the form of double cyanide of gold and potassium;
  • the bath comprises from 10 to 60 gl -1 of copper metal in the form of copper iodide;
  • the bath comprises from 10 mg.l -1 to 1 gl -1 of silver metal in the form of double cyanide of silver and potassium;
  • the bath comprises from 3 to 35 g -1 of cyanide;
  • the wetting agent has a concentration of between 0.05 and 10 ml.l -1 ;
  • the wetting agent is chosen from the polyoxyalcoilene, etherphosphate, lauryl sulfate, diamethydodecylamine-N-oxide and dimethyldodecylammonium propane sulfonate types;
  • the bath comprises an amine concentration of between 0.01 and 5 ml.l -1 ;
  • the bath comprises a depolarizer with a concentration of between 0.1 and 20 mg.l -1 ;
  • the bath comprises conducting salts of phosphates, carbonates, citrates, sulphates, tartrates, gluconates and / or phosphonates;
  • the temperature of the bath is maintained between 50 and 90 ° 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 .

L'invention se rapporte également à un dépôt électrolytique sous forme d'un alliage d'or obtenu à partir d'un procédé conforme à l'une des revendications précédentes dont l'épaisseur est comprise entre 1 et 800 µm et qui comporte du cuivre caractérisé en ce qu'il comprend de l'argent comme troisième composé principal selon une proportion en masse de 75% d'or, 19% de cuivre et 6% d'argent permettant d'obtenir une teinte brillante 3N.The invention also relates to an electrolytic deposit in the form of a gold alloy obtained from a process according to one of the preceding claims whose thickness is between 1 and 800 μm and which comprises copper characterized in that it comprises silver as the third main compound in a mass proportion of 75% gold, 19% copper and 6% silver to obtain a brilliant shade 3N.

Description détaillée des modes de réalisation préférésDetailed Description of the Preferred Embodiments

L'invention concerne un dépôt électrolytique d'un alliage d'or de teinte 3N qui, de manière surprenante, comporte des composés principaux par ordre d'importance qui sont Au-Cu-Ag et 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 3N gold alloy which, surprisingly, comprises principal compounds in order of importance which are Au-Cu-Ag and whose proportions are not known to obtain the 3N color, that is to 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 et de zinc, de teinte 3N jaune, d'une épaisseur de 200 µm, 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 and zinc, 3N yellow, 200 μm thick, 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 :20 g.l-1
  • Ag : 40 mg.l-1
  • CN : 5 g.l-1
  • pH : 10,5
  • Température : 80°C
  • Densité de Courant : 0,3 A.dm-2
  • Mouillant : 0,05 ml.l-1 NN-Diméthyldodécyl N-Oxyde
  • 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: 20 gl -1
  • Ag: 40 mg.l -1
  • CN: 5 gl -1
  • pH: 10.5
  • Temperature: 80 ° C
  • Current Density: 0.3 A.dm -2
  • Wetting: 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 .

Par conséquent, le bain respecte une proportion en masse d'environ 21,53% d'or, 78,31 % de cuivre et 0,16% d'argent entre ces trois matériaux principaux.As a result, the bath has a mass proportion of about 21.53% gold, 78.31% copper and 0.16% silver between these three main materials.

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 to obtain an optimal quality deposit.

Ces conditions permettent d'obtenir un rendement cathodique de 95 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 efficiency of 95 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 19% de cuivre et de 6% 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% of gold, 19% of copper and 6% of silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion of the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% of gold, 12.5% of copper and 12.5% of 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 may further contain a brightener. This is preferably a butynediol derivative, a pyridinio-propanesulfonate or a mixture of both, 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. Bath heating is achieved by thermo-plungers in quartz, PTFE, porcelain or stabilized stainless steel. Good cathodic stirring as well as a flow of the electrolyte must be maintained. The anodes are platinized 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 illustrated example but is susceptible of various variations and modifications that will occur to those skilled in the art. In particular, the bath may contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantity.

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

Claims (14)

  1. Method for the galvanoplastic deposition of a gold alloy on an electrode dipped into a bath including gold metal, organometallic compounds, a wetting agent, a sequestering agent and free cyanide, the alloy metals being copper metal and silver metal allowing a mirror-bright yellow gold alloy to be deposited on the electrode characterized in that the bath respects a proportion in weight of 21.53% gold, 78.31% copper and 0.16% silver.
  2. Method according to claim 1, characterized in that the bath includes from 1 to 10 g.l-1 of gold metal in double gold and potassium cyanide form.
  3. Method according to claim 1 or 2, characterized in that the bath includes from 10 to 60 g.l-1 of copper metal in copper iodide 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 double silver and potassium cyanide form.
  5. Method according to any of the preceding claims, characterized in that the bath includes from 3 to 35 g.l-1 of cyanide.
  6. 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.
  7. Method according to any of the preceding claims, characterized in that the wetting agent is chosen from among poly-oxy-alkenic, ether phosphate, lauryl sulphate, dimethyldodecylamine-N-oxide, dimethyl(dodecyl) ammonium propane sulfonate types.
  8. 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.
  9. Method according to any of the preceding claims, characterized in that the bath includes a concentration of depolariser of between 0.1 to 20 mg.l-1.
  10. 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.
  11. Method according to any of the preceding claims, characterized in that the temperature of the bath is kept between 50 and 90°C.
  12. Method according to any of the preceding claims, characterized in that the pH of the bath is kept between 8 and 12.
  13. Method according to any of the preceding claims, characterized in that the method is performed at a current density of between 0.05 to 1.5 A.dm-2.
  14. Electrolytic deposition in the form of a gold alloy obtained from a method according to any of the preceding claims, the thickness of which is between 1 and 800 microns and which includes copper, characterized in that it includes silver as the third main compound and in that the deposition is made of 75% gold, 19% copper and 6% silver, allowing a bright 3N colour to be obtained.
EP11160669.5A 2011-03-31 2011-03-31 Process for obtaining a gold alloy deposit of 18 carat 3N Active EP2505691B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP11160669.5A EP2505691B1 (en) 2011-03-31 2011-03-31 Process for obtaining a gold alloy deposit of 18 carat 3N
US13/427,558 US10053789B2 (en) 2011-03-31 2012-03-22 Method of obtaining a 18 caracts 3N gold alloy
CN201210113840.XA CN102732920B (en) 2011-03-31 2012-03-30 Process for obtaining gold alloy deposit of 18 carat 3n
JP2012083556A JP5627629B2 (en) 2011-03-31 2012-04-02 18 carat 3N gold alloy and method for precipitation thereof
HK13104533.1A HK1177235A1 (en) 2011-03-31 2013-04-15 Method of obtaining a 18 caracts 3n gold alloy 18 3n
US16/038,662 US10793961B2 (en) 2011-03-31 2018-07-18 Method of obtaining a 18 carats 3N gold alloy

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Application Number Priority Date Filing Date Title
EP11160669.5A EP2505691B1 (en) 2011-03-31 2011-03-31 Process for obtaining a gold alloy deposit of 18 carat 3N

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EP2505691A1 EP2505691A1 (en) 2012-10-03
EP2505691B1 true EP2505691B1 (en) 2014-03-12

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EP (1) EP2505691B1 (en)
JP (1) JP5627629B2 (en)
CN (1) CN102732920B (en)
HK (1) HK1177235A1 (en)

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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

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CN101392392A (en) * 2008-10-22 2009-03-25 山东招金万足金珠宝有限公司 Rigid pure gold ornamental article processing technology
EP2312021B1 (en) * 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals
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US10793961B2 (en) 2020-10-06
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US10053789B2 (en) 2018-08-21
US20180320283A1 (en) 2018-11-08
EP2505691A1 (en) 2012-10-03
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CN102732920B (en) 2015-07-22
US20120247968A1 (en) 2012-10-04

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