EP1961840B1 - Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze - Google Patents

Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze Download PDF

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Publication number
EP1961840B1
EP1961840B1 EP07003097A EP07003097A EP1961840B1 EP 1961840 B1 EP1961840 B1 EP 1961840B1 EP 07003097 A EP07003097 A EP 07003097A EP 07003097 A EP07003097 A EP 07003097A EP 1961840 B1 EP1961840 B1 EP 1961840B1
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EP
European Patent Office
Prior art keywords
electrolyte
acid
copper
tin
phosphonic acid
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.)
Not-in-force
Application number
EP07003097A
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German (de)
English (en)
Other versions
EP1961840A1 (fr
Inventor
Klaus Dipl.-Ing. Bronder
Bernd Dipl.-Ing. Weyhmüller
Frank Oberst
Sascha Dr. Berger
Michael Dr. Lauster
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.)
Umicore Galvanotechnik GmbH
Original Assignee
Umicore Galvanotechnik GmbH
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 Umicore Galvanotechnik GmbH filed Critical Umicore Galvanotechnik GmbH
Priority to PL07003097T priority Critical patent/PL1961840T3/pl
Priority to AT07003097T priority patent/ATE453740T1/de
Priority to EP07003097A priority patent/EP1961840B1/fr
Priority to DE502007002479T priority patent/DE502007002479D1/de
Priority to TW097101536A priority patent/TW200844266A/zh
Priority to CN2008800069531A priority patent/CN101622379B/zh
Priority to PCT/EP2008/000534 priority patent/WO2008098666A1/fr
Priority to US12/526,727 priority patent/US8211285B2/en
Priority to JP2009549787A priority patent/JP2010518260A/ja
Publication of EP1961840A1 publication Critical patent/EP1961840A1/fr
Application granted granted Critical
Publication of EP1961840B1 publication Critical patent/EP1961840B1/fr
Priority to HK10102901.2A priority patent/HK1137785A1/xx
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper

Definitions

  • the invention relates to a copper-tin electrolyte which is free of toxic ingredients such as cyanides or thio compounds. Furthermore, the invention relates to a method for depositing decorative bronze layers on consumer goods and technical objects using the electrolyte according to the invention.
  • Commodities or articles of daily use are refined for decorative reasons and to prevent corrosion with thin, oxidation-stable metal layers. These layers must be mechanically stable and should not show tarnish or signs of wear even after prolonged use. Since 2001, the sale of consumer goods coated with nickel-containing refining alloys is no longer permitted in Europe under EU Directive 94/27 / EC or only under strict conditions, as it is nickel and nickel-containing metal layers about contact allergens. In particular, bronze alloys have become established as a substitute for nickel-containing finishing layers, with which commodity-representing consumer goods in galvanic drum or frame coating processes can be inexpensively refined into allergen-free, handsome products.
  • EP 1 111 097 A2 an electrolyte which contains, in addition to an organosulfonic acid and ions of tin and copper dispersants and brighteners, and optionally antioxidants.
  • EP 1408 141 A1 describes a process for the electrodeposition of bronzes in which an acidic electrolyte is used which, in addition to tin and copper ions, contains an alkylsulfonic acid and an aromatic nonionic wetting agent.
  • the DE 100 46 600 A1 describes a bath containing alkyl or alkanolsulfonic acid, which in addition to soluble tin and copper salts contains organic sulfur compounds, and a method using this bath.
  • a major disadvantage of such produced on the basis of organosulfonic electrolytes is their high corrosivity.
  • baths based on methanesulfonic acids often have pH values below one.
  • the high degree of corrosivity of these baths limits their field of application with regard to the substrate materials to be refined and requires the use of particularly corrosion-resistant working materials for carrying out the process.
  • EP 1 146 148 A2 describes a cyanide-free copper-tin electrolyte based on diphosphoric acid, which contains a cationic surfactant in addition to the reaction product of an amine and an epihalohydrin in a molar ratio of 1: 1.
  • WO 2004/005528 describes a cyanide-free diphosphoric acid copper-tin electrolyte containing an additive composed of an amine derivative, an epihalohydrin and a glycidyl ether compound.
  • Electrolytes based on diphosphoric acid generally have very limited long-term stability and must be renewed frequently.
  • the solderability of the resulting layer and optionally its mechanical adhesive strength are the decisive properties of the layer to be produced.
  • the appearance of the layers is generally less significant than their functionality for use in this area.
  • the decorative effect of the resulting layer in addition to the long shelf life the layer with as unchanged as possible the essential target parameters.
  • an electrolyte which, in addition to the metals to be deposited copper and tin or copper, tin and zinc, which are present in the form of water-soluble salts, contains one or more phosphonic acid derivatives as complexing agents.
  • Toxic ingredients such as cyanides and thio compounds such as thiourea derivatives and thiol derivatives are not included in the electrolyte of the invention.
  • a method is provided by means of which decorative bronze alloy layers can be applied to consumer goods and technical articles using the non-toxic electrolyte according to the invention.
  • Non-toxic in the sense of this document is understood to mean that in the so-called electrolyte according to the invention no substances are contained, which according to the regulations in force in Europe for handling dangerous goods and hazardous substances as “toxic” (T) or “very toxic "(T + ) are to be classified.
  • the metals are incorporated in the form of water-soluble salts, which are preferably selected from the group of sulfites, sulfates, phosphates, diphosphates, nitrites, nitrates, halides, hydroxides, oxide hydroxides and oxides, or combinations thereof.
  • Which salts in which amount are introduced into the electrolyte determines the color of the resulting decorative bronze layers and can be adjusted according to customer requirements.
  • the electrolyte according to the invention for applying decorative bronze layers to consumer goods and technical articles contains between 0.2 and 5 grams per liter of copper, between 0.5 and 20 grams per liter of tin and between 0 and 5 grams per liter of zinc, based in each case Volume of the electrolyte.
  • Particularly preferred for the processing of consumer goods is the introduction of the metals to be deposited as sulfates, phosphates, diphosphates, or chlorides in the In such a way that the resulting ion concentration ranges from 0.3 to 3 grams of copper, 2 to 10 grams of tin and 0 to 3 grams of zinc, each per liter of electrolyte.
  • the application of decorative bronze layers on durable goods and technical items with the electrolyte according to the invention is carried out in a galvanic process. It is important that the metals to be deposited are kept permanently in solution during the process, regardless of whether the galvanic coating takes place in a continuous or in a discontinuous process.
  • the electrolyte according to the invention contains phosphonic acid derivatives as complexing agents.
  • aminophosphonic acid AP 1-aminomethylphosphonic acid AMP, amino-tris (methylenephosphonic acid) ATMP, 1-aminoethylphosphonic acid AEP, 1-aminopropylphosphonic acid APP, (1-acetylamino-2,2,2-trichloroethyl) -phosphonic acid, (1 Amino-1-phosphono-octyl) -phosphonic acid, (1-benzoylamino-2,2,2-trichloroethyl) -phosphonic acid, (1-benzoylamino-2,2-dichlorovinyl) -phosphonic acid, (4-chlorophenyl-hydroxymethyl) -phosphonic acid , Diethylenetriaminepenta (methylenephosphonic acid) DTPMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP, hydroxyethylamino
  • Particular preference is given to using one or more compounds selected from the group consisting of amino-tris (methylenephosphonic acid) ATMP, diethylenetriamine-penta (methylenephosphonic acid) DTPMP, ethylenediamine-tetra (methylenephosphonic acid) EDTMP, 1-hydroxyethane- (1,1-di-phosphonic acid ) HEDP, hydroxyethylamino-di (methylenephosphonic acid) HEMPA, hexamethylenediamine tetra (methylphosphonic acid) HDTMP, salts derived therefrom or condensates derived therefrom, or combinations thereof.
  • Preference is given to using 50 to 200 grams of phosphonic acid derivatives in liters of electrolyte, more preferably 75 to 125 grams per liter of electrolyte.
  • the pH of the electrolyte according to the invention which is greatly influenced by the type and amount of phosphonic acid derivatives used and an important predictor for the long-term stability of the electrolyte is set between 6 and 14, preferably between 8 and 12.
  • the electrolyte may contain organic additives which perform functions as brighteners, wetting agents or stabilizers.
  • the addition of brightener and wetting agent is preferred only for special requirements on the appearance of the decorative bronze layers to be deposited. With their help - in addition to the color of the bronze layers, which largely depends on the ratio of the metals to be deposited - the layer gloss can be adjusted in all gradations between semi-gloss and high gloss.
  • the addition of one or more compounds is selected from the group of mono- and dicarboxylic acids, the alkanesulfonic acids and the aromatic nitro compounds. These compounds act as Elektrolytbadstabilisatoren. Particularly preferred is the use of oxalic acid, of alkanesulfonic acids or of nitrobenzotriazoles or of mixtures thereof.
  • the electrolyte according to the invention is characterized by the fact that it is free of hazardous substances classified as toxic (T) or very toxic (T + ). There are no cyanides, no thiourea derivatives and no thiol derivatives. In particular, the addition of said thio compounds adversely affects the coating result.
  • Bronze plating that has been electrodeposited from thio-compounded baths has a mottled or dull-fogged appearance and is therefore unsuitable for the decorative coating of consumer goods.
  • the non-toxic electrolyte according to the invention is particularly suitable for the electroplating of decorative bronze layers on consumer goods and technical articles. It can be used in drum, rack, belt or continuous galvanic systems.
  • the consumer goods and technical articles to be coated dip into the non-toxic electrolyte according to the invention and form the cathode.
  • the electrolyte is preferably tempered in a range of 20 to 70 ° C.
  • a current density is set in the range 0.01 to 100 amperes per square decimeter [A / dm 2 ] and which depends on the type of coating system.
  • a / dm 2 amperes per square decimeter
  • current densities between 0.05 and 0.50 A / dm 2 are particularly preferred.
  • preference is given to choosing current densities between 0.2 and 10 A / dm 2 , particularly preferably 0.2 to 5 A / dm 2 .
  • anodes When using the non-toxic electrolyte according to the invention, various anodes can be used. Soluble or insoluble anodes are also suitable, as is the combination of soluble and insoluble anodes.
  • soluble anodes those made of a material selected from the group consisting of electrolytic copper, phosphorus-containing copper, tin, tin-copper alloy, zinc-copper alloy and zinc-tin-copper alloy are preferably used. Particularly preferred are combinations of different soluble anodes from these materials, as well as the combinations of soluble tin anodes with insoluble anodes.
  • Preferred insoluble anodes are those made of a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon" DLC) or combinations of these anodes.
  • iridium-ruthenium mixed oxide iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide.
  • insoluble anodes are used, this is a particularly preferred embodiment of the method if the substrates to be provided with decorative bronze layers, which constitute the cathode, are separated from the insoluble anode by an ion exchange membrane in such a way that a cathode space and form an anode space.
  • the cathode compartment is filled with the non-toxic electrolyte according to the invention.
  • the anode compartment there is preferably an aqueous solution which contains only one conductive salt.
  • a non-toxic electrolyte for drum deposition of yellow bronze layers, a non-toxic electrolyte according to the invention was used which contained 120 g / L of hydroxyethylamino-di (methylene phosphonic acid) HEMPA, 2 g / L copper in copper sulfate, 6 g / L tin in tin sulfate and 0.1 g / L low molecular weight polyethyleneimine in water.
  • the pH of the electrolyte was 11.
  • the electrolyte was heated at 60 ° C.
  • a set current density of 0.1 to 0.2 A / dm 2 in an apparatus for drum coatings, optically uniform bronze layers having the yellowish coloration typical for bronze were obtained.
  • a non-toxic electrolyte according to the invention containing 100 g / L of ethylenediamine tetra (methylenephosphonic acid) EDTMP, 4 g / L of copper in copper diphosphate , 5 g / L of tin in tin diphosphate and 3 g / L of zinc in zinc diphosphate dissolved in water.
  • the bath also contained 15 g / L of methanesulfonic acid as a stabilizer.
  • the pH of the bath was 8.
  • an electrolyte was used which in aqueous solution contained 50 g / L ethylenediamine tetra (methylenephosphonic acid) EDTMP and 50 g / L 1-hydroxyethane- (1,1-di-phosphonic acid) HEDP.
  • metals to be deposited 0.5 g / L copper in copper sulfate, 4.0 g / L tin in tin sulfate and 2 g / L zinc in zinc sulfate.
  • the non-toxic electrolyte according to the invention had a pH of 10. At a bath temperature of 50 ° C. and a current density of 0.1 to 0.2 A / dm 2 , mechanically stable and considerable white bronze layers were obtained in drum and frame coating processes.
  • an electrolyte according to the invention which contains 100 g / L ethylenediamine tetra (methylenephosphonic acid) EDTMP, 0.5 g / L copper in copper diphosphate, 5 g / L tin in tin diphosphate, 2 g / L zinc in zinc diphosphate and 15 g / L of the stabilizing methanesulfonic acid in water.
  • the pH of the electrolyte was 10. During the deposition process, a temperature of 50 ° C was carried out.
  • an electrolyte according to the invention which, in addition to 0.5 g / L of copper in copper chloride, 5 g / L of tin in tin chloride and 1.5 g / L of vaniline, contained the sodium salt of diethylenetriaminepenta (methylenephosphonic acid) DTPMP in a concentration of 80 g / L, had a pH of 8 and was tempered at 50 ° C, could also be at a set current density of 0.1 to 0.2 A / dm 2 produce optically flawless white bronze layers in rack and drum coating process.
  • DTPMP diethylenetriaminepenta (methylenephosphonic acid)
  • an electrolyte according to the invention in addition to 0.5 g / L copper in copper diphosphate, 5 g / L tin in tin diphosphate, 2 g / L zinc in zinc diphosphate and 20 g / L methanesulfonic acid ethylenediaminetetra (methylenephosphonic) EDTMP in a concentration of 80 g / L and 10 g / L of amino-tris (methylenephosphonic acid) ATMP contained, had a pH of 10 and was heated at 50 ° C, allowed at a set current density of 0.1 A / dm 2 optically flawless bronze layers produce an anthracite gray to black color, which had good mechanical properties.
  • the selected process parameters corresponded to the conditions set in Example 2.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Physical Vapour Deposition (AREA)

Claims (13)

  1. Electrolyte non toxique pour le dépôt de couches décoratives en alliage de cuivre-étain-bronze sur des objets utilitaires et techniques, qui contient les métaux à déposer sous forme de sels solubles dans l'eau, caractérisé en ce que l'électrolyte contient un ou plusieurs dérivés de l'acide phosphonique comme complexant(s) et est libre de cyanures, de dérivés de thio-urée et de dérivés de thiol et contient, comme métaux à séparer, du cuivre et de l'étain ou du cuivre, de l'étain et du zinc.
  2. Electrolyte selon la revendication 1, caractérisé en ce qu'il contient comme dérivés de l'acide phosphonique un ou plusieurs composés choisis dans le groupe constitué par l'acide aminophosphonique AP, l'acide 1-aminométhylphosphonique AMP, l'aminotris(acide méthylènephosphonique) ATMP, l'acide 1-aminoéthylphosphonique AEP, l'acide 1-aminopropylphosphonique APP, l'acide (1-acétylamino-2,2,2-trichloroéthyl)-phosphonique, l'acide (1-amino-1-phosphonooctyl)-phosphonique, l'acide (1-benzoylamino-2,2,2-trichloroéthyl)-phosphonique, l'acide (1-benzoylamino-2,2-dichlorovinyl)-phosphonique, l'acide (4-chlorophénylhydroxyméthyl)-phosphonique, le diéthylènetriaminepenta(acide méthylènephosphonique) DTPMP, l'éthylènediaminetétra(acide méthylènephosphonique) EDTMP, le 1-hydroxyéthane-(acide 1,1-diphosphonique) HEDP, l'hydroxyéthylaminodi(acide méthylènephosphonique) HEMPA, l'hexaméthylènediamintétra(acide méthylphosphonique) HDTMP, l'acide ((hydroxyméthylphosphonométhylamino)-méthyl)-phosphonique, le nitrilotris(acide méthylènephosphonique) NTMP, l'acide 2,2,2-trichloro-1-(furanne-2-carbonyl)-aminoéthylphosphonique, les sels dérivés de ceux-ci ou les produits de condensation dérivés de ceux-ci ou leurs combinaisons.
  3. Electrolyte selon la revendication 1, caractérisé en ce que le pH de l'électrolyte est situé entre 6 et 14.
  4. Electrolyte selon la revendication 1, caractérisé en ce qu'un ou plusieurs composés à effet de stabilisation sont contenus, choisis dans le groupe des acides monocarboxyliques, dicarboxyliques, alcanesulfoniques et des composés nitro aromatiques.
  5. Electrolyte selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les sels solubles dans l'eau des métaux à séparer sont choisis dans le groupe des sulfites, sulfates, phosphates, diphosphates, nitrites, nitrates, halogénures, hydroxydes, oxyde-hydroxydes, oxydes ou des combinaisons de ceux-ci.
  6. Electrolyte selon la revendication 5, caractérisé en ce que les métaux à déposer se trouvent sous forme dissoute ionique, la concentration en ions de cuivre se situant dans la plage de 0,2 à 5 grammes par litre d'électrolyte, la concentration en ions d'étain se situant dans la plage de 0,5 à 20 grammes par litre d'électrolyte et la concentration en ions de zinc se situant dans la plage de 0 à 5 grammes par litre d'électrolyte.
  7. Procédé pour l'application par galvanisation de couches décoratives en alliage de cuivre-étain-bronze sur des objets utilitaires et techniques, les substrats à revêtir étant plongés dans un électrolyte qui contient les métaux à déposer sous forme de sels solubles dans l'eau, caractérisé en ce qu'on utilise un électrolyte non toxique, qui contient un ou plusieurs dérivés de l'acide phosphonique comme complexant(s) et qui est exempt de cyanures, de dérivés de thio-urée et de dérivés de thiol.
  8. Procédé selon la revendication 7, caractérisé en ce que l'électrolyte est thermostaté dans la plage de 20 jusqu'à 70°C.
  9. Procédé selon la revendication 8, caractérisé en ce qu'on règle une densité de courant qui se situe dans la plage de 0,01 à 100 ampères par décimètre carré.
  10. Procédé selon la revendication 9, caractérisé en ce qu'on utilise des anodes solubles en un matériau choisi dans le groupe constitué par le cuivre électrolytique, le cuivre contenant du phosphore, l'étain, un alliage d'étain-cuivre, un alliage de zinc-cuivre et un alliage de zinc-étain-cuivre ou des combinaisons de ces anodes.
  11. Procédé selon la revendication 9, caractérisé en ce qu'on utilise des anodes insolubles en un matériau choisi dans le groupe constitué par le titane platiné, le graphite, un oxyde mixte d'iridium-métal de transition et un matériau spécial à base de carbone ("Diamond Like Carbon" DLC) ou des combinaisons de ces anodes.
  12. Procédé selon la revendication 10, caractérisé en ce qu'on utilise des anodes insolubles en un matériau choisi dans le groupe constitué par le titane platiné, le graphite, un oxyde mixte d'iridium-métal de transition et un matériau spécial à base de carbone ("Diamond Like Carbon" DLC) ou des combinaisons de ces anodes.
  13. Procédé selon la revendication 11 ou 12, caractérisé en ce que la cathode et l'anode insoluble sont séparées l'une de l'autre par une membrane échangeuse d'ions en formant un espace cathodique et un espace anodique et seul l'espace cathodique contient l'électrolyte non toxique, de manière telle que l'oxydation anodique de Sn2+ en Sn4+ soit supprimée.
EP07003097A 2007-02-14 2007-02-14 Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze Not-in-force EP1961840B1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
PL07003097T PL1961840T3 (pl) 2007-02-14 2007-02-14 Elektrolit miedziowo-cynowy i sposób osadzania warstw brązu
AT07003097T ATE453740T1 (de) 2007-02-14 2007-02-14 Kupfer-zinn-elektrolyt und verfahren zur abscheidung von bronzeschichten
EP07003097A EP1961840B1 (fr) 2007-02-14 2007-02-14 Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze
DE502007002479T DE502007002479D1 (de) 2007-02-14 2007-02-14 Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
TW097101536A TW200844266A (en) 2007-02-14 2008-01-15 Copper-tin electrolyte and process for the deposition of bronze layers
PCT/EP2008/000534 WO2008098666A1 (fr) 2007-02-14 2008-01-24 Électrolyte cuivre-étain et procédé de dépôt de couches de bronze
CN2008800069531A CN101622379B (zh) 2007-02-14 2008-01-24 铜-锡-电解液和沉积青铜层的方法
US12/526,727 US8211285B2 (en) 2007-02-14 2008-01-24 Copper-tin electrolyte and method for depositing bronze layers
JP2009549787A JP2010518260A (ja) 2007-02-14 2008-01-24 銅−スズ電解液及び青銅層の析出法
HK10102901.2A HK1137785A1 (en) 2007-02-14 2010-03-19 Copper-tin electrolyte and method for depositing bronze layers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP07003097A EP1961840B1 (fr) 2007-02-14 2007-02-14 Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze

Publications (2)

Publication Number Publication Date
EP1961840A1 EP1961840A1 (fr) 2008-08-27
EP1961840B1 true EP1961840B1 (fr) 2009-12-30

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EP07003097A Not-in-force EP1961840B1 (fr) 2007-02-14 2007-02-14 Electrolyte de cuivre-étain et procédé pour le dépôt de couches de bronze

Country Status (10)

Country Link
US (1) US8211285B2 (fr)
EP (1) EP1961840B1 (fr)
JP (1) JP2010518260A (fr)
CN (1) CN101622379B (fr)
AT (1) ATE453740T1 (fr)
DE (1) DE502007002479D1 (fr)
HK (1) HK1137785A1 (fr)
PL (1) PL1961840T3 (fr)
TW (1) TW200844266A (fr)
WO (1) WO2008098666A1 (fr)

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DE102008032398A1 (de) * 2008-07-10 2010-01-14 Umicore Galvanotechnik Gmbh Verbesserter Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten
DE102011121799B4 (de) 2011-12-21 2013-08-29 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle
DE102011121798B4 (de) 2011-12-21 2013-08-29 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle
DE102012008544A1 (de) 2012-05-02 2013-11-07 Umicore Galvanotechnik Gmbh Verchromte Verbundwerkstoffe ohne Nickelschicht
AT514818B1 (de) * 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
EP2878713A1 (fr) * 2013-11-28 2015-06-03 Abbott Laboratories Vascular Enterprises Limited Composition électrolytique et procédé pour le traitement de polissage électrolytique d'alliages de nickel-titane et/ou d'autres substrats métalliques comprenant des alliages de tungstène, niobate et tantale
DE102013226297B3 (de) * 2013-12-17 2015-03-26 Umicore Galvanotechnik Gmbh Wässriger, cyanidfreier Elektrolyt für die Abscheidung von Kupfer-Zinn- und Kupfer-Zinn-Zink-Legierungen aus einem Elektrolyten und Verfahren zur elektrolytischen Abscheidung dieser Legierungen
DE102013021502A1 (de) * 2013-12-19 2015-06-25 Schlenk Metallfolien Gmbh & Co. Kg Elektrisch leitende Flüssigkeiten auf der Basis von Metall-Diphosphonat-Komplexen
CN103755738B (zh) * 2014-01-13 2016-06-01 孙松华 一种络合剂及其制备方法和用途
JP2018119169A (ja) * 2017-01-23 2018-08-02 学校法人関東学院 電気めっき液、電気めっき方法及び電気めっき皮膜
CN108658321B (zh) * 2018-05-18 2019-08-09 深圳市祺鑫天正环保科技有限公司 扩散渗析处理硝酸型退锡废液的系统及方法
DE102021117095A1 (de) 2021-07-02 2023-01-05 Umicore Galvanotechnik Gmbh Bronzeschichten als Edelmetallersatz
DE202021004169U1 (de) 2021-07-02 2022-12-07 Umicore Galvanotechnik Gmbh Bronzeschicht als Edelmetallersatz in Smart Cards

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TW200844266A (en) 2008-11-16
US20100147696A1 (en) 2010-06-17
PL1961840T3 (pl) 2010-06-30
CN101622379A (zh) 2010-01-06
ATE453740T1 (de) 2010-01-15
CN101622379B (zh) 2011-05-25
JP2010518260A (ja) 2010-05-27
HK1137785A1 (en) 2010-08-06
DE502007002479D1 (de) 2010-02-11
EP1961840A1 (fr) 2008-08-27
US8211285B2 (en) 2012-07-03
WO2008098666A1 (fr) 2008-08-21

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