EP2505691A1 - 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 PDFInfo
- Publication number
- EP2505691A1 EP2505691A1 EP11160669A EP11160669A EP2505691A1 EP 2505691 A1 EP2505691 A1 EP 2505691A1 EP 11160669 A EP11160669 A EP 11160669A EP 11160669 A EP11160669 A EP 11160669A EP 2505691 A1 EP2505691 A1 EP 2505691A1
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- EP
- European Patent Office
- Prior art keywords
- bath
- process according
- gold
- silver
- copper
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910001020 Au alloy Inorganic materials 0.000 title claims description 11
- 239000003353 gold alloy Substances 0.000 title claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010931 gold Substances 0.000 claims abstract description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 9
- 238000009713 electroplating Methods 0.000 claims abstract description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 4
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 3
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 150000003892 tartrate salts Chemical class 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 2
- NYUQKKWCYPVQGE-UHFFFAOYSA-N dodecyl(dimethyl)azanium;propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O.CCCCCCCCCCCC[NH+](C)C NYUQKKWCYPVQGE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 239000010930 yellow gold Substances 0.000 abstract description 2
- 229910001097 yellow gold Inorganic materials 0.000 abstract description 2
- 239000002738 chelating agent Substances 0.000 abstract 1
- 229910001092 metal group alloy Inorganic materials 0.000 abstract 1
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005494 tarnishing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- IPZMTZLUAIKVKD-UHFFFAOYSA-N 1-pyridin-1-ium-1-ylpropane-1-sulfonate Chemical compound CCC(S([O-])(=O)=O)[N+]1=CC=CC=C1 IPZMTZLUAIKVKD-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 235000011779 Menyanthes trifoliata Nutrition 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- WREDNSAXDZCLCP-UHFFFAOYSA-N methanedithioic acid Chemical compound SC=S WREDNSAXDZCLCP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
Definitions
- the invention relates to electrolytic deposition in the form of a gold alloy in a thick layer and 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 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 microns 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 color, 200 microns 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.
Abstract
Description
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 and to its method of manufacture.
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 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 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 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.
- 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 microns 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 microns 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.
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 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 and zinc, 3N yellow color, 200 microns 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.
- 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)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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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 |
Applications Claiming Priority (1)
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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 true EP2505691A1 (en) | 2012-10-03 |
EP2505691B1 EP2505691B1 (en) | 2014-03-12 |
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US (2) | US10053789B2 (en) |
EP (1) | EP2505691B1 (en) |
JP (1) | JP5627629B2 (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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2013
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Also Published As
Publication number | Publication date |
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US10053789B2 (en) | 2018-08-21 |
JP2012214899A (en) | 2012-11-08 |
HK1177235A1 (en) | 2013-08-16 |
EP2505691B1 (en) | 2014-03-12 |
US20180320283A1 (en) | 2018-11-08 |
US20120247968A1 (en) | 2012-10-04 |
US10793961B2 (en) | 2020-10-06 |
CN102732920B (en) | 2015-07-22 |
CN102732920A (en) | 2012-10-17 |
JP5627629B2 (en) | 2014-11-19 |
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