EP2313541A1 - Cyanidfreies elektrolyt zur galvanischen abscheidung von gold oder legierungen davon - Google Patents

Cyanidfreies elektrolyt zur galvanischen abscheidung von gold oder legierungen davon

Info

Publication number
EP2313541A1
EP2313541A1 EP10724310A EP10724310A EP2313541A1 EP 2313541 A1 EP2313541 A1 EP 2313541A1 EP 10724310 A EP10724310 A EP 10724310A EP 10724310 A EP10724310 A EP 10724310A EP 2313541 A1 EP2313541 A1 EP 2313541A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
gold
electrolyte according
group
ligands
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
Application number
EP10724310A
Other languages
English (en)
French (fr)
Other versions
EP2313541B1 (de
Inventor
Hubert Schmidbaur
Jean-Jacques Duprat
Davide Rossi
Ester Falletta
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 EP2313541A1 publication Critical patent/EP2313541A1/de
Application granted granted Critical
Publication of EP2313541B1 publication Critical patent/EP2313541B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C25D3/48—Electroplating: Baths therefor from solutions 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
    • C25D3/56—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 invention relates to a cyanide-free electrolyte for galvanic deposition of gold or alloys thereof, which has a neutral or alkaline aqueous solution of at least one gold complex and possibly of a complex of an alloy former for gold, the complexes being present in anionic form.
  • the electrolyte according to the invention is used in galvanic deposition, in particular in coatings made of gold and alloys thereof.
  • galvanic baths based on gold- sulphite complexes are known.
  • US 4,435,253 teaches a galvanic bath which contains an alkali metal or ammonium-gold-sulphite and also, as further additives, thallium, which is toxic, and a carboxylic acid.
  • the disadvantage of galvanic baths which contain gold-sulphite complexes is however their low stability so that the result is formation of colloidal metallic gold in the galvanic bath, as a result of which the electrolyte becomes unusable.
  • Galvanic baths in which the gold is present as thio- sulphate complex are known from EP 0 611 840 Al.
  • a sulphinate is added here since these baths also have problems with respect to the stability of the complexes.
  • a further disadvantage in the just-mentioned galvanic baths concerns the fact that the current densities which can be applied are limited here since decomposition takes place at high current densities. Furthermore, the result with galvanic baths of this type can be odour problems .
  • a cyanide- free electrolyte for galvanic deposition of gold or gold alloys from a neutral or alkaline aqueous solution comprising at least one anionic complex of the general formula I
  • the gold is thereby present in the anionic complex in the oxidation state +1.
  • the electrolyte according to the invention leads to an entire series of important technological, ecological and economic advantages.
  • the ligands used according to the invention are easy to handle, in particular with respect to transport, storage, metering and disposal. Furthermore, these ligands are miscible without limitation with water.
  • the aqueous solutions are colourless, practically odour-free because of the low vapour pressure and stable thermally and in light and air within a wide temperature range (-30 to +100 0 C) .
  • the ligands according to the invention thereby have a low molecular weight, e.g. thioglycerine 108 g/mol or cysteamine 77 g/mol , so that the gold contents of their complexes are very high (above 50%) , which implies a low extraneous material ballast.
  • the stability of the complexes is assisted further by the presence of excess ligand concentrations because this counteracts the reverse dissociation of the complexes. It is further advantageous that the same ligand can be used for a plurality of metals, which facilitates the deposition of alloys .
  • the cyanide-containing electrolytes known from the prior art can no longer be tolerated by the legislator without onerous conditions with respect to worker safety, storage and disposal for medical and ecological reasons due to the toxicity of the hydrogen cya- nide and of the cyanides.
  • the toxicity of the inventive ligands L is in contrast low.
  • thioglycerine and cysteamine are used for example partially even in the pharmaceutical and cosmetic field without hesitation.
  • the use of the inventive electrolyte in galvanic equipments can thereby represent in many respects great progress .
  • ligands L which are soluble in water and cause the water solubility of the complexes are thereby preferred. Likewise, these compounds should have no toxic potential so that handling is not critical.
  • at least a part of the ligands L is selected from the group of the anions of 1- and 2 -thioglycerine, monothioglycol, mercapto-n-butane- triol, mercapto-i-butanetriol, mercaptopentanetetrol, cysteamine or combinations hereof .
  • thioglycerol is distinguished in that it is colourless and essentially odour- free.
  • the new invented electrolyte can contain an excess of ligand for improving the stability of the various metal complexes depending on ion strength, pH or anodic oxidation.
  • the number n of ligand is usually 4 but an excess of ligand at least added in the make-up of the first electrolyte gives a better convenient plating maintenance.
  • the additional number of ligand can vary from 0 to 10.
  • the ligands have a hydrophilic group which is selected from the group of hydroxyl, amino, amido, phosphate, sulphate, phosphonate, car- boxylate, and carbonyl groups or combinations hereof.
  • the alloy former for gold is preferably selected from the group consisting of copper, silver, iron, ruthenium, indium, gallium, germanium, tin, palladium, antimony, bismuth, cobalt, rhodium, iridium, nickel, zinc, cadmium, zirconium and lead.
  • These metals are preferably present in the following oxidation states in the complexes: Cu(I) or Cu(II), Ag(I), Fe(II) or Fe(III), In(III), Ga(III), Ge(IV), Sn(II) or Sn(IV), Pd(II), Sb(III) or Sb(V), Bi(III) or Bi(V), Co(II), Ni(II), Zn(II), Cd(II), Ru (III), Rh (III), Ir (III), Ir(IV) , Zr(IV) , Pb(II) .
  • the electrolyte can comprise further complex formers .
  • complex formers There are included herein in particular ethylenedia- minetetraacetate, nitrilotriacetate, oxalate, car- boxylates, ammonia, tartrate or 8-oxyquinoline and also mixtures hereof. These can also act as conductivity additives and as buffers .
  • complexes of the further metals with the ligand L or with other ligands common for these metals, in particular the above-mentioned complex formers, are added to the electrolyte.
  • the metal content of the electrolyte for gold as for each individual further metal present in the electrolyte is preferably in the range of 0.1 to 50 g/1 electrolyte, in particular of 0.1 to 15 g/1 electro- Iyte.
  • the electrolyte comprises further supplements or additives.
  • brighteners there are included herein in particular brighteners, wetting agents, conducting salts and mixtures hereof.
  • the brightener is thereby comprised preferably in a concentration of 0.001 to 5 g/1 in the electrolyte.
  • brighteners there are suitable inorganic bright- eners, in particular selenium or tellurium compounds, or organic brighteners, in particular pyridine-3- sulphonic acid, benzaldehyde, 2-butin-l, 4-diol and/or sodium nicotinate, amines and polyamines : Amines and reaction products between amine and chloro derivatives (epichlorhydrin, dichlordiethylether, chloro- bromo propane), e.g.
  • the wetting agent is preferably comprised in a concentration of 0.001 to 5 g/1 in the electrolyte.
  • concentration is in the range of 0.2 to 2 g/1.
  • the wetting agent is thereby preferably selected from the group of cationic, ani- onic, non- ionic or amphoteric surfactants.
  • Cationic surfactants include for example tetraal- kylammonium halides, alkyltrimethylammonium halides, hydroxyethylalkylimidazolines, polyoxyethylenealkyl- methylammonium halides, alkyldimethylammonium halides, alkyldimethylbenzylammonium halides, alkylamine hydrochlorides, alkylamine acetates, alkylamine oleates, alkylaminoethylglycines and alkylpyridinium halides .
  • anionic surfactants e.g.
  • alkyl- ⁇ -naphthalene sulphonic acids or salts thereof saponified fats, alkylsulphonates, ⁇ -olefin sulpho- nates, alkylbenzene sulphonates, alkylnaphthalene sulphonates, alkyldiphenylether disulphonates, al- kylether sulphonates, alkylsulphuric acid esters, polyoxyethylenealkylether sulphuric acid esters, polyoxyethylenealkylphenolether sulphuric acid esters, phosphoric acid monoesters of higher alcohols, polyoxyalkylenealkylether phosphoric acids and esters thereof, polyoxyalkylenealkylphenyl ether phosphates, polyoxyalkylenephenylether phosphates, poloxyethyl- enealkylether phosphates, polyoxyethylenealkylether acetates, alkanoylsarcosines, alkanoides
  • non-ionic surfactants there are used e.g. poly- oxyalkylenealkyl ethers or esters , polyoxyalkylene phenylethers, polyoxyalkylenenaphthyl (or alkyl- naphthyl) ethers, polyoxyalkylenebisphenolethers, polyoxyethylene-polyoxypropylene block copolymers, polyoxyalkylenesorbitan fatty acid esters, polyoxyal- kylenesorbitol fatty acid esters, polyethylene glycol fatty acid esters, polyoxyalkylene glycerine fatty acid esters, polyoxyalkylenealkylamines, polyoxyalkylene condensates of ethylene diamine, polyoxy- alkylenealkylphenylformalin condensates, glycerine fatty acid esters, polyglycerine fatty acid asters, pentaerythritol fatty acid esters, sorbitan mono fatty acid esters, higher fatty acid
  • amphoteric surfactants are preferably selected from the group consisting of 2-alkyl-N-carboxymethyl- N-hydroxyethylimidazolinium betaines, 2-alkyl-N- carboxyethyl-N-hydroxyethylimidazolinium betaines, 2- alkyl-N-carboxymethyl-N-carboxymethyloxyethylimidazo- linium betaines, 2-alkyl-N-carboxyethyl-N-carboxy- methyloxyethylimidazolinium betaines, dimethylalkyl betaines, N-alkyl- ⁇ -amino propionic acid or sodium salts thereof, alkylaminoethylglycine, N-alkyl-N- methyl-p-alanines or sodium salts thereof and fatty acid amidopropyldimethylaminoacetic acid betaines.
  • the electrolyte preferably comprises at least one conducting salt in a concentration of 0.01 to 250 g/1, in particular 0.01 to 100 g/1 or 0.01 to 50 g/1.
  • conducting salts preferably inorganic conducting salts, in particular from the group of sulphates, phosphates and pyrophosphates, or organic conducting salts, in particular from the group of salts of weak organic acids like formic, citric or acetic acid or preferably sodium citrate.
  • the conducting salt thereby serves to reduce the voltage with appropriate current density. During the electrolysis on the anode, it must thereby have sufficient stability.
  • the electrolyte preferably has a pH value in the range of 7 to 14, in particular of 10 to 13.
  • a caustic solution in particular NaOH, is thereby preferably used.
  • the inventive electrolyte is preferably free of chlo- rides, as a result of which formation of chlorine and resulting products in the galvanic bath can be avoided.
  • the inventive electrolyte is preferably thermally stable in the range of 20 to 85°C so that it can be used in standard temperature conditions by galvanic baths .
  • the number of ligands L of the complexes contained in the electrolyte corresponds at least to the sum of the coordination numbers of gold and also to the metals which are present. It is thereby preferred that an excess of ligands is present relative to the stoichiometrically fixed number of ligands for complete coordination of all metals, including gold. As a result, an improvement in the solubility and stability of the electrolyte can be ensured.
  • the inventive electrolyte is used preferably for the deposition of coatings made of gold and alloys thereof .
  • the inventive electrolyte can be used for flash plating of layers with a thickness of 0.03 ⁇ m to 0.5 ⁇ m.
  • the inventive electrolyte can be used for thick plating of layers with a thickness of 0.05 ⁇ m to 20 ⁇ m.
  • the present invention allows the electroforming of layers with a thickness of 20 ⁇ m to 500 ⁇ m.
  • Example 1 The subject according to the invention is intended to be explained in more detail with reference to the subsequent examples without wishing to restrict said subject to the special embodiments represented here.
  • Example 1 The subject according to the invention is intended to be explained in more detail with reference to the subsequent examples without wishing to restrict said subject to the special embodiments represented here.
  • Example 1 The subject according to the invention is intended to be explained in more detail with reference to the subsequent examples without wishing to restrict said subject to the special embodiments represented here.
  • This solution (50 ml, pH 13) with a content of 4.2 gl "1 gold (Au) is stable over at least 10 days in air in the temperature range 20 - 80 0 C, colourless and odour-free and can be used directly or with additives for galvanic gold deposition on various substrates.
  • Well tested electrolyte addi- tives are secondary potassium phosphate K 2 HPO 4 , sodium-potassium-tartrate NaKC 4 H 6 O 6 , tetrasodium ethyl- enediaminetetraacetate Na 4 Ci 0 H 8 N 2 O 8 (Na 4 EDTA) and others.
  • the thus produced electrolyte, without or with additives also represents a suitable original or storage solution for the galvanic deposition of gold alloys. For this purpose, there are admixed therewith corresponding proportions of original solutions of the desired other alloy components.
  • substrates made of copper, brass, bronze etc. are galvanically gold plated (1 Adm "2 , 3.1 V, 55°C, 5 min) .
  • the desired surface characteristic of the obtained coatings is adjusted by known methods (pre- and post-treatment of the substrates) and additives to the electrolyte (in particular brighteners) .
  • An electrolyte for gold- indium alloy has been made up with 2 g/L of gold thioglycerol and 0,4 g/L of indium thioglycerol .
  • 100 g/L of sodium formiate gave the needed electrical conductivity while the pH was stabilized at 11 with potassium hydroxide.
  • An anode of platinated titanium and a stirring agitation allows to pass 1,5 A/dm 2 at 50 0 C without burning at high current density.
  • the deposit is bright enough up to 1 ⁇ m plated in 10 min.
  • the alloy composition is Au 80% and In 20%.
  • the colour of the deposit in L, a, b values according Minolta colorimeter values is 85.0, 1,29 and 11,49, respectively, close to the IN or 2N colour.

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)
EP10724310.7A 2009-06-09 2010-06-09 Cyanidfreies elektrolyt zur galvanischen abscheidung von goldlegierungen Not-in-force EP2313541B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102009024396A DE102009024396A1 (de) 2009-06-09 2009-06-09 Cyanid-freier Elektrolyt zur galvanischen Abscheidung von Gold oder dessen Legierungen
US18578909P 2009-06-10 2009-06-10
PCT/EP2010/003465 WO2010142437A1 (en) 2009-06-09 2010-06-09 Cyanide-free electrolyte for galvanic deposition of gold or alloys thereof

Publications (2)

Publication Number Publication Date
EP2313541A1 true EP2313541A1 (de) 2011-04-27
EP2313541B1 EP2313541B1 (de) 2016-01-13

Family

ID=43069719

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10724310.7A Not-in-force EP2313541B1 (de) 2009-06-09 2010-06-09 Cyanidfreies elektrolyt zur galvanischen abscheidung von goldlegierungen

Country Status (4)

Country Link
EP (1) EP2313541B1 (de)
DE (1) DE102009024396A1 (de)
ES (1) ES2562005T3 (de)
WO (1) WO2010142437A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3604626A1 (de) * 2018-08-03 2020-02-05 COVENTYA S.p.A. Galvanisches bad zur abscheidung einer schwarzen legierung, verfahren zur elektrochemischen abscheidung einer schwarzen legierung auf einem substrat, schwarze legierung und mit solch einer schwarzen legierung beschichteter artikel

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FR2978765A1 (fr) * 2011-08-04 2013-02-08 Commissariat Energie Atomique Nouveaux liquides ioniques utilisables pour entrer dans la composition d'electrolyte pour dispositifs a stockage d'energie
CN103122471B (zh) * 2013-03-01 2015-10-28 沈阳师范大学 一种无氰镀铟的电镀液
CN103741180B (zh) * 2014-01-10 2015-11-25 哈尔滨工业大学 无氰光亮电镀金添加剂及其应用
CN105499560B (zh) * 2015-11-25 2017-11-28 国家纳米科学中心 一种促进银在金纳米球表面再生长的方法及其应用
CN106932511A (zh) * 2017-02-14 2017-07-07 中国环境科学研究院 一种环境水体中不同价态锑的检测方法
KR20200010340A (ko) 2017-05-23 2020-01-30 삭소니아 에델메탈레 게엠베하 귀금속 염 물질, 그 제조 방법 및 전기 도금용 용도
CN108950617B (zh) * 2018-07-11 2020-11-24 广州传福化学技术有限公司 一种含碲的锌镍合金电镀液及其电镀工艺
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
CN109881223B (zh) * 2019-03-11 2020-02-14 深圳市联合蓝海科技开发有限公司 无氰镀金液及其制备方法和应用
CN111411376A (zh) * 2020-03-09 2020-07-14 中国工程物理研究院激光聚变研究中心 无氰亚硫酸盐体系电镀金液及电镀方法
CN119392325B (zh) * 2024-12-31 2025-04-01 深圳创智芯联科技股份有限公司 用于微盲孔镀金的无氰镀金液及电镀方法

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EP3604626A1 (de) * 2018-08-03 2020-02-05 COVENTYA S.p.A. Galvanisches bad zur abscheidung einer schwarzen legierung, verfahren zur elektrochemischen abscheidung einer schwarzen legierung auf einem substrat, schwarze legierung und mit solch einer schwarzen legierung beschichteter artikel
WO2020025448A1 (en) * 2018-08-03 2020-02-06 Coventya S.P.A. Electroplating bath for depositing a black alloy, method for the electrochemical deposition of a black alloy on a substrate, a black alloy and an article coated with such black alloy

Also Published As

Publication number Publication date
EP2313541B1 (de) 2016-01-13
WO2010142437A1 (en) 2010-12-16
DE102009024396A1 (de) 2010-12-16
ES2562005T3 (es) 2016-03-02

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