WO2009037180A1 - Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques - Google Patents

Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques Download PDF

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Publication number
WO2009037180A1
WO2009037180A1 PCT/EP2008/062042 EP2008062042W WO2009037180A1 WO 2009037180 A1 WO2009037180 A1 WO 2009037180A1 EP 2008062042 W EP2008062042 W EP 2008062042W WO 2009037180 A1 WO2009037180 A1 WO 2009037180A1
Authority
WO
WIPO (PCT)
Prior art keywords
bath
bath comprises
copper
gold
indium
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.)
Ceased
Application number
PCT/EP2008/062042
Other languages
English (en)
French (fr)
Inventor
Giuseppe Aliprandini
Michel Caillaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swatch Group Research and Development SA
G Aliprandini
Original Assignee
Swatch Group Research and Development SA
G Aliprandini
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39967872&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2009037180(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to IN2464CHN2014 priority Critical patent/IN2014CN02464A/en
Application filed by Swatch Group Research and Development SA, G Aliprandini filed Critical Swatch Group Research and Development SA
Priority to DE602008005184T priority patent/DE602008005184D1/de
Priority to AT08804009T priority patent/ATE499461T1/de
Priority to JP2010525308A priority patent/JP5563462B2/ja
Priority to CN200880107881XA priority patent/CN101815814B/zh
Priority to EP08804009A priority patent/EP2205778B1/fr
Priority to HK11101836.3A priority patent/HK1147782B/xx
Priority to US12/678,984 priority patent/US10233555B2/en
Priority to KR1020107008598A priority patent/KR101280675B1/ko
Publication of WO2009037180A1 publication Critical patent/WO2009037180A1/fr
Anticipated expiration legal-status Critical
Priority to US14/244,071 priority patent/US9683303B2/en
Priority to US16/259,444 priority patent/US10619260B2/en
Ceased legal-status Critical Current

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
    • C25D3/62—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)
PCT/EP2008/062042 2007-09-21 2008-09-11 Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques Ceased WO2009037180A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
HK11101836.3A HK1147782B (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
EP08804009A EP2205778B1 (fr) 2007-09-21 2008-09-11 Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques
DE602008005184T DE602008005184D1 (de) 2007-09-21 2008-09-11 Verfahren zur herstellung eines überzugs aus gelber goldlegierung durch galvanisieren ohne verwendung von toxischen metallen oder metalloiden
AT08804009T ATE499461T1 (de) 2007-09-21 2008-09-11 Verfahren zur herstellung eines überzugs aus gelber goldlegierung durch galvanisieren ohne verwendung von toxischen metallen oder metalloiden
JP2010525308A JP5563462B2 (ja) 2007-09-21 2008-09-11 有毒金属または半金属を使用することなく電気めっき法により黄色金合金析出物を得る方法
CN200880107881XA CN101815814B (zh) 2007-09-21 2008-09-11 不使用有毒金属或类似金属由电铸获得黄色金合金沉积物的方法
US12/678,984 US10233555B2 (en) 2007-09-21 2008-09-11 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
IN2464CHN2014 IN2014CN02464A (enExample) 2007-09-21 2008-09-11
KR1020107008598A KR101280675B1 (ko) 2007-09-21 2008-09-11 독성 금속 또는 독성 반금속의 사용 없이 전기도금에 의해 황색 금 합금 코팅을 수득하는 방법
US14/244,071 US9683303B2 (en) 2007-09-21 2014-04-03 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US16/259,444 US10619260B2 (en) 2007-09-21 2019-01-28 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH01494/07A CH710184B1 (fr) 2007-09-21 2007-09-21 Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques.
CH01494/07 2007-09-21

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US12/678,984 A-371-Of-International US10233555B2 (en) 2007-09-21 2008-09-11 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US14/244,071 Division US9683303B2 (en) 2007-09-21 2014-04-03 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US16/259,444 Continuation US10619260B2 (en) 2007-09-21 2019-01-28 Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids

Publications (1)

Publication Number Publication Date
WO2009037180A1 true WO2009037180A1 (fr) 2009-03-26

Family

ID=39967872

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/062042 Ceased WO2009037180A1 (fr) 2007-09-21 2008-09-11 Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques

Country Status (11)

Country Link
US (3) US10233555B2 (enExample)
EP (1) EP2205778B1 (enExample)
JP (2) JP5563462B2 (enExample)
KR (1) KR101280675B1 (enExample)
CN (1) CN101815814B (enExample)
AT (1) ATE499461T1 (enExample)
CH (1) CH710184B1 (enExample)
DE (1) DE602008005184D1 (enExample)
IN (1) IN2014CN02464A (enExample)
TW (2) TWI507571B (enExample)
WO (1) WO2009037180A1 (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
ITFI20120103A1 (it) * 2012-06-01 2013-12-02 Bluclad Srl Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni.
US9683303B2 (en) 2007-09-21 2017-06-20 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH714243B1 (fr) * 2006-10-03 2019-04-15 Swatch Group Res & Dev Ltd Procédé d'électroformage et pièce ou couche obtenue par ce procédé.
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
WO2016020812A1 (en) * 2014-08-04 2016-02-11 Nutec International Srl Electrolytic bath, electrolytic deposition method and item obtained with said method
CN109504991B (zh) * 2019-01-21 2020-08-07 南京市产品质量监督检验院 一种无氰18k金电铸液、其制备方法及其应用

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CH455434A (de) * 1963-08-15 1968-07-15 Werner Fluehmann Galvanische A Verfahren zur Herstellung von Weissgoldüberzügen
GB1134615A (en) * 1966-02-10 1968-11-27 Technic Gold electroplating bath
GB1156186A (en) * 1966-09-26 1969-06-25 Sel Rex Corp Gold Plating
DE1696087A1 (de) * 1968-03-08 1972-01-13 Sel Rex Corp Elektrolyt zur Abscheidung von Goldkupferlegierungen
GB1294601A (en) * 1969-01-07 1972-11-01 Western Electric Co Electrolytic plating solutions for deposition of noble metals
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9683303B2 (en) 2007-09-21 2017-06-20 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US10233555B2 (en) 2007-09-21 2019-03-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US10619260B2 (en) 2007-09-21 2020-04-14 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
US9567684B2 (en) 2009-10-15 2017-02-14 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
ITFI20120103A1 (it) * 2012-06-01 2013-12-02 Bluclad Srl Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni.
EP2669407A1 (en) * 2012-06-01 2013-12-04 Bluclad S.R.L. Galvanic baths for obtaining a low-carat gold alloy, and galvanic process that uses said baths

Also Published As

Publication number Publication date
JP2014194087A (ja) 2014-10-09
JP5887381B2 (ja) 2016-03-16
DE602008005184D1 (de) 2011-04-07
US20140299481A1 (en) 2014-10-09
CN101815814A (zh) 2010-08-25
KR101280675B1 (ko) 2013-07-01
EP2205778A1 (fr) 2010-07-14
US10233555B2 (en) 2019-03-19
US9683303B2 (en) 2017-06-20
CN101815814B (zh) 2012-05-16
EP2205778B1 (fr) 2011-02-23
ATE499461T1 (de) 2011-03-15
CH710184B1 (fr) 2016-03-31
JP2010539335A (ja) 2010-12-16
US20190153608A1 (en) 2019-05-23
TW201428143A (zh) 2014-07-16
US10619260B2 (en) 2020-04-14
TW200930844A (en) 2009-07-16
US20100206739A1 (en) 2010-08-19
JP5563462B2 (ja) 2014-07-30
IN2014CN02464A (enExample) 2015-08-07
TWI441959B (zh) 2014-06-21
TWI507571B (zh) 2015-11-11
HK1147782A1 (en) 2011-08-19
KR20100075935A (ko) 2010-07-05

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