EP2505691A1 - Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N - Google Patents
Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 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
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- 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.
Landscapes
- 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)
- Electroplating Methods And Accessories (AREA)
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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- De plus, le mouillant peut être de tout type susceptible de mouiller en milieu cyanuré alcalin.
Claims (14)
- 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.
- Procédé selon la revendication 1, caractérisé en ce que le bain comporte de 1 à 10 g.l-1 d'or métal sous forme de cyanure double d'or et de potassium.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que le bain comporte de 10 à 60 g.l-1 de cuivre métal sous forme d'iodure de cuivre.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que 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.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte de 3 à 35 g.l-1 de cyanure.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le mouillant comporte une concentration comprise entre 0,05 et 10 ml.l-1.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le mouillant est choisi parmi les types polyoxyalcoilenique, étherphosphate, lauryl sulfate, diaméthydodécylamine-N-oxide, diméthyldodécyl ammonium propane sulfonate.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte une amine de concentration comprise entre 0,01 et 5 ml.l-1.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte un dépolarisant de concentration comprise entre 0,1 et 20 mg.l-1.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le bain comporte des sels conducteurs du type phosphates, carbonates, citrates, sulfates, tartrates, gluconates et/ou phosphonates.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que la température du bain est maintenue entre 50 et 90°C.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le pH du bain est maintenu entre 8 et 12.
- Procédé selon l'une des revendications précédentes, caractérisé en ce que le procédé est réalisé à une densité de courant comprise entre 0,05 et 1,5 A.dm-2.
- 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.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11160669.5A EP2505691B1 (fr) | 2011-03-31 | 2011-03-31 | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
| US13/427,558 US10053789B2 (en) | 2011-03-31 | 2012-03-22 | Method of obtaining a 18 caracts 3N gold alloy |
| CN201210113840.XA CN102732920B (zh) | 2011-03-31 | 2012-03-30 | 18开3n金合金的制备方法 |
| JP2012083556A JP5627629B2 (ja) | 2011-03-31 | 2012-04-02 | １８カラット３ｎ金合金およびこれの析出方法 |
| HK13104533.1A HK1177235A1 (zh) | 2011-03-31 | 2013-04-15 | 金合金的製備方法 |
| US16/038,662 US10793961B2 (en) | 2011-03-31 | 2018-07-18 | Method of obtaining a 18 carats 3N gold alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11160669.5A EP2505691B1 (fr) | 2011-03-31 | 2011-03-31 | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2505691A1 true EP2505691A1 (fr) | 2012-10-03 |
| EP2505691B1 EP2505691B1 (fr) | 2014-03-12 |
Family
ID=44021909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11160669.5A Active EP2505691B1 (fr) | 2011-03-31 | 2011-03-31 | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US10053789B2 (fr) |
| EP (1) | EP2505691B1 (fr) |
| JP (1) | JP5627629B2 (fr) |
| CN (1) | CN102732920B (fr) |
| HK (1) | HK1177235A1 (fr) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2505691B1 (fr) | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
| CN117802543B (zh) * | 2024-01-10 | 2024-10-22 | 深圳市联合蓝海应用材料科技股份有限公司 | 用于制备耐磨抗氧化镀层的金银电镀液、电镀方法及产品 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62164890A (ja) * | 1986-01-16 | 1987-07-21 | Seiko Instr & Electronics Ltd | 金銀銅合金めつき液 |
| EP0416342A1 (fr) * | 1989-09-06 | 1991-03-13 | Degussa Aktiengesellschaft | Bain d'alliage d'or galvanique |
| EP0566054A1 (fr) * | 1992-04-15 | 1993-10-20 | LeaRonal, Inc. | Electrodéposition d'alliages or-cuivre-argent |
| EP1728898A2 (fr) * | 2005-06-02 | 2006-12-06 | Rohm and Haas Electronic Materials LLC | Electrolyte pour le dêpot des alliages à base d'or |
| EP2312021A1 (fr) * | 2009-10-15 | 2011-04-20 | 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 |
Family Cites Families (13)
| 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 |
| US3642589A (en) * | 1969-09-29 | 1972-02-15 | Fred I Nobel | Gold alloy electroplating baths |
| JPS62164889A (ja) * | 1986-01-16 | 1987-07-21 | Seiko Instr & Electronics Ltd | 金銀銅合金めつき液 |
| EP0304315B1 (fr) * | 1987-08-21 | 1993-03-03 | Engelhard Limited | Bain de déposition électrolytique d'un alliage or-cuivre-zinc |
| US5045411A (en) * | 1990-01-10 | 1991-09-03 | P.M. Refining, Inc. | Alloy compositions |
| JPH051393A (ja) * | 1990-07-19 | 1993-01-08 | Electroplating Eng Of Japan Co | 銀銅合金メツキ浴及び銀銅合金ロウ材 |
| JP2832344B2 (ja) * | 1996-05-21 | 1998-12-09 | 大蔵省造幣局長 | メッキ体の製造方法 |
| US7273540B2 (en) * | 2002-07-25 | 2007-09-25 | Shinryo Electronics Co., Ltd. | Tin-silver-copper plating solution, plating film containing the same, and method for forming the plating film |
| CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
| JP2008291287A (ja) * | 2007-05-22 | 2008-12-04 | Nippon New Chrome Kk | 耐連続衝撃性に優れた銅−錫合金めっき製品の製造方法 |
| 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. |
| CN101392392A (zh) * | 2008-10-22 | 2009-03-25 | 山东招金万足金珠宝有限公司 | 硬质千足金黄金饰品加工工艺 |
| EP2505691B1 (fr) | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
-
2011
- 2011-03-31 EP EP11160669.5A patent/EP2505691B1/fr active Active
-
2012
- 2012-03-22 US US13/427,558 patent/US10053789B2/en active Active
- 2012-03-30 CN CN201210113840.XA patent/CN102732920B/zh active Active
- 2012-04-02 JP JP2012083556A patent/JP5627629B2/ja active Active
-
2013
- 2013-04-15 HK HK13104533.1A patent/HK1177235A1/zh unknown
-
2018
- 2018-07-18 US US16/038,662 patent/US10793961B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62164890A (ja) * | 1986-01-16 | 1987-07-21 | Seiko Instr & Electronics Ltd | 金銀銅合金めつき液 |
| EP0416342A1 (fr) * | 1989-09-06 | 1991-03-13 | Degussa Aktiengesellschaft | Bain d'alliage d'or galvanique |
| EP0566054A1 (fr) * | 1992-04-15 | 1993-10-20 | LeaRonal, Inc. | Electrodéposition d'alliages or-cuivre-argent |
| EP1728898A2 (fr) * | 2005-06-02 | 2006-12-06 | Rohm and Haas Electronic Materials LLC | Electrolyte pour le dêpot des alliages à base d'or |
| EP2312021A1 (fr) * | 2009-10-15 | 2011-04-20 | 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 |
Non-Patent Citations (1)
| Title |
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| MAEDA S ET AL: "Gold-silver-copper alloy plating soln. - contg. cyanide of alkali gold, silver and copper, potassium citrate, potassium thiosulphate and nonionic surfactant", WPI / THOMSON,, 21 July 1987 (1987-07-21), XP002574602 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5627629B2 (ja) | 2014-11-19 |
| CN102732920A (zh) | 2012-10-17 |
| US10793961B2 (en) | 2020-10-06 |
| EP2505691B1 (fr) | 2014-03-12 |
| US10053789B2 (en) | 2018-08-21 |
| CN102732920B (zh) | 2015-07-22 |
| HK1177235A1 (zh) | 2013-08-16 |
| US20180320283A1 (en) | 2018-11-08 |
| JP2012214899A (ja) | 2012-11-08 |
| US20120247968A1 (en) | 2012-10-04 |
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