EP2312021B1 - Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques - Google Patents
Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques Download PDFInfo
- Publication number
- EP2312021B1 EP2312021B1 EP09173198.4A EP09173198A EP2312021B1 EP 2312021 B1 EP2312021 B1 EP 2312021B1 EP 09173198 A EP09173198 A EP 09173198A EP 2312021 B1 EP2312021 B1 EP 2312021B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- copper
- gold
- cyanide
- silver
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 18
- 229910052751 metal Inorganic materials 0.000 title claims description 11
- 239000002184 metal Substances 0.000 title claims description 11
- 229910045601 alloy Inorganic materials 0.000 title claims description 6
- 239000000956 alloy Substances 0.000 title claims description 6
- 239000010930 yellow gold Substances 0.000 title claims description 3
- 229910001097 yellow gold Inorganic materials 0.000 title claims description 3
- 150000002739 metals Chemical class 0.000 title description 4
- 231100000331 toxic Toxicity 0.000 title description 3
- 230000002588 toxic effect Effects 0.000 title description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- 229910001020 Au alloy Inorganic materials 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000003353 gold alloy Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000001412 amines 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
- 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
- 150000003839 salts Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910002065 alloy metal Inorganic materials 0.000 claims 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims 1
- 229940050410 gluconate Drugs 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical group [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims 1
- 239000003352 sequestering agent Substances 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229940095064 tartrate Drugs 0.000 claims 1
- 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
- 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 description 2
- 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
- 150000001204 N-oxides Chemical class 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 229940043264 dodecyl sulfate Drugs 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 150000003892 tartrate salts Chemical class 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 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
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005275 alloying Methods 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
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 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
- 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
- 238000007747 plating Methods 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium 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
- 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
- 238000009736 wetting Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/005—Jewels; Clockworks; Coins
Definitions
- the invention relates to electrolytic deposition in the form of a thick layer gold alloy as well as its manufacturing process.
- the deposits obtained by these known methods have cadmium contents of between 1 and 10%.
- Cadmium facilitates the deposition of thick layers, that is to say between 1 and 800 microns and makes it possible to obtain an alloy of yellow color by reducing the quantity of copper contained in the alloy; however cadmium is extremely toxic and banned in some countries.
- the object of the present invention is to overcome all or part of the drawbacks mentioned above, a manufacturing process allowing the deposition in a thick layer of a yellow gold alloy having neither zinc nor cadmium as main constituents.
- the invention relates to a process for the galvanoplastic deposition of a gold alloy on an electrode immersed in a bath comprising metal gold in the form of alkaline aurocyanide, organometallic compounds, a wetting agent, a complexing agent, free cyanide, the alloying metals being copper in the form of double cyanide of copper and potassium, and silver in cyanide form, characterized in that the bath respects a percentage by weight proportion of 9.08% of gold, of 90.85% of copper and of 0.07% of silver making it possible to deposit on the electrode a gold alloy of the shiny mirror yellow type, said bath being free of cadmium.
- the invention relates to an electrolytic deposition of a gold alloy of shade 3N which, surprisingly, comprises main compounds Au-Cu-Ag whose proportions are not known to obtain shade 3N, that is to say - say bright yellow.
- a gold alloy free of toxic metals or metalloids, in particular free of cadmium, of 3N yellow tint, with a thickness of 200 microns, of excellent gloss and having a very high resistance to wear and tarnishing.
- the electrolysis is preferably followed by a heat treatment at a temperature between 200 and 450 degrees Celsius for 1 to 30 minutes in order to obtain a deposit of optimal quality.
- the bath according to the invention makes it possible to obtain a deposit substantially in a proportion of 75% gold, 21% copper and 4% silver corresponding to a deposit of shade 3N to 18 carats which is a very different proportion from the usual electrolytic deposits for this shade which are rather deposits according to substantially 75% gold, 12.5% copper and 12.5% silver.
- the bath can also contain a brightener.
- a brightener This is preferably a derivative of butynediol, a pyridinio-propanesulfonate or a mixture of the two, a tin salt, sulfonated beaver oil, methylimidozole, dithiocarboxylic acid such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.
- the electrolytic bath contained in a polypropylene or PVC tank with heat-insulating coating.
- the bath is heated by quartz, PTFE, porcelain or stabilized stainless steel immersion heaters. Good cathodic agitation and circulation of the electrolyte must be maintained.
- the anodes are made of platinum titanium, stainless steel, ruthenium, iridium or alloys of the latter two.
- the bath can contain the following metals Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi in negligible quantities.
- the wetting agent can be of any type capable of wetting in an alkaline cyanide medium.
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)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09173198.4A EP2312021B1 (fr) | 2009-10-15 | 2009-10-15 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
| CN201010552012.7A CN102041527B (zh) | 2009-10-15 | 2010-10-15 | 通过电铸在不使用有毒金属的情况下获得黄色金合金沉积物的方法 |
| US12/905,788 US20110089040A1 (en) | 2009-10-15 | 2010-10-15 | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials |
| JP2010232903A JP5563421B2 (ja) | 2009-10-15 | 2010-10-15 | 毒性金属を使用することなく電気めっき法により黄色の金合金析出物を得る方法 |
| KR1020100100585A KR101297476B1 (ko) | 2009-10-15 | 2010-10-15 | 독성 금속을 사용하지 않고 전기주조에 의하여 황색 금 합금 전착물을 수득하는 방법 |
| HK11111618.6A HK1157415A1 (zh) | 2009-10-15 | 2011-10-27 | 通過電鑄在不使用有毒金屬的情況下獲得黃色金合金沉積物的方法 |
| US14/452,364 US9567684B2 (en) | 2009-10-15 | 2014-08-05 | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials |
| US15/898,330 US20180171499A1 (en) | 2009-10-15 | 2018-02-16 | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials |
| US16/847,699 US20200240030A1 (en) | 2009-10-15 | 2020-04-14 | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09173198.4A EP2312021B1 (fr) | 2009-10-15 | 2009-10-15 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2312021A1 EP2312021A1 (fr) | 2011-04-20 |
| EP2312021B1 true EP2312021B1 (fr) | 2020-03-18 |
Family
ID=41820241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09173198.4A Active EP2312021B1 (fr) | 2009-10-15 | 2009-10-15 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
Country Status (6)
| Country | Link |
|---|---|
| US (4) | US20110089040A1 (zh) |
| EP (1) | EP2312021B1 (zh) |
| JP (1) | JP5563421B2 (zh) |
| KR (1) | KR101297476B1 (zh) |
| CN (1) | CN102041527B (zh) |
| HK (1) | HK1157415A1 (zh) |
Families Citing this family (3)
| 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 |
| WO2018066007A1 (en) * | 2016-10-06 | 2018-04-12 | Valmet Plating S.R.L. | A galvanic and thermal process to obtain the coloration of metals, in particular precious metals |
| CN107299364A (zh) * | 2017-06-07 | 2017-10-27 | 常州富思通管道有限公司 | 一种镀锌光亮剂及其制备方法 |
Family Cites Families (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2127676A (en) * | 1938-04-21 | 1938-08-23 | Claude H Coleman | Process of tempering gold and silver alloys |
| US2141157A (en) * | 1938-08-23 | 1938-12-20 | Metals & Controls Corp | Alloy |
| US2229463A (en) * | 1939-10-21 | 1941-01-21 | Handy & Harman | Alloy |
| US2596454A (en) * | 1949-09-10 | 1952-05-13 | Metals & Controls Corp | Gold alloys |
| US2660554A (en) * | 1950-11-10 | 1953-11-24 | Barnet D Ostrow | Bright gold and gold alloy plating baths |
| CH286123A (fr) * | 1952-05-08 | 1952-10-15 | Spreter Victor | Bain pour le dépôt par voie galvanique d'alliages d'or. |
| US2976180A (en) * | 1957-12-17 | 1961-03-21 | Hughes Aircraft Co | Method of silver plating by chemical reduction |
| FR1259407A (fr) | 1960-03-10 | 1961-04-28 | Maison Murat | Bain électrolytique pour dépôt épais d'alliage or-cuivre |
| DE1460993A1 (de) | 1965-07-23 | 1970-07-23 | Kieninger & Obergfell | Elektrisches Programmsteuergeraet,vorzugsweise fuer elektrische Haushaltsgeraete,insbesondere Waschmaschinen und Geschirrspuelmaschinen |
| US3475292A (en) | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
| GB1156186A (en) | 1966-09-26 | 1969-06-25 | Sel Rex Corp | Gold Plating |
| BE743946A (zh) | 1969-01-07 | 1970-05-28 | ||
| US3642589A (en) * | 1969-09-29 | 1972-02-15 | Fred I Nobel | Gold alloy electroplating baths |
| US3666640A (en) * | 1971-04-23 | 1972-05-30 | Sel Rex Corp | Gold plating bath and process |
| DE2121150C3 (de) | 1971-04-24 | 1980-08-21 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Verfahren zur galvanischen Abscheidung von Goldlegierungen |
| CH529843A (fr) | 1971-07-09 | 1972-10-31 | Oxy Metal Finishing Europ S A | Bain pour le dépôt électrolytique d'alliages d'or et son utilisation en galvanoplastie |
| FR2181455B1 (zh) * | 1972-04-25 | 1974-08-30 | Parker Ste Continentale | |
| DE2244434C3 (de) * | 1972-09-06 | 1982-02-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen |
| US3834879A (en) * | 1973-05-11 | 1974-09-10 | J Chin | Plated coins |
| JPS6014115B2 (ja) * | 1977-07-05 | 1985-04-11 | オクシ メタル インダストリ−ズ コ−ポレ−シヨン | 光沢のある低カラツト銀−金電着 |
| CH621367A5 (en) | 1977-07-08 | 1981-01-30 | Systemes Traitements Surfaces | Electrolytic bath for plating gold-copper-cadmium alloys and its use in galvanoplasty |
| JPS5433834A (en) * | 1977-08-22 | 1979-03-12 | Citizen Watch Co Ltd | Golddcopper alloy plating solution |
| CH622829A5 (zh) * | 1977-08-29 | 1981-04-30 | Systemes Traitements Surfaces | |
| FR2405312A1 (fr) | 1977-10-10 | 1979-05-04 | Oxy Metal Industries Corp | Bains electrolytiques pour le depot d'alliages d'or |
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-
2009
- 2009-10-15 EP EP09173198.4A patent/EP2312021B1/fr active Active
-
2010
- 2010-10-15 CN CN201010552012.7A patent/CN102041527B/zh active Active
- 2010-10-15 KR KR1020100100585A patent/KR101297476B1/ko active IP Right Grant
- 2010-10-15 US US12/905,788 patent/US20110089040A1/en not_active Abandoned
- 2010-10-15 JP JP2010232903A patent/JP5563421B2/ja active Active
-
2011
- 2011-10-27 HK HK11111618.6A patent/HK1157415A1/zh unknown
-
2014
- 2014-08-05 US US14/452,364 patent/US9567684B2/en active Active
-
2018
- 2018-02-16 US US15/898,330 patent/US20180171499A1/en not_active Abandoned
-
2020
- 2020-04-14 US US16/847,699 patent/US20200240030A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011084815A (ja) | 2011-04-28 |
| EP2312021A1 (fr) | 2011-04-20 |
| US20150027898A1 (en) | 2015-01-29 |
| KR20110041424A (ko) | 2011-04-21 |
| US20200240030A1 (en) | 2020-07-30 |
| US9567684B2 (en) | 2017-02-14 |
| US20180171499A1 (en) | 2018-06-21 |
| CN102041527B (zh) | 2014-09-17 |
| HK1157415A1 (zh) | 2012-06-29 |
| CN102041527A (zh) | 2011-05-04 |
| JP5563421B2 (ja) | 2014-07-30 |
| US20110089040A1 (en) | 2011-04-21 |
| KR101297476B1 (ko) | 2013-08-16 |
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