EP2313541B1 - Cyanidfreies elektrolyt zur galvanischen abscheidung von goldlegierungen - Google Patents

Cyanidfreies elektrolyt zur galvanischen abscheidung von goldlegierungen Download PDF

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Publication number
EP2313541B1
EP2313541B1 EP10724310.7A EP10724310A EP2313541B1 EP 2313541 B1 EP2313541 B1 EP 2313541B1 EP 10724310 A EP10724310 A EP 10724310A EP 2313541 B1 EP2313541 B1 EP 2313541B1
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Prior art keywords
electrolyte
gold
electrolyte according
group
mercapto
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French (fr)
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EP2313541A1 (de
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Hubert Schmidbaur
Jean-Jacques Duprat
Davide Rossi
Ester Falletta
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Coventya SpA
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Coventya SpA
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    • 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 alloys, which has a neutral or alkaline aqueous solution of at least one gold complex and 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 alloys.
  • the galvanic deposition of gold has been effected for many years using electrolytes based on gold-cyanide complexes.
  • electrolytes based on gold-cyanide complexes In the alkaline range, proportions of toxic alkali cyanides are present and also the remaining metal cyanides are extremely toxic.
  • the cyanide released during electrolysis can escape in the form of toxic hydrogen cyanide or cyanogen.
  • This toxicity and problematic handling associated therewith represents one of the substantial disadvantages of cyanide-containing electrolytes.
  • a further problem relates to disposal of the cyanides contained in the depleted electrolyte.
  • 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 thiosulphate complex are known from EP 0 611 840 A1 .
  • 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.
  • US 2004/069641 A1 and US 6,733,651 B1 disclose a non-cyanogen type electrolytic solution for plating pure gold comprising a gold-complexing agent.
  • US 6,251,249 discloses a iodide-free and cyanide-free aqueous solution for deposition of precious metals, like e.g. gold, comprising an organosulfur compound or carboxylic acid complexing agent.
  • US 3,238,488 discloses a cyanide-free solution for electroplating metals like tin, copper, cadmium or zinc comprising a thioglycerol complexing agent.
  • EP 1 300 488 A2 discloses a plating bath for plating metals like copper comprising organic compounds that increase the life of the plating bath and improve the efficiency of the plating process.
  • JP 2003/171789 discloses a cyanide-free gold-tin alloy plating bath comprising a sulfureous complexing agent for complexing gold and a carboxylic or polyamine complexing agent for complexing tin.
  • a cyanide-free electrolyte for galvanic deposition of gold alloys from a neutral or alkaline aqueous solution comprising at least one anionic complex of the general formula I [Au(L) n ] (n-1)
  • 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°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 cyanide 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.
  • the ligand 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. It forms soluble complexes with gold but also with copper, tin, indium, silver, iron, palladium, bismuth, zinc, cobalt, nickel, cadmium, gallium, germanium and antimony.
  • a further advantage resides in the fact that thioglycerol is very easy to handle.
  • 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 alloy former for gold is 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.
  • 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/l electrolyte, in particular of 0.1 to 15 g/l electrolyte.
  • the electrolyte comprises further supplements or additives.
  • wetting agents for example wetting agents, conducting salts and mixtures hereof.
  • the brightener is comprised preferably in a concentration of 0.001 to 5 g/l in the electrolyte.
  • inorganic brighteners in particular selenium or tellurium compounds, or organic brighteners, in particular pyridine-3-sulphonic acid, benzaldehyde, 2-butin-1,4-diol and/or sodium nicotinate, amines and polyamines: Amines and reaction products between amine and chloro derivatives (epichlorhydrin, dichlorodiethylether, chloro-bromo propane), e.g.
  • condensation product of N, N'-bis ⁇ 3-(dimethylamino)propyl) urea on dichlorodiethyl ether polyethylene-imine and derivatives (oxidized or ethylenated), e.g. polyethylene-imine of molecular weight lower than 1000, aldehydes and ketones, sulfonated or solubilised by solvent or hydrotrope, e.g. anisaldehyde, vanillin, piperonal, benzyliden acetone, aryl sulfonates, e.g.
  • the wetting agent is preferably comprised in a concentration of 0.001 to 5 g/l in the electrolyte.
  • concentration is in the range of 0.2 to 2 g/l.
  • the wetting agent is thereby preferably selected from the group of cationic, anionic, non-ionic or amphoteric surfactants.
  • Cationic surfactants include for example tetraalkylammonium halides, alkyltrimethylammonium halides, hydroxyethylalkylimidazolines, polyoxyethylenealkylmethylammonium 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 sulphonates, alkylbenzene sulphonates, alkylnaphthalene sulphonates, alkyldiphenylether disulphonates, alkylether 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, polyoxyethylenealkylether phosphates, polyoxyethylenealkylether acetates, alkanoylsarcosines, alkan
  • non-ionic surfactants there are used e.g. polyoxyalkylenealkyl ethers or esters, polyoxyalkylene phenylethers, polyoxyalkylenenaphthyl (or alkylnaphthyl) ethers, polyoxyalkylenebisphenolethers, polyoxyethylene-polyoxypropylene block copolymers, polyoxyalkylenesorbitan fatty acid esters, polyoxyalkylenesorbitol fatty acid esters, polyethylene glycol fatty acid esters, polyoxyalkylene glycerine fatty acid esters, polyoxyalkylenealkylamines, polyoxyalkylene condensates of ethylene diamine, polyoxyalkylenealkylphenylformalin condensates, glycerine fatty acid esters, polyglycerine fatty acid asters, pentaerythritol fatty acid esters, sorbitan mono fatty acid esters, higher fatty acid monoethanolamides,
  • 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-carboxymethyloxyethylimidazolinium betaines, 2-alkyl-N-carboxyethyl-N-carboxymethyloxyethylimidazolinium 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/l, in particular 0.01 to 100 g/l or 0.01 to 50 g/l.
  • 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 chlorides, 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 of 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 of 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 for the deposition of coatings made of gold alloys.
  • 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.
  • 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°C, colourless and odour-free and can be used directly or with additives for galvanic gold deposition on various substrates.
  • Well tested electrolyte additives are secondary potassium phosphate K 2 HPO 4 , sodium-potassium-tartrate NaKC 4 H 6 O 6 , tetrasodium ethylenediaminetetraacetate Na 4 C 10 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.
  • 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°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 1N or 2N color.

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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 (18)

  1. Cyanidfreier Elektrolyt zur galvanischen Abscheidung von Goldlegierungen enthaltend eine neutrale oder eine alkalische wässrige Lösung von mindestens einem anionischen Komplex der allgemeinen Formel I

            [Au(L)n](n-1)-     I

    mit
    L ausgewählt aus der Gruppe der Anionen von 1- und 2-Thioglycerin, Monothioglycol, Mercapto-n-butantriol, Mercapto-iso-butantriol, Mercaptopentantetrol, Cysteamin oder Kombinationen hiervon, und n = 2 bis 5
    und mindestens einem anionischen Komplex der allgemeinen Formel II

            [M(L)m]x-     II

    mit
    M= Legierungsbildner für Gold ausgewählt aus der Gruppe umfassend Cu, Ag, Fe, Ru, In, Ga, Ge, Sn, Pd, Sb, Bi, Co, Rh, Ir, Ni, Zn, Cd, Zr und Pb,
    L ausgewählt aus der Gruppe der Anionen von 1- und 2-Thioglycerin, Monothioglycol, Mercapto-n-butantriol , Mercapto-i-butantriol, Mercaptopentantetrol, Cysteamin oder Kombinationen hiervon, und m = 2 bis 6 und x = 1 bis 4,
    dadurch gekennzeichnet, dass der Elektrolyt mindestens einen optischen Aufheller beinhaltet.
  2. Elektrolyt gemäß Anspruch 1,
    dadurch gekennzeichnet, dass der Elektrolyt als Gegenion zu dem anionischen Komplex mindestens ein Kation E enthält, ausgewählt aus der Gruppe umfassend Alkaliionen, insbesondere Na+ und K+, quaternäre Ionen, insbesondere NH4 +, NR4 +, PR4 + mit R = C1-C12-Alkyl oder Aryl, oder Diazonium-Ionen und Kombinationen hiervon.
  3. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt weitere Komplexbildner, insbesondere Ethylendiamintetraacetat, Nitrilotriacetat, Ammoniak, Tartrat oder 8-Oxychinolin, enthält.
  4. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Metallgehalt des Elektrolytes für jedes einzelne Metall im Bereich von 0,1 bis 50 g/L Elektrolyt, insbesondere 0,1 bis 15 g/L Elektrolyt liegt.
  5. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt als weitere Additive Benetzungsreagenzien, leitfähige Salze oder Mischungen hiervon enthält.
  6. Elektrolyt gemäß Anspruch 5, dadurch gekennzeichnet, dass der mindestens eine optische Aufheller in einer Konzentration von 0,001 bis 5 g/L in dem Elektrolyt enthalten ist.
  7. Elektrolyt gemäß Anspruch 5 oder 6, dadurch gekennzeichnet, dass ein anorganischer optischer Aufheller als optischer Aufheller enthalten ist, insbesondere eine Selen- oder Tellur-Verbindung, oder ein organischer optischer Aufheller, insbesondere Pyridin-3-Schwefelsäure, Benzaldehyd, 2-Butin-1,4-diol und/oder Natriumnicotinat.
  8. Elektrolyt gemäß einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, dass das mindestens eine Benetzungsreagenz in einer Konzentration von 0,001 bis 5 g/L, insbesondere von 0,2 bis 2 g/L in dem Elektrolyt enthalten ist.
  9. Elektrolyt gemäß einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, dass das Benetzungsreagenz aus der Gruppe der Kationen, Anionen, Nicht-Ionen, amphoteren Beschichtungsreagenzien oder aus Mischungen hiervon ausgewählt ist.
  10. Elektrolyt gemäß einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, dass das mindestens eine leitfähige Salz in einer Konzentration von 0,01 bis 250 g/L, insbesondere von 0,01 bis 100 g/L enthalten ist.
  11. Elektrolyt gemäß einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, dass das mindestens eine leitfähige Salz ein anorganisches leitfähiges Salz ist, insbesondere ausgewählt aus der Gruppe der Sulfate, Phosphate und Pyrophosphate, oder ein organisches leitfähiges Salz, insbesondere ausgewählt aus der Gruppe der Salze schwacher organischer Säuren, bevorzugt Ameisen-, Zitronen- oder Essigsäure.
  12. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der pH-Wert des Elektrolyts im Bereich von 7 bis 14, insbesondere von 10 bis 13 liegt.
  13. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt frei von Chloriden ist.
  14. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt im Bereich von 20 bis 85°C thermisch stabil ist.
  15. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Anzahl der Liganden L der in dem Elektrolyt enthaltenen Komplexe mindestens der Summe der maximalen Koordinationszahl von Gold und auch von den anwesenden Metallen entspricht.
  16. Elektrolyt gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Elektrolyt durch Lösen von mindestens einem Goldsalz, mindestens einem Komplex bei dem L vorher aus der Gruppe der Anionen von 1- und 2-Thioglycerin, Monothioglycol, Mercapto-n-butantriol, Mercapto-i-butantriol , Mercaptopentantetrol, Cysteamin oder Kombinationen hiervon ausgewählt wurde, einer Ammonium oder Alkali-haltigen Ätzlösung und einem Salz eines Legierungsbildners für Gold ausgewählt aus der Gruppe von Cu, Ag, Fe, Ru, In, Ga, Ge, Sn, Pd, Sb, Bi, Co, Rh, Ir, Ni, Zn, Cd, Zr und Pb, hergestellt wird.
  17. Verwendung des Elektrolyts gemäß einem der vorhergehenden Ansprüche für die Abscheidung von Beschichtungen auf Basis von Goldlegierungen.
  18. Verwendung des Elektrolyts gemäß dem vorhergehenden Anspruch für die Vorbeschichtung von Schichten mit einer Dicke von 0,03 µm bis 0,05 µm, für die Dicklagenbeschichtung von Schichten mit einer Dicke von 0,05 µm bis 20 µm oder für die Galvanoformung von Schichten mit einer Dicke von 20 µm bis 500 µm.
EP10724310.7A 2009-06-09 2010-06-09 Cyanidfreies elektrolyt zur galvanischen abscheidung von goldlegierungen Active EP2313541B1 (de)

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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

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

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Publication number Priority date Publication date Assignee Title
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
CN109881223A (zh) * 2019-03-11 2019-06-14 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

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