EP1983077B1 - Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen - Google Patents

Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen Download PDF

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Publication number
EP1983077B1
EP1983077B1 EP07007963.7A EP07007963A EP1983077B1 EP 1983077 B1 EP1983077 B1 EP 1983077B1 EP 07007963 A EP07007963 A EP 07007963A EP 1983077 B1 EP1983077 B1 EP 1983077B1
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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.)
Not-in-force
Application number
EP07007963.7A
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English (en)
French (fr)
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EP1983077A1 (de
Inventor
Guy Desthomas
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MacDermid Enthone Inc
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Enthone Inc
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Application filed by Enthone Inc filed Critical Enthone Inc
Priority to EP07007963.7A priority Critical patent/EP1983077B1/de
Priority to EP16197251.8A priority patent/EP3170924A1/de
Priority to CN2008100934716A priority patent/CN101289756B/zh
Publication of EP1983077A1 publication Critical patent/EP1983077A1/de
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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 watersoluble compounds.
  • European patent application EP 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.
  • Further patent documents disclosing the deposition of gold-copper alloys are for instance EP 0 193 848 A1 , GB 1 375 611 A and GB 2 053 276 A .
  • 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 [FEA].
  • 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.
  • Zinc and nickel can function as grain refiner as well as stabilizerto 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.

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  • 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)

Claims (14)

  1. Elektrolyt zum elektrolytischen Abscheiden einer Gold-Kupfer-Legierung auf einer Substratoberfläche, wobei der Elektrolyt neben einer Quelle für Gold und Kupfer freies Kaliumcyanid (KCN) in einer Konzentration (in g/l) aufweist, welche geeignet ist, das Verhältnis von Kupfer zu freiem KCN im Bereich von 3 bis 7 zu halten und mindestens einen Komplexbildner aus der Gruppe bestehend aus Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure [EDTA], Diethylentriaminpentaessigsäure, Nitrilotriessigsäure [NTA], Hydroxyethyliminodiessigsäure [HEIDA], Nitrilopropiondiessigsäure [NPDA], Iminodiessigsäure [IDA], Nitrilotrimethylphosphorsäure [NTMA, Dequest 2000] und Triethanolamin [TEA] aufweist, wobei der Elektrolyt dazu geeignet ist, dicke und glänzende Goldlegierungsschichten ohne Zugabe von Cadmium abzuscheiden.
  2. Elektrolyt nach Anspruch 1, aufweisend Gold in einer Konzentration zwischen 2 und 20 g/l und Kupfer in einer Konzentration zwischen 10 und 50 g/l.
  3. Elektrolyt nach Anspruch 1 oder 2, wobei der mindestens eine Komplexbildner aus der Gruppe bestehend aus Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure [EDTA], Diethylentriaminpentaessigsäure, Nitrilotriessigsäure [NTA], Hydroxyethyliminodiessigsäure [HEIDA], Nitrilopropiondiessigsäure [NPDA], Iminodiessigsäure [IDA], Nitrilotrimethylphosphorsäure [NTMA, Dequest 2000] und Triethanolamin [TEA] in einer Konzentration zwischen 0,05 und 0,6 Mol/l vorhanden ist.
  4. Elektrolyt nach einem der Ansprüche 1 bis 3, ferner mit Ionen mindestens eines Metalls aus der Gruppe bestehend aus Te, Sb, Se, Ag, Pt, Ni und Zn.
  5. Elektrolyt nach Anspruch 4, mit den Ionen mindestens eines Metall aus der Gruppe bestehend aus Sb, Se, Ag, Pt, Ni und Zn in einer Menge zwischen 0,1 mg/l und 10 g/l.
  6. Elektrolyt nach einem der Ansprüche 1 bis 5, ferner mit einem oberflächenaktiven Mittel.
  7. Elektrolyt nach Anspruch 6, wobei das oberflächenaktive Mittel ein Natriumlauryletherphosphat ist.
  8. Elektrolyt nach Anspruch 7, wobei das oberflächenaktive Mittel in einer Menge von 0,1 bis 5 ml/l vorhanden ist.
  9. Elektrolyt nach einem der Ansprüche 1 bis 8, ferner mit einem sekundären Glanzbildner und/oder Stabilisierungsmitteln.
  10. Elektrolyt nach einem der Ansprüche 1 bis 4, wobei der pH-Wert des Elektrolyts im Bereich von 8 bis 13 liegt.
  11. Verfahren zum Abscheiden einer Gold-Kupfer-Legierungsschicht auf einer Substratoberfläche, wobei das Verfahren die Schritte aufweist:
    - Vorbehandeln der zu metallisierenden Substratoberfläche;
    - Inkontaktbringen der zu metallisierenden Substratoberfläche mit einem Elektrolyten nach einem der Ansprüche 1 bis 10; und
    - Erzeugen eines Stromflusses zwischen dem Substrat und einer Anode.
  12. Verfahren nach Anspruch 11, wobei die Stromdichte des zwischen dem Substrat und der Anode fließenden Stroms im Bereich von 0,2 bis 2 A/dm2 liegt.
  13. Verfahren nach Anspruch 11 oder 12, wobei die Temperatur des Elektrolyten im Bereich von 70°C bis 90°C liegt.
  14. Gold-Kupfer-Legierungsbeschichtung, die durch ein Verfahren nach einem der Ansprüche 11 bis 13 auf einer Substratoberfläche abgeschieden wird, wobei die Dicke der Beschichtung > 20 µm beträgt und ihre Karatzahl im Bereich von 12 bis 19 kt liegt.
EP07007963.7A 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen Not-in-force EP1983077B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP07007963.7A EP1983077B1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen
EP16197251.8A EP3170924A1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen
CN2008100934716A CN101289756B (zh) 2007-04-19 2008-04-21 用于金铜合金电解沉积的电解组合物及方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07007963.7A EP1983077B1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen

Related Child Applications (3)

Application Number Title Priority Date Filing Date
EP16197251.8A Division-Into EP3170924A1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen
EP16197251.8A Division EP3170924A1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen
EP16197251.8A Previously-Filed-Application EP3170924A1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen

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EP1983077A1 EP1983077A1 (de) 2008-10-22
EP1983077B1 true EP1983077B1 (de) 2016-12-28

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EP16197251.8A Withdrawn EP3170924A1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen
EP07007963.7A Not-in-force EP1983077B1 (de) 2007-04-19 2007-04-19 Elektrolyt und verfahren zur elektrolytischen ablagerung von gold-kupfer-legierungen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022180650A1 (en) 2021-02-23 2022-09-01 Italfimet Srl Process for galvanic electrodeposition and associated galvanic bath

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EP2312021B1 (de) * 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Verfahren zum erhalten einer gelben goldlegierungsablagerung durch galvanoplastik ohne verwendung von giftigen metallen
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
KR102214110B1 (ko) * 2016-02-18 2021-02-09 닛폰세이테츠 가부시키가이샤 금속 화합물 입자의 추출 방법, 그 금속 화합물 입자의 분석 방법, 및 그것들에 사용되는 전해액
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

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GB1375611A (de) 1972-03-28 1974-11-27
EP0304315A1 (de) 1987-08-21 1989-02-22 Engelhard Limited Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung
EP0384679A1 (de) 1989-02-20 1990-08-29 Engelhard Corporation Elektroplattierung von Gold enthaltenden Legierungen
EP0416342A1 (de) 1989-09-06 1991-03-13 Degussa Aktiengesellschaft Galvanisches Goldlegierungsbad
EP0566054A1 (de) 1992-04-15 1993-10-20 LeaRonal, Inc. Elektroplattierte Gold-Kupfer-Silber Legierungen
EP1103637A1 (de) 1999-11-29 2001-05-30 ENTHONE-OMI, Inc. Verfahren zur Herstellung einer AuCuGa-Legierungsbeschichtung unter Verwendung von Elektrolyse und nach diesem Verfahren hergestellte Legierungen
EP1728898A2 (de) 2005-06-02 2006-12-06 Rohm and Haas Electronic Materials LLC Elektrolyte zur Abscheidung von Goldlegierungen

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CH632533A5 (fr) * 1979-06-14 1982-10-15 Aliprandini P Procede pour le depot galvanoplastique d'un alliage d'or.
CH662583A5 (fr) * 1985-03-01 1987-10-15 Heinz Emmenegger Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc.

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GB1375611A (de) 1972-03-28 1974-11-27
EP0304315A1 (de) 1987-08-21 1989-02-22 Engelhard Limited Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung
EP0384679A1 (de) 1989-02-20 1990-08-29 Engelhard Corporation Elektroplattierung von Gold enthaltenden Legierungen
EP0416342A1 (de) 1989-09-06 1991-03-13 Degussa Aktiengesellschaft Galvanisches Goldlegierungsbad
EP0566054A1 (de) 1992-04-15 1993-10-20 LeaRonal, Inc. Elektroplattierte Gold-Kupfer-Silber Legierungen
EP1103637A1 (de) 1999-11-29 2001-05-30 ENTHONE-OMI, Inc. Verfahren zur Herstellung einer AuCuGa-Legierungsbeschichtung unter Verwendung von Elektrolyse und nach diesem Verfahren hergestellte Legierungen
EP1728898A2 (de) 2005-06-02 2006-12-06 Rohm and Haas Electronic Materials LLC Elektrolyte zur Abscheidung von Goldlegierungen

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I.-M. MIHAESCU: "Cyanide Determination with a modified Ninhydrin Reagent using N- Acetyl Cysteine in the presence of Heavy Metal Ions", J. CHIL. CHEM. SOC., vol. 55, no. 4, 2010, pages 467 - 468, XP055425848
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022180650A1 (en) 2021-02-23 2022-09-01 Italfimet Srl Process for galvanic electrodeposition and associated galvanic bath

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Publication number Publication date
EP1983077A1 (de) 2008-10-22
CN101289756B (zh) 2012-06-20
EP3170924A1 (de) 2017-05-24
CN101289756A (zh) 2008-10-22

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