EP0907767A1 - Cyanide-free electroplating bath for deposition of gold and gold alloys - Google Patents
Cyanide-free electroplating bath for deposition of gold and gold alloysInfo
- Publication number
- EP0907767A1 EP0907767A1 EP97933686A EP97933686A EP0907767A1 EP 0907767 A1 EP0907767 A1 EP 0907767A1 EP 97933686 A EP97933686 A EP 97933686A EP 97933686 A EP97933686 A EP 97933686A EP 0907767 A1 EP0907767 A1 EP 0907767A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- cyanide
- free
- acid
- bath
- 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.)
- Granted
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 a cyanide-free galvanic bath for the deposition of gold and gold alloy coatings, with 0.5 to 30 g / 1 gold in the form of a complex of a sulfur-containing compound, 0 to 50 g / 1 of an alloy metal in the form of water-soluble compounds of silver, copper, Indium, cadmium, zinc, tin, bismuth, arsenic and / or antimony, 1 to 200 g / 1 of the free sulfur-containing compound, 0 to 200 g / 1 conductive and buffer salts in the form of alkali borates, phosphates, citrates, tartrates and / or gluconates and given all wetting agents and brighteners.
- Electrolytic deposition of gold is mainly used for the electrodeposition of gold
- Gold cyanide complexes are used, which also contain larger amounts of toxic alkali cyanides, at least in the alkaline range. In the acidic and neutral range, the cyanide released during electrolysis at least partially escapes as highly toxic hydrocyanic acid. In addition to the strong toxicity, cyanide baths cause problems in detoxifying the cyanide, which in practice is mainly done with alkali hypochlorite. So-called adsorbable halogen compounds (AOX) can form, which cause difficulties in wastewater treatment. The efforts to produce galvanic gold baths without the use of the toxic complexing agent cyanide therefore go back a long time. However, apart from baths based on gold sulfite complexes, no technically usable bath has yet been produced.
- AOX adsorbable halogen compounds
- Contain thiosulfato complex (DE-PS 24 45 538), are not much more stable. They decompose, like other well-known gold complexes with sulfur-containing compounds, sometimes when standing for a long time. In EP-OS 0 611 840, the gold thiosulfato complexes are therefore stabilized by adding sulfinates. The applicable current density is limited in these baths and decomposition usually occurs at current densities above 1 A / dm. In addition, these baths usually cause unpleasant smells.
- the bath contains a mercaptosulfonic acid, a disulfide sulfonic acid, or mixtures of these compounds as the sulfur-containing compound of the gold complex.
- the salts preferably the alkali salts, of these compounds are also suitable.
- the baths preferably contain 1 to 200 g / l of the free sulfur-containing compound or its alkali metal salts in excess of the stoichiometric composition of the corresponding gold complex.
- the baths contain 0.01 to 10 g / l of wetting agent in the form of surfactants and 0.1 to 1000 mg / l of brightener in the form of selenium and / or tellurium compounds.
- the bath is advantageously operated at a pH of 7 to 12.
- the sulfur-containing compounds which are suitable for the baths according to the invention show good solubility in water and great stability, combined with a low vapor pressure, so that no bad smell is perceptible.
- the sulfur-containing compounds to be used according to the invention can be represented by the general formula I.
- Typical compounds of formula I are:
- the corresponding gold complexes are obtained by simply reacting soluble gold compounds, such as, for example, tetrachloroauric acid, sodium aurate solutions or the like, with the stoichiometric amount or an excess of these sulfur-containing compounds in aqueous solution. Note the stoichiometric amount of sulfur-containing compounds required for the reduction to gold (I). If the electroplating bath is to be free of chloride ions, gold must first be precipitated with ammonia solution as gold, washed thoroughly and dissolved in an aqueous solution of the sulfur-containing compound.
- the solution of the gold complex can be used directly to prepare the galvanic bath.
- the bath preferably contains an excess of sulfur-containing compounds of 1-200 g / 1.
- Semi-metals arsenic and antimony They are used either in the form of the corresponding sulfur compounds, as is preferred for silver and copper, or in the form of other complexes with hydroxyl ions, with nitrilotriacetic acid, or ethylenediaminetetraacetic acid (EDTA), as complexes with hydroxycarboxylic acids, such as gluconic acid, citric acid and tartaric acid, as complexes with dicarboxylic acids , such as oxalic acid, with amines, such as ethylenediamine, with phosphonic acids, such as 1-hydroxyethane diphosphonic acid, e
- Bismuth is preferably used as citrate or EDTA complex
- tin is preferably used as oxalatostannnate (IV) or tin (II) - gluconate complex and indium is used as gluconate or EDTA complex.
- Arsenic and antimony are used primarily to increase hardness and gloss. Arsenic is preferably used in the form of alkali arsenite compounds, antimony is preferably used in the form of alkali mononyl tartrate.
- the concentration of the alloy metals can vary within wide limits between 10 mg / 1 and 50 g / 1.
- the concentration of free complexing agents in the bath can be between 0.1 and 200 g / l.
- conductive and buffer substances such as borates, tetraborates, phosphates, citrates, tartrates or gluconates of the alkali metals in concentrations of 1-200 g / 1 increase the conductivity and spreadability of the bath.
- ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ethers with end groups as alcohol, sulfate, sulfonate or phosphate, and perfluorinated compounds, such as Perfluoroalkane carboxylates or sulfonates and cationic surfactants, for example tetraalkyammonium perfluoroalkane sulfonates.
- the baths thus contain:
- conductive and buffer substances from the group of alkali borates, phosphates, citrates, tartrates,
- 0-50 g / 1 alloy metal from the group silver, copper, cadmium, indium, tin, zinc, bismuth, arsenic and antimony in the form of the complexes and compounds mentioned.
- wetting agent e.g. ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ether with end groups as alcohol, sulfate, sulfonate or phosphate and perfluorinated compounds such as perfluoroalkane carboxylates or sulfonates as well as cationic surfactants, e.g.
- ionic and nonionic surfactants of the ethylene oxide adduct type such as alkyl (fatty acid) or nonylphenol polyglycol ether with end groups as alcohol, sulfate, sulfonate or phosphate and perfluorinated compounds such as perfluoroalkane carboxylates or sulfonates as well as cationic surfactants, e.g.
- Tetraalkyammonium perfluoroalkanesulfonates are intended to illustrate the invention:
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
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19629658A DE19629658C2 (en) | 1996-07-23 | 1996-07-23 | Cyanide-free galvanic bath for the deposition of gold and gold alloys |
DE19629658 | 1996-07-23 | ||
PCT/EP1997/003903 WO1998003700A1 (en) | 1996-07-23 | 1997-07-21 | Cyanide-free electroplating bath for deposition of gold and gold alloys |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0907767A1 true EP0907767A1 (en) | 1999-04-14 |
EP0907767B1 EP0907767B1 (en) | 2002-02-13 |
Family
ID=7800576
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97933686A Expired - Lifetime EP0907767B1 (en) | 1996-07-23 | 1997-07-21 | Cyanide-free electroplating bath for deposition of gold and gold alloys |
Country Status (6)
Country | Link |
---|---|
US (1) | US6165342A (en) |
EP (1) | EP0907767B1 (en) |
JP (1) | JPH11513078A (en) |
KR (1) | KR20000064256A (en) |
DE (2) | DE19629658C2 (en) |
WO (1) | WO1998003700A1 (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1146147A4 (en) * | 1999-10-07 | 2006-08-16 | Tanaka Precious Metal Ind | Gold plating liquid and method of plating using the gold plating liquid |
EP1162289A1 (en) * | 2000-06-08 | 2001-12-12 | Lucent Technologies Inc. | Palladium electroplating bath and process for electroplating |
DE10110743A1 (en) * | 2001-02-28 | 2002-09-05 | Wieland Dental & Technik Gmbh | Bath for the electrodeposition of gold and gold alloys and its use |
CN100392155C (en) * | 2001-02-28 | 2008-06-04 | 威兰牙科技术有限责任两合公司 | Bath for galvanic deposition of gold and gold alloys, and use thereof |
US6736954B2 (en) * | 2001-10-02 | 2004-05-18 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
JP3985220B2 (en) * | 2001-12-06 | 2007-10-03 | 石原薬品株式会社 | Non-cyan gold-tin alloy plating bath |
CA2365749A1 (en) | 2001-12-20 | 2003-06-20 | The Governors Of The University Of Alberta | An electrodeposition process and a layered composite material produced thereby |
JP2006111960A (en) * | 2004-09-17 | 2006-04-27 | Shinko Electric Ind Co Ltd | Non-cyanide electroless gold plating solution and process for electroless gold plating |
JP4759416B2 (en) * | 2006-03-20 | 2011-08-31 | 新光電気工業株式会社 | Non-cyanide electroless gold plating solution and electroless gold plating method |
CH710184B1 (en) | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids. |
DE102009024396A1 (en) | 2009-06-09 | 2010-12-16 | Coventya Spa | Cyanide-free electrolyte for electrodeposition of gold or its alloys |
EP2312021B1 (en) | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals |
JP5529497B2 (en) * | 2009-11-05 | 2014-06-25 | 三菱重工印刷紙工機械株式会社 | Ink cleaning method and apparatus for flexographic printing machine |
DE102010053676A1 (en) | 2010-12-07 | 2012-06-14 | Coventya Spa | Electrolyte for the electrodeposition of gold alloys and process for its production |
DE102012004348B4 (en) | 2012-03-07 | 2014-01-09 | Umicore Galvanotechnik Gmbh | Use of organic thiourea compounds to increase the galvanic deposition rate of gold and gold alloys |
ITFI20120103A1 (en) * | 2012-06-01 | 2013-12-02 | Bluclad Srl | GALVANIC BATHROOMS FOR THE ACHIEVEMENT OF A LEAGUE OF LOW-CARATHED GOLD AND GALVANIC PROCESS THAT USES THESE BATHROOMS. |
CN102731536A (en) * | 2012-06-29 | 2012-10-17 | 长沙铂鲨环保设备有限公司 | Anionic type gold complex and application thereof |
CN104428934B (en) * | 2012-07-13 | 2017-12-08 | 东洋钢钣株式会社 | Separator for fuel battery, cell of fuel cell, the manufacture method of fuel cell pack and separator for fuel battery |
CN103741180B (en) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | Non-cyanide bright electrogilding additive and application thereof |
CN104233385A (en) * | 2014-10-22 | 2014-12-24 | 华文蔚 | Electroplating liquid for non-cyanide plating gold by thiazole and electroplating method thereof |
JP6207655B1 (en) * | 2016-04-12 | 2017-10-04 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Non-cyan Au-Sn alloy plating solution |
CN106757201B (en) * | 2016-12-29 | 2019-01-15 | 三门峡恒生科技研发有限公司 | A kind of no cyanogen faintly acid electroplate liquid, and preparation method thereof and application method |
DE102019202899B3 (en) * | 2019-03-04 | 2019-11-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Aqueous formulation for producing a layer of gold and silver |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US35513A (en) * | 1862-06-10 | Improvement in window-sash | ||
US3057789A (en) * | 1959-02-26 | 1962-10-09 | Paul T Smith | Gold plating bath and process |
DE2355581C3 (en) * | 1973-11-07 | 1979-07-12 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Galvanic bright gold bath with high deposition rate |
DE2445538C2 (en) * | 1974-09-20 | 1984-05-30 | Schering AG, 1000 Berlin und 4709 Bergkamen | Cyanide-free bath and process for the electrodeposition of precious metal alloys |
JPS5337149A (en) * | 1976-09-20 | 1978-04-06 | Toho Kasei Kougiyou Kk | Gold plating method |
JPS5384829A (en) * | 1976-12-30 | 1978-07-26 | Seiko Instr & Electronics | Nonncyanogen gold alloy plating liquid |
CH622829A5 (en) * | 1977-08-29 | 1981-04-30 | Systemes Traitements Surfaces | |
US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
EP0693579B1 (en) * | 1994-07-21 | 1997-08-27 | W.C. Heraeus GmbH | Palladium-silver alloys electroplating bath |
JP3365866B2 (en) * | 1994-08-01 | 2003-01-14 | 荏原ユージライト株式会社 | Non-cyanide precious metal plating bath |
-
1996
- 1996-07-23 DE DE19629658A patent/DE19629658C2/en not_active Expired - Fee Related
-
1997
- 1997-07-21 DE DE59706393T patent/DE59706393D1/en not_active Expired - Fee Related
- 1997-07-21 WO PCT/EP1997/003903 patent/WO1998003700A1/en not_active Application Discontinuation
- 1997-07-21 JP JP10506567A patent/JPH11513078A/en active Pending
- 1997-07-21 US US09/043,416 patent/US6165342A/en not_active Expired - Fee Related
- 1997-07-21 EP EP97933686A patent/EP0907767B1/en not_active Expired - Lifetime
- 1997-07-21 KR KR1019980702064A patent/KR20000064256A/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9803700A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1998003700A1 (en) | 1998-01-29 |
US6165342A (en) | 2000-12-26 |
DE19629658A1 (en) | 1998-01-29 |
DE59706393D1 (en) | 2002-03-21 |
KR20000064256A (en) | 2000-11-06 |
DE19629658C2 (en) | 1999-01-14 |
JPH11513078A (en) | 1999-11-09 |
EP0907767B1 (en) | 2002-02-13 |
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