EP2649223A2 - Électrolyte pour dépôt par voie galvanique d'alliages d'or et son procédé de production - Google Patents

Électrolyte pour dépôt par voie galvanique d'alliages d'or et son procédé de production

Info

Publication number
EP2649223A2
EP2649223A2 EP11799631.4A EP11799631A EP2649223A2 EP 2649223 A2 EP2649223 A2 EP 2649223A2 EP 11799631 A EP11799631 A EP 11799631A EP 2649223 A2 EP2649223 A2 EP 2649223A2
Authority
EP
European Patent Office
Prior art keywords
gold
electrolyte
group
electrolyte according
sulfite
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Withdrawn
Application number
EP11799631.4A
Other languages
German (de)
English (en)
Inventor
Davide Rossi
Ester Falletta
Hubert Schmidbaur
Jean-Jaques Duprat
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.)
Coventya SpA
Original Assignee
Coventya SpA
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
Application filed by Coventya SpA filed Critical Coventya SpA
Publication of EP2649223A2 publication Critical patent/EP2649223A2/fr
Withdrawn legal-status Critical Current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

Definitions

  • the present invention relates to cyanide-free electrolytes for the electrodeposition of binary and polynary alloys of gold which contain an alkaline solution of anionic thiolate complexes of gold and gold-alloyed metals.
  • These electrolytes can be prepared in a simple environmentally friendly and economical manner from commercially available aqueous solutions of sulfite complexes of gold and a multiplicity of salts of the corresponding alloying metals by addition of the thiols and setting of an alkaline pH of the galvanic bath.
  • Electrolytes show long-term stability and can be used for the electrodeposition of gold alloys.
  • the present invention relates to a process for the preparation of said electrolyte.
  • the electrodeposition of gold has been carried out for many years using electrolytes based on gold-cyanide complexes.
  • In the alkaline range there are portions of toxic alkali cyanides and also the other metal cyanides are extremely toxic.
  • the cyanide liberated during the electrolysis escapes in the form of toxic hydrogen cyanide or dicyan. This toxicity and associated problematic handling is one of the major disadvantages of cyanide-containing electrolytes.
  • Another problem relates to the disposal of the cyanides contained in the depleted electrolyte.
  • EP 0611840 AI galvanic baths are be ⁇ known in which there is gold as thiosulfate complex. To stabilize these complexes, a sulfinate is added here, since these baths also have problems with regard to the stability of the complexes.
  • Another disadvantage with the last mentioned galvanic baths concerns the fact that the reversible current densities are limited here, since decomposition takes place at high current densities. Furthermore, odors can occur in such galvanic baths.
  • US Pat. No. 6,165,342 presents electrolysis baths for the separation of gold and gold alloys in which gold complexes with mercaptosulfonic acids and disulfide disulfonic acids are used. These compounds have the disadvantage that, because of the high molecular weights of the sulfonic acids and the excess acid functions to be neutralized, they have a high proportion of foreign substances and thus only small amounts of gold. This circumstance also leads to corresponding processing and disposal problems.
  • Electrolyte is significantly improved.
  • This task is performed by the cyanide-free electrolyte for the electrodeposition of gold or gold.
  • a cyanide-free electrolyte is provided for the electrodeposition of binary or polynary gold alloys containing at least 50% by weight of gold, which consists of a neutral or alkaline solution which contains the following components:
  • At least one alloying agent for gold selected from the group consisting of Cu, Ag, In, Fe, Co, Ni, Zn, Ru and Pd,
  • a complexing agent selected from the group of the anions of 1- and 2-thioglycerol, monothioglycol, mercapto-n-butanetriol, mercapto-i-butanetriol, mercaptopentantetrol, cysteamine or combinations thereof and
  • the gold content of the electrolyte is obtained from a safe, environmentally sound, easy-to-use and economical source and can be adjusted to the desired concentrations.
  • a halogen-free composition of the electrolyzer ⁇ th is possible.
  • the electrolyte has a high long-term stability compared to cyanide-based electrolyzer ⁇ th. •
  • the components of the electrolyte show a high solubility in a wide pH range of 7 to 14 and there is no anodic precipitation.
  • the electrolyte has a content of gold in the range of 0.01 to 5 wt .-%, in particular from 0.05 to 1.5 wt .-% to.
  • the electrolyte contains at least one alloying agent in an amount of 0.1 to 35 wt .-%, in particular 0.1 to 10 wt .-%.
  • the electrolyte contains further metals selected from the group consisting of Ga, Ge, Sn, Sb, Bi, Rh, Ir, Zr. These metals are preferably contained in an amount of 0.1 to 5 wt .-%.
  • the electrolyte contains more complexing agents. These include in particular ethylenediaminetetra acetate, nitrilotriacetate, ammonia, tartrate or 8-oxyquinoline.
  • the electrolyte may contain additives selected from the following group:
  • Brightening agents in particular in a concentration of 0.01 to 5 wt .-%
  • Wetting agents in particular in a concentration of 0.05 to 0.5% by weight
  • Conducting salts in particular in a concentration of 1 to 20 wt .-%
  • the brightener is preferably an inorganic brightener, in particular a selenium and / or tellurium compound, or an organic brightener, in particular pyridine-3-sulfonic acid, benzaldehyde, 2-butyne-1, 4-diol and / or sodium nicotinate.
  • the wetting agent is preferably at least one surfactant selected from the group of cationic, anionic, nonionic, amphoteric surfactants or mixtures thereof.
  • the conductive salt is preferably an inorganic
  • Conducting salt in particular from the group of sulfates and phosphates, or an organic conductive salt, in particular from the group of citrates.
  • the pH of the electrolyte is preferably in the range from 7 to 14, in particular from 9 to 12.
  • Da ⁇ in the electrolyte is thermally stable in the range of 20 to 85 ° C.
  • the number of ligands of the complexes contained in the electrolyte at least equal to the sum of the maximum coordination numbers of gold and the metals present.
  • a particular advantage of the electrolyte according to the invention is that it is halogen-free.
  • a particularly preferred electrolyte contains the following components: Gold (I) ions,
  • At least one alloying agent for gold selected from the group consisting of Cu, Ag, In, Fe, Co, Ni, Zn, Ru and Pd,
  • the invention likewise provides a process for the preparation of a cyanide-free electrolyte as described above, in which an aqueous gold (I) sulfite solution is a metal salt selected from the group consisting of Cu, Ag, In, Fe, Co, Ni, Zn, Ru and Pd or mixtures thereof and a stoichiometric amount for complexing the contained gold and metal ions exceeding amount of a complexing agent selected from the group of the anions of 1- and 2-thioglycerol, monothioglycol, mercapto-n-butanetriol , Mercapto-i-butanetriol, mercapto-pentantetrol, cysteamine, or combinations thereof, and the pH of the solution is adjusted in the range of 7 to 14.
  • an aqueous gold (I) sulfite solution is a metal salt selected from the group consisting of Cu, Ag, In, Fe, Co, Ni, Zn, Ru and Pd or mixtures thereof and a stoichiometric amount
  • an electrolyte is prepared containing 100 g / L sodium formate, 100 g / L sodium sulfite, 4 g / L gold, 30 g / L taurine and 0.1 ml / L Sodium benzyl nicotinate be added. Furthermore, the calculated amounts of indium (III) sulfate and potassium stannate IV) and the corresponding equivalents of thioglycerol (> 4 equivalents per metal atom) are added. This sets the concentrations of indium and tin to 0.6 g / L and 0.3 g / 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)

Abstract

L'invention concerne des électrolytes exempts de cyanure utilisés pour le dépôt par voie galvanique d'alliages d'or binaires et polynaires, qui contiennent une solution alcaline de complexes thiolate anioniques d'or et de métaux formant des alliages avec l'or. Lesdits électrolytes peuvent être produits de manière aisée, écophile et économique, à partir de solutions aqueuses de complexes sulfite d'or, du commerce, et d'une pluralité de sels des métaux générateurs d'alliages correspondants, par adjonction des thiols et ajustement d'un pH alcalin du bain galvanique. Lesdits électrolytes présentent une stabilité à long terme et peuvent s'utiliser pour le dépôt galvanique d'alliages d'or. L'invention concerne également un procédé pour produire de tels électrolytes.
EP11799631.4A 2010-12-07 2011-12-07 Électrolyte pour dépôt par voie galvanique d'alliages d'or et son procédé de production Withdrawn EP2649223A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010053676A DE102010053676A1 (de) 2010-12-07 2010-12-07 Elektrolyt für die galvanische Abscheidung von Gold-Legierungen und Verfahren zu dessen Herstellung
PCT/EP2011/006155 WO2012076174A2 (fr) 2010-12-07 2011-12-07 Électrolyte pour dépôt par voie galvanique d'alliages d'or et son procédé de production

Publications (1)

Publication Number Publication Date
EP2649223A2 true EP2649223A2 (fr) 2013-10-16

Family

ID=45401026

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11799631.4A Withdrawn EP2649223A2 (fr) 2010-12-07 2011-12-07 Électrolyte pour dépôt par voie galvanique d'alliages d'or et son procédé de production

Country Status (3)

Country Link
EP (1) EP2649223A2 (fr)
DE (1) DE102010053676A1 (fr)
WO (1) WO2012076174A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699713A (zh) * 2019-11-21 2020-01-17 长春黄金研究院有限公司 一种无氰金合金电铸液及其使用方法

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AU2015388446B2 (en) 2015-03-25 2021-09-16 Essilor International Anti-reflective sputtering stack with low RV and low RUV
EP3371645A1 (fr) 2015-11-06 2018-09-12 Essilor International Article optique protégeant de la lumière bleue
JP2018536894A (ja) 2015-11-06 2018-12-13 エシロール アンテルナショナルＥｓｓｉｌｏｒ Ｉｎｔｅｒｎａｔｉｏｎａｌ 青色光及びｕｖ光から保護する光学物品
EP3371647A1 (fr) 2015-11-06 2018-09-12 Essilor International Article optique réduisant la lumière bleue
EP3327488B1 (fr) 2016-11-23 2021-01-06 Essilor International Article d'optique comportant un colorant résistant à la photodégradation
EP3327091B1 (fr) 2016-11-23 2023-01-18 Essilor International Composition époxy fonctionnelle protégeant des colorants de la photodégradation et revêtements durcis préparés à partir de celle-ci
EP3457197A1 (fr) 2017-09-19 2019-03-20 Essilor International Lentille optique pour corriger la vision des couleurs
DE102019202899B3 (de) * 2019-03-04 2019-11-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wässrige Formulierung zum Herstellen einer Schicht aus Gold und Silber
CN114635043B (zh) * 2020-12-16 2023-03-21 东北大学 一种以酒石酸为稳定剂的铜-硫代硫酸盐浸金工艺
CN112536046B (zh) * 2020-12-23 2023-10-03 郑州轻工业大学 具有高效还原活性的片状硫化铟锌光催化剂的制备方法
CN113809408A (zh) * 2021-08-20 2021-12-17 青岛科技大学 一种水系锌离子电池添加剂、电池电解液及其应用

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US4048023A (en) * 1976-06-09 1977-09-13 Oxy Metal Industries Corporation Electrodeposition of gold-palladium alloys
DE2744962A1 (de) * 1977-10-06 1979-04-19 Oxy Metal Industries Corp Galvanisches bad fuer die abscheidung von goldlegierungen
US6565732B1 (en) * 1999-10-07 2003-05-20 Tanaka Kikinzoku Kogyo K.K. Gold plating solution and plating process

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US3238112A (en) * 1962-07-03 1966-03-01 Du Pont Electroplating of metals using mercapto-metal complex salts
GB1594011A (en) * 1977-10-06 1981-07-30 Oxy Metal Industries Corp Gold alloy plating bath
US4366035A (en) * 1979-04-24 1982-12-28 Engelhard Corporation Electrodeposition of gold alloys
US4435253A (en) 1983-01-28 1984-03-06 Omi International Corporation Gold sulphite electroplating solutions and methods
US5302278A (en) 1993-02-19 1994-04-12 Learonal, Inc. Cyanide-free plating solutions for monovalent metals
DE19629658C2 (de) 1996-07-23 1999-01-14 Degussa Cyanidfreies galvanisches Bad zur Abscheidung von Gold und Goldlegierungen
JP3985220B2 (ja) * 2001-12-06 2007-10-03 石原薬品株式会社 非シアン系の金−スズ合金メッキ浴
JP2004176171A (ja) 2002-09-30 2004-06-24 Shinko Electric Ind Co Ltd 非シアン電解金めっき液

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048023A (en) * 1976-06-09 1977-09-13 Oxy Metal Industries Corporation Electrodeposition of gold-palladium alloys
DE2744962A1 (de) * 1977-10-06 1979-04-19 Oxy Metal Industries Corp Galvanisches bad fuer die abscheidung von goldlegierungen
US6565732B1 (en) * 1999-10-07 2003-05-20 Tanaka Kikinzoku Kogyo K.K. Gold plating solution and plating process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2012076174A2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110699713A (zh) * 2019-11-21 2020-01-17 长春黄金研究院有限公司 一种无氰金合金电铸液及其使用方法

Also Published As

Publication number Publication date
WO2012076174A8 (fr) 2012-08-23
DE102010053676A1 (de) 2012-06-14
WO2012076174A3 (fr) 2013-02-14
WO2012076174A2 (fr) 2012-06-14

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