EP3170924A1 - Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre - Google Patents
Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre Download PDFInfo
- Publication number
- EP3170924A1 EP3170924A1 EP16197251.8A EP16197251A EP3170924A1 EP 3170924 A1 EP3170924 A1 EP 3170924A1 EP 16197251 A EP16197251 A EP 16197251A EP 3170924 A1 EP3170924 A1 EP 3170924A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- electrolyte
- gold
- nitrilo
- 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.)
- Withdrawn
Links
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
- C25D3/58—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
- 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
- This invention relates to an electrolyte as well as a method for the electrolytic deposition of a gold-copper alloy on a substrate surface.
- alloy layers which can be varied in respect of their physical properties like brightness, hardness, wear resistance or colour. These properties are influenced by the composites of the alloys, e. g. the metals co-plated, as well as by the composition of the bath used for the deposition of the alloy, e. g. the electrolyte. Further, also the method and the plating parameters like temperature and current density are influencing the plating result in important ways.
- U.S. patent 5,006,208 discloses a galvanic gold alloying bath which contains beneath gold and copper in form of cyanide compounds a selenium compound.
- the deposit achieved from this galvanic bath is soft, light yellow and matt.
- the gold-alloy containing is constituted by 14 - 18 carat.
- European patent EP 0 384 679 B1 discloses a bath for the electrolytic deposition of gold-copper alloy as well as a method for electroplating articles using such a bath.
- An electrolyte is disclosed which contains gold in form of a cyanide compound, copper in the form of a cyanide compound as well as tellurium or bismuth in the form of water soluble compounds.
- European patent application 0 566 054 A1 discloses a solution for electroplating gold-copper alloys.
- an electrolyte comprising a soluble gold compound present as a gold cyanide complex, a soluble copper compound present as a copper cyanide complex as well as a soluble divalent sulfur compound in an amount sufficient to brighten the alloys.
- the brightening additive may be a thiocyanate, thiomalic acid, imidazolidinethione, a sulfite or thiobarbituric acid.
- an electrolyte for the electrolytic deposition of a gold-copper alloy on a substrate surface wherein the electrolyte comprises beneath a source of gold and copper potassium cyanide (KCN) in a concentration capable to maintain a copper to KCN ratio in the range of 3 to 7, and at least one complexing agent of the group consisting of ethylenediamine tetraacetic acid [EDTA], diethylenetriamine pentaacetic acid and nitrilo-triacetic acid [NTA] hydroxyethyl imino diacetic acid [HEIDA], nitrilo propionic diacetic acid [NPDA], imino diacetic acid [IDA], nitrilo trimethylphosphoric acid [NTMA, Dequest 2000], triethanol amine [TEA].
- EDTA ethylenediamine tetraacetic acid
- NDA nitrilo-triacetic acid
- HEIDA hydroxyethyl imino diacetic acid
- NPDA nitri
- the electrolyte according to the invention can comprise gold in a concentration between 2 to 20 g/l and copper in a concentration between 10 to 50 g/l.
- the at least one complexing agent of the group mentioned above is comprised in the inventive electrolyte in a concentration between 0,05 to 0,6 mol/l. It is believed that the strong chelating agents beneath functioning as complexing agent will contribute to the conductivity of the electrolyte.
- the inventive electrolyte may further comprise one of at least one metal of the group consisting of Sb, Se, Ag, Pt, Ni and Zn.
- selenium functions as brightener for the deposit. The same is true for tellurium and antimony.
- Zinc and nickel can function as grain refiner as well as stabilizer to the free KCN.
- Gold is believed to function as efficiency booster to yield in higher plating velocity and carat.
- the metals mentioned above can be comprised in the inventive electrolyte in an amount between 0,1 mg/l and 10 g/l. It is within the scope of the invention that the electrolyte can comprise further additive metals to influence the physical properties of the deposit.
- the inventive electrolyte can further comprise a surface active agent or wetting agent which will function as brightener.
- a capable surface active agent which can be comprised in the electrolyte is for example sodium-lauryl-etherphosphate.
- commercially available products known by name of nonionic, cationic, or amphoteric surfactants can be employed single or in combinations.
- the amount of the surface active agent in the inventive electrolyte may vary in a range of 0,1 ti 5 ml/l.
- the electrolyte can comprise secondary brightener and/or stabilizing agents.
- secondary brightener and/or stabilizing agents are pyridin sulfonic acid and ammonium hydrogene difluoride.
- the amount of these secondary brightener and/or stabilizing agents may vary in a range between 0,1 g/l to 10 g/l.
- the pH-value of the inventive electrolyte may vary in a range of pH 8 to pH 13, with a preferred pH-value of about 11.
- the inventive electrolyte may comprise alkaline hydroxide or alkaline earth hydroxide.
- the current density conducted between the substrate and the anode may vary in a range of 0,2 to 2 A/dm 2 .
- the temperature of the electrolyte is in the range of 70° C to 90° C.
- the inventive electrolyte together with the inventive method permits to produce a large range of carat suitable for plating and electroforming producing accurate value of carat between 18 and 14.
- the value of carat can be controlled by measurement of efficiency in Mg/A.nm. According to the relationship of temperature and current density disclosed above, the right efficiency for an adequate value of carat is obtained by tuning the current density and temperature respectively.
- a further advantage of the deposit yield by the inventive electrolyte and the inventive method is the possibility to heat-treat the deposited alloys in order to get an optimum ductility for a gold alloy. This is advantageously for both decorative and functional applications.
- heat-treating the alloys deposited a relatively high hardness is achieved. Relatively high in these terms means higher than that of the metallurgical alloy.
- the hardness rises from 280 HV to 380 HV while the aspect of surface isn't changed by oxidation.
- a further advantage of the deposits obtained from the inventive electrolyte is the good solder ability of the alloys. This characteristic is especially important in electroforming when it is necessary to close holes done to empty the mandrels and for further artistic work.
- the electrolyte Due to the strong complexing power of the complexing agent used according to this invention, the electrolyte is relatively none-sensitive to possible contaminations from various metals like Sn, Zn, Ag, Ni or Cr coming from different sources like drag ins from pre-treatment, mandrels composition or replenishment products. Generally, such types of contamination create an instability of the relation between current density and efficiency which may cause problems during electroforming processes. So, the non-sensity of the electrolyte to this contaminations is a further advance of this invention.
- gold-copper alloy deposits on substrate surfaces are obtainable showing a thickness of > 20 microns and a carat in the range of 12 to 19 carat.
- gold-copper alloy deposits on substrate surfaces are obtainable showing a thickness of > 20 microns and a carat in the range of 12 to 19 carat.
- electroforming at a thickness of 200 microns and more is possible.
- inventive electrolyte is also of high economic interest since it shows a minimum turn-over of 0,25 kg/l.
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)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16197251.8A EP3170924A1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16197251.8A EP3170924A1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
EP07007963.7A EP1983077B1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
Related Parent Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07007963.7A Division-Into EP1983077B1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
EP07007963.7A Division EP1983077B1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
EP07007963.7A Previously-Filed-Application EP1983077B1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3170924A1 true EP3170924A1 (fr) | 2017-05-24 |
Family
ID=38093067
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16197251.8A Withdrawn EP3170924A1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
EP07007963.7A Not-in-force EP1983077B1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07007963.7A Not-in-force EP1983077B1 (fr) | 2007-04-19 | 2007-04-19 | Électrolyte et procédé pour le dépôt électrolytique d'alliages or-cuivre |
Country Status (2)
Country | Link |
---|---|
EP (2) | EP3170924A1 (fr) |
CN (1) | CN101289756B (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2312021B1 (fr) * | 2009-10-15 | 2020-03-18 | 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 |
CN105506686A (zh) * | 2015-12-23 | 2016-04-20 | 苏州市金星工艺镀饰有限公司 | 一种装饰性镍铜金三元合金电镀液的电镀方法 |
CN108139306B (zh) * | 2016-02-18 | 2021-03-26 | 日本制铁株式会社 | 金属化合物粒子的提取方法、分析方法及其使用的电解液 |
CN105671602A (zh) * | 2016-03-15 | 2016-06-15 | 大连理工大学 | 一种无氰亚硫酸盐的Au-Cu合金电镀液及应用 |
CN109680310B (zh) * | 2019-01-04 | 2020-07-07 | 中国计量大学 | 一种镍锑电镀液及其制备方法 |
CN110699721B (zh) * | 2019-11-20 | 2021-08-20 | 长春黄金研究院有限公司 | 一种无氰镀金铜合金电镀液及其应用 |
CN111962104A (zh) * | 2020-08-21 | 2020-11-20 | 深圳国韵黄金文化有限公司 | 一种22k无氰电铸黄金及其制备工艺 |
CN114875456B (zh) * | 2021-06-25 | 2024-03-08 | 深圳市铭轩珠宝首饰有限公司 | 一种铜-金复合包金方法及其应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1375611A (fr) * | 1972-03-28 | 1974-11-27 | ||
GB2053276A (en) * | 1979-06-14 | 1981-02-04 | Aliprandini P | Electrodeposition of gold alloy |
EP0193848A1 (fr) * | 1985-03-01 | 1986-09-10 | Heinz Emmenegger | Bain galvanique pour le dépôt électrolytique d'alliages d'or |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ATE86313T1 (de) | 1987-08-21 | 1993-03-15 | Engelhard Ltd | Bad fuer das elektroplattieren einer gold-kupfer- zink-legierung. |
GB8903818D0 (en) | 1989-02-20 | 1989-04-05 | Engelhard Corp | Electrolytic deposition of gold-containing alloys |
DE3929569C1 (fr) | 1989-09-06 | 1991-04-18 | Degussa Ag, 6000 Frankfurt, De | |
US5256275A (en) | 1992-04-15 | 1993-10-26 | Learonal, Inc. | Electroplated gold-copper-silver alloys |
EP1103637A1 (fr) | 1999-11-29 | 2001-05-30 | ENTHONE-OMI, Inc. | Procédé de fabrication d'une couche en alliage AuCuGa en utilisant l'électrolyse et les alliages obtenus par ce procédé |
SG127854A1 (en) | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
-
2007
- 2007-04-19 EP EP16197251.8A patent/EP3170924A1/fr not_active Withdrawn
- 2007-04-19 EP EP07007963.7A patent/EP1983077B1/fr not_active Not-in-force
-
2008
- 2008-04-21 CN CN2008100934716A patent/CN101289756B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1375611A (fr) * | 1972-03-28 | 1974-11-27 | ||
GB2053276A (en) * | 1979-06-14 | 1981-02-04 | Aliprandini P | Electrodeposition of gold alloy |
EP0193848A1 (fr) * | 1985-03-01 | 1986-09-10 | Heinz Emmenegger | Bain galvanique pour le dépôt électrolytique d'alliages d'or |
Also Published As
Publication number | Publication date |
---|---|
EP1983077B1 (fr) | 2016-12-28 |
EP1983077A1 (fr) | 2008-10-22 |
CN101289756B (zh) | 2012-06-20 |
CN101289756A (zh) | 2008-10-22 |
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