EP2205778A1 - Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids - Google Patents
Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloidsInfo
- Publication number
- EP2205778A1 EP2205778A1 EP08804009A EP08804009A EP2205778A1 EP 2205778 A1 EP2205778 A1 EP 2205778A1 EP 08804009 A EP08804009 A EP 08804009A EP 08804009 A EP08804009 A EP 08804009A EP 2205778 A1 EP2205778 A1 EP 2205778A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- copper
- gold
- indium
- bath comprises
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 10
- 239000000956 alloy Substances 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 24
- 150000002739 metals Chemical class 0.000 title claims description 7
- 238000009713 electroplating Methods 0.000 title claims description 4
- 239000010930 yellow gold Substances 0.000 title abstract description 5
- 229910001097 yellow gold Inorganic materials 0.000 title abstract description 5
- 231100000331 toxic Toxicity 0.000 title description 5
- 230000002588 toxic effect Effects 0.000 title description 5
- 229910052752 metalloid Inorganic materials 0.000 title description 4
- 150000002738 metalloids Chemical class 0.000 title description 4
- 239000011248 coating agent Substances 0.000 title description 2
- 238000000576 coating method Methods 0.000 title description 2
- 239000010949 copper Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010931 gold Substances 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000000080 wetting agent Substances 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 229910001020 Au alloy Inorganic materials 0.000 claims description 7
- 239000003353 gold alloy Substances 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 235000021317 phosphate Nutrition 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 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 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
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000003892 tartrate salts Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 125000002524 organometallic group Chemical group 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005494 tarnishing Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910052709 silver Inorganic materials 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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 241000499489 Castor canadensis Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 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
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-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
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 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
- 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
- -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
- 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
- 239000004332 silver Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 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
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- the invention relates to an electrolytic deposit in the form of a gold alloy in a thick layer and its production process.
- the object of the present invention is to overcome all or part of the disadvantages mentioned above by proposing a method for the deposition in thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.
- the invention relates to an electrolytic deposit in the form of a gold alloy whose thickness is between 1 and 800 microns and comprises copper characterized in that it comprises indium as third main compound.
- the deposit is substantially free of toxic metals or metalloids; the deposit has a hue between the domains 1 N and 3N (according to ISO 8654); the deposit is bright and has a very high resistance to corrosion.
- the invention also relates to a method for the electroplating of a gold alloy on an electrode immersed in a bath comprising gold metal in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, a free cyanide characterized in that the alloying metals are copper in the form of copper and potassium double cyanide, and indium in aminocarboxylic or aminophosphonic complexed form for depositing on the electrode a yellow gold alloy brilliant mirror.
- the bath comprises from 1 to 10 g.1-1 of gold metal in the form of alkaline aurocyanide and preferably 5 g.1-1; the bath comprises from 30 to 80 g / l of copper metal in the form of double alkaline cyanide and preferably 50 g / l; the bath comprises from 10 mg.l-1 to 5 g.1-1 of indium metal in complexed form and preferably comprises 1 g.1-1; the bath contains from 15 to 35 g.1-1 of free cyanide
- the wetting agent has a concentration of between 0.05 and
- the wetting agent is chosen from polyoxyalkylene, phosphate ether, lauryl sulfate, dimethyldodecylamine-N-oxide, dimethyldodecyl ammonium propane sulphonate or any other type capable of wetting in an alkaline cyanide medium;
- the aminocarboxylic complexing agent has a concentration of between 0.1 and 20 g / l;
- the bath has an amine concentration of between 0.01 and 5 ml.1-1;
- the bath comprises a depolarizer with a concentration of between 0.1 mg.l-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 80 ° C;
- the pH of the bath is maintained between 8 and 12; the process is carried out at current densities between
- the electrolysis is preferably followed by a heat treatment at least 450 degrees Celsius for at least 30 minutes to obtain an optimal quality deposit.
- 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.
- This deposit is obtained by electrolysis in an electrolytic bath of the type:
- the electrolytic bath is 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 Ag, Cd, 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 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)
- Physical Vapour Deposition (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH01494/07A CH710184B1 (en) | 2007-09-21 | 2007-09-21 | Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids. |
PCT/EP2008/062042 WO2009037180A1 (en) | 2007-09-21 | 2008-09-11 | Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2205778A1 true EP2205778A1 (en) | 2010-07-14 |
EP2205778B1 EP2205778B1 (en) | 2011-02-23 |
Family
ID=39967872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08804009A Active EP2205778B1 (en) | 2007-09-21 | 2008-09-11 | Method of obtaining a yellow gold alloy coating by electroplating without the use of toxic metals or metalloids |
Country Status (12)
Country | Link |
---|---|
US (3) | US10233555B2 (en) |
EP (1) | EP2205778B1 (en) |
JP (2) | JP5563462B2 (en) |
KR (1) | KR101280675B1 (en) |
CN (1) | CN101815814B (en) |
AT (1) | ATE499461T1 (en) |
CH (1) | CH710184B1 (en) |
DE (1) | DE602008005184D1 (en) |
HK (1) | HK1147782A1 (en) |
IN (1) | IN2014CN02464A (en) |
TW (2) | TWI441959B (en) |
WO (1) | WO2009037180A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH714243B1 (en) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Electroforming process and part or layer obtained by this method. |
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. |
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 |
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 |
ITFI20120103A1 (en) * | 2012-06-01 | 2013-12-02 | Bluclad Srl | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
WO2016020812A1 (en) * | 2014-08-04 | 2016-02-11 | Nutec International Srl | Electrolytic bath, electrolytic deposition method and item obtained with said method |
CN109504991B (en) * | 2019-01-21 | 2020-08-07 | 南京市产品质量监督检验院 | Cyanide-free 18k gold electroforming solution, and preparation method and application thereof |
Citations (1)
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JP2001198693A (en) | 2000-01-17 | 2001-07-24 | Ishifuku Metal Ind Co Ltd | Gold brazing filler metal for industrial use and jewel and ornament |
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-
2007
- 2007-09-21 CH CH01494/07A patent/CH710184B1/en unknown
-
2008
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001198693A (en) | 2000-01-17 | 2001-07-24 | Ishifuku Metal Ind Co Ltd | Gold brazing filler metal for industrial use and jewel and ornament |
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US20100206739A1 (en) | 2010-08-19 |
JP5887381B2 (en) | 2016-03-16 |
TW201428143A (en) | 2014-07-16 |
JP2010539335A (en) | 2010-12-16 |
DE602008005184D1 (en) | 2011-04-07 |
US9683303B2 (en) | 2017-06-20 |
IN2014CN02464A (en) | 2015-08-07 |
ATE499461T1 (en) | 2011-03-15 |
KR20100075935A (en) | 2010-07-05 |
HK1147782A1 (en) | 2011-08-19 |
TW200930844A (en) | 2009-07-16 |
WO2009037180A1 (en) | 2009-03-26 |
US10619260B2 (en) | 2020-04-14 |
US20190153608A1 (en) | 2019-05-23 |
JP2014194087A (en) | 2014-10-09 |
JP5563462B2 (en) | 2014-07-30 |
US10233555B2 (en) | 2019-03-19 |
TWI441959B (en) | 2014-06-21 |
CN101815814B (en) | 2012-05-16 |
CH710184B1 (en) | 2016-03-31 |
US20140299481A1 (en) | 2014-10-09 |
KR101280675B1 (en) | 2013-07-01 |
CN101815814A (en) | 2010-08-25 |
TWI507571B (en) | 2015-11-11 |
EP2205778B1 (en) | 2011-02-23 |
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