EP1918426A1 - Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates - Google Patents
Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates Download PDFInfo
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- EP1918426A1 EP1918426A1 EP06021174A EP06021174A EP1918426A1 EP 1918426 A1 EP1918426 A1 EP 1918426A1 EP 06021174 A EP06021174 A EP 06021174A EP 06021174 A EP06021174 A EP 06021174A EP 1918426 A1 EP1918426 A1 EP 1918426A1
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- Prior art keywords
- silver
- electrolyte composition
- sulfonic acid
- composition according
- substrate
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- 0 CC(*)(C(N1)=O)NC1=O Chemical compound CC(*)(C(N1)=O)NC1=O 0.000 description 1
Classifications
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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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Definitions
- the present invention relates to a cyanide-free electrolyte composition for depositing a silver or silver alloy layer on a substrate. Moreover, the present invention relates to a method of depositing such layers using the cyanide-free electrolyte composition of the present invention.
- Galvanic electrolyte compositions for the deposition of silver or silver alloy layers are known both for use in the field of decorative surfaces and in the technical field. It is customary in the prior art to use soluble silver compounds, usually in the form of cyanide compounds such as potassium silver cyanide or in the form of sulfur-containing complexes such as sulfite, thiosulfate or thiocyanate and ammonium complexes.
- soluble silver compounds usually in the form of cyanide compounds such as potassium silver cyanide or in the form of sulfur-containing complexes such as sulfite, thiosulfate or thiocyanate and ammonium complexes.
- electrolyte compositions are generally unstable without the addition of other complexing or stabilizing agents, it is customary to use the complexing agent components in excess, so that such electrolyte compositions often have very high cyanide, sulfur-containing complexing agent or ammonium concentrations.
- the electrolyte compositions produced in this way are characterized by a wide range of applications. Cyanidic compositions are stable but toxic and therefore of environmental concern. The others mentioned have a lower risk potential, but tend to instability. Despite the significantly lower risk potential with respect to cyanides, the environmental relevance contained in such electrolyte compositions is not negligible and, because of their allergenic potential, can pose a threat to persons working with these electrolyte compositions.
- a low-pollutant to pollutant-free aqueous electrolyte composition for the electrodeposition of noble metals and noble metal alloys, which have to be deposited noble metal and optionally used alloying metals in the form of water-soluble compounds of protein amino acids or their salts or in the form of sulfonic acid compounds.
- the electrolyte compositions according to the DE 199 28 47 A1 have these water-soluble nitro compounds. These may be, for example, 3-nitrophthalic acid, 4-nitrophthalic acid or m-nitrobenzenesulfonic acid.
- these may include organic acids such as nicotinic acid or succinic acid.
- cyanide-free electrolyte compositions are known for depositing silver or silver alloys comprising silver in the form of imides of organic dicarboxylic acids.
- the reaction products of water-soluble silver salts with pyrrolidinediones may serve as silver sources in corresponding electrolyte compositions.
- silver can be used in the form of succinimides or maleimides.
- U.S. Patent No. 4,246,077 discloses the use of silver in the form of pyrrolidinediones as silver source in corresponding electrolyte compositions for depositing silver or silver alloy layers.
- the U.S. Patent 5,601,696 discloses the use of hydantoin as a complexing reagent in electrolyte compositions for depositing silver or silver alloy layers on substrates.
- hydantoin as a complexing reagent in electrolyte compositions for depositing silver or silver alloy layers on substrates.
- 1-methylhydantoin, 1,3-dimethylhydantoin, 5,5-dimethylhydantoin, 1-methanol-5,5-dimethylhydantoin or also 5,5-diphenylhydantoin can be used as complexing reagents.
- WO 2005/083156 discloses a hydantoin-containing electrolyte composition for depositing also mirror-finished silver or silver alloy layers.
- these electrolyte compositions have other environmentally harmful compounds such as 2,2'-bipyridine.
- 2,2'-bipyridine can lead to an inhibition of carboxypeptidases, which play a crucial role, for example, in the digestion of proteins in the small intestine, which justifies the toxicity of this class of compounds and requires extremely careful handling of these compounds.
- a cyanide-free electrolyte composition for depositing a silver or silver alloy layer on a substrate containing at least a silver ion source, a sulfonic acid and / or a derivative of a sulfonic acid, a wetting agent and a hydantoin of the general formula wherein R 1 and R 2 independently of one another may be an H, an alkyl group having 1 to 5 carbon atoms or a substituted or unsubstituted aryl group.
- the electrolyte composition according to the invention comprises the sulfonic acid and / or a derivative of a sulfonic acid in a concentration between 50 g / l and 500 g / l, preferably between 100 g / l and 300 g / l, more preferably between 130 g / l and 200 g / l ,
- the electrolyte composition according to the invention preferably comprises potassium methanesulfonate.
- methanesulfonates such as, for example, sodium methanesulfonate, but also sulfates and other compounds suitable as electrolyte salt are suitable for use in the electrolyte composition according to the invention.
- the electrolyte composition of the invention may have a silver concentration between 10 to 50 g / l, preferably between 20 and 40 g / l, more preferably between 25 and 35 g / l.
- the electrolyte composition of the present invention has at least one silver salt of a sulfonic acid.
- other silver ion sources may include inorganic silver salts selected from the group consisting of silver oxide, silver nitrate and silver sulfate in the electrolyte composition.
- the electrolyte composition of the present invention may have corresponding sources of alloy metal ions.
- corresponding alloying metals are used in the form of their sulfonic acid salts, oxides, nitrates or sulfates.
- the electrolyte composition according to the invention may for example comprise a naphthalenesulfonic acid-formaldehyde polycondensate and / or a sulfopropylated polyalkoxylated naphthol.
- the electrolyte composition may comprise other wetting agents or surfactants.
- the pH of the electrolyte composition of the invention is between pH 8 and pH 14, preferably between pH 9.0 and pH 12.5, more preferably between pH 9.5 and pH 12.0.
- the object is achieved by a method for depositing a silver or silver alloy layer on a substrate , wherein the substrate to be coated at a set current density between 0.1 and 1 A / dm 2 , preferably 0.3 to 0.8 A. / dm 2 is contacted with the electrolyte composition according to the invention.
- the deposition of lustrous, ductile silver or silver alloy layers in a wide range of applications is possible.
- layers for applications in the jewelery, electronics or automotive industry can be deposited with the aid of the electrolyte composition according to the invention.
- inventive method and the electrolyte composition of the invention are particularly applicable to suitable substrates such as gold-plated, nickel-plated and other, not prone to sedimentation sheets.
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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)
Abstract
Description
Die vorliegende Erfindung betrifft eine cyanidfreie Elektrolytzusammensetzung zur Abscheidung einer Silber- oder Silberlegierungsschicht auf einem Substrat. Darüber hinaus betrifft die vorliegende Erfindung ein Verfahren zur Abscheidung solcher Schichten unter Verwendung der erfindungsgemäßen cyanidfreien Elektrolytzusammensetzung.The present invention relates to a cyanide-free electrolyte composition for depositing a silver or silver alloy layer on a substrate. Moreover, the present invention relates to a method of depositing such layers using the cyanide-free electrolyte composition of the present invention.
Galvanische Elektrolytzusammensetzungen zur Abscheidung von Silber- oder Silberlegierungsschichten sind sowohl für die Anwendung im Bereich dekorativer Oberflächen als auch im technischen Bereich bekannt. Hierbei ist es im Stand der Technik üblich, lösliche Silberverbindungen, meistens in Form von Cyanidverbindungen wie beispielsweise Kaliumsilbercyanid oder in Form von schwefelhaltigen Komplexen wie Sulfit-, Thiosulfat- oder Thiocyanat- sowie Ammoniumkomplexe einzusetzen.Galvanic electrolyte compositions for the deposition of silver or silver alloy layers are known both for use in the field of decorative surfaces and in the technical field. It is customary in the prior art to use soluble silver compounds, usually in the form of cyanide compounds such as potassium silver cyanide or in the form of sulfur-containing complexes such as sulfite, thiosulfate or thiocyanate and ammonium complexes.
Da solche aus dem Stand der Technik bekannten Elektrolytzusammensetzungen in der Regel ohne Zusatz weiterer Komplexierungs- oder Stabilisierungsmittel instabil sind, ist es üblich, die Komplexbildnerkomponenten im Überschuß einzusetzen, so daß solche Elektrolytzusammensetzungen oftmals sehr hohe Cyanid-, schwefelhaltige Komplexbildner oder Ammoniumkonzentrationen aufweisen.Since such known from the prior art electrolyte compositions are generally unstable without the addition of other complexing or stabilizing agents, it is customary to use the complexing agent components in excess, so that such electrolyte compositions often have very high cyanide, sulfur-containing complexing agent or ammonium concentrations.
Die so hergestellten Elektrolytzusammensetzungen zeichnen sich durch einen großen Anwendungsbereich aus. Cyanidische Zusammensetzungen sind stabil aber toxisch und damit unter Umweltgesichtspunkten bedenklich. Die übrigen genannten weisen ein geringeres Gefährdungspotential auf, neigen aber zur Instabilität. Trotz des deutlich geringeren Gefährdungspotentials gegenüber Cyaniden zeigen die in solchen Elektrolytzusammensetzungen enthaltenen eine nicht zu vernachlässigende Umweltrelevanz und können aufgrund ihres allergenen Potentials eine Gefährdung der mit diesen Elektrolytzusammensetzungen arbeitenden Personen darstellen.The electrolyte compositions produced in this way are characterized by a wide range of applications. Cyanidic compositions are stable but toxic and therefore of environmental concern. The others mentioned have a lower risk potential, but tend to instability. Despite the significantly lower risk potential with respect to cyanides, the environmental relevance contained in such electrolyte compositions is not negligible and, because of their allergenic potential, can pose a threat to persons working with these electrolyte compositions.
Der Einsatz solcher Elektrolytzusammensetzungen führt, bedingt durch das ökologische Gefährdungspotential der eingesetzten Verbindungen, zu sehr hohen Kosten bei der Aufarbeitung oder Entsorgung verbrauchter Elektrolytzusammensetzungen. Dies stellt einen deutlichen ökonomischen Nachteil dieser aus dem Stand der Technik bekannten Elektrolytzusammensetzungen dar.Due to the ecological hazard potential of the compounds used, the use of such electrolyte compositions leads to very high costs in the processing or disposal of spent electrolyte compositions. This represents a significant economic disadvantage of these known from the prior art electrolyte compositions.
Dies berücksichtigend ist es seit längerem die Intention, Elektrolytzusammensetzungen bereitzustellen, welche über die guten Anwendungseigenschaften und Beschichtungsergebnisse cyanidhaltiger Elektrolytzusammensetzungen verfügen, jedoch gänzlich oder zumindest weitestgehend frei von umweltgefährdenden Verbindungen sind.Taking this into account, it has long been the intention to provide electrolyte compositions which have the good application properties and coating results of cyanide-containing electrolyte compositions, but are wholly or at least largely free of environmentally hazardous compounds.
So offenbart beispielsweise
Aus der
Auch
Das
Ausgehend von diesem Stand der Technik ist es die Aufgabe der vorliegenden Erfindung, eine verbesserte cyanidfreie Elektrolytzusammensetzung bereitzustellen, mit welcher es möglich ist, rißfreie und duktile Silber- oder Silberlegierungsschichten abzuscheiden und welche darüber hinaus frei von gesundheitsgefährdenden Verbindungen ist. Des Weiteren ist es die Aufgabe der vorliegenden Erfindung, ein entsprechendes Verfahren zur Abscheidung solcher Schichten unter Verwendung der erfindungsgemäßen Elektrolytzusammensetzung bereitzustellen.Starting from this prior art, it is the object of the present invention to provide an improved cyanide-free electrolyte composition, with which it is possible to deposit crack-free and ductile silver or silver alloy layers and which, moreover, is free from harmful compounds. Furthermore, it is the task of the present invention to provide a corresponding method for depositing such layers using the electrolyte composition of the present invention.
Gelöst wird diese Aufgabe hinsichtlich der Elektrolytzusammensetzung durch eine cyanidfreie Elektrolytzusammensetzung zur Abscheidung einer Silber- oder Silberlegierungsschicht auf einem Substrat, welche wenigstens eine Silberionenquelle, eine Sulfonsäure und/oder ein Derivat einer Sulfonsäure, ein Netzmittel sowie ein Hydantoin der allgemeinen Formel
Die erfindungsgemäße Elektrolytzusammensetzung weist die Sulfonsäure und/oder ein Derivat einer Sulfonsäure in einer Konzentration zwischen 50 g/l und 500 g/l, bevorzugt zwischen 100 g/l und 300g/l, noch bevorzugter zwischen 130g/l und 200 g/l auf. Bevorzugt weist die erfindungsgemäße Elektrolytzusammensetzung Kaliummethansulfonat auf.The electrolyte composition according to the invention comprises the sulfonic acid and / or a derivative of a sulfonic acid in a concentration between 50 g / l and 500 g / l, preferably between 100 g / l and 300 g / l, more preferably between 130 g / l and 200 g / l , The electrolyte composition according to the invention preferably comprises potassium methanesulfonate.
Neben Kaliummethansulfonat eignen sich andere Methansulfonate wie beispielsweise Natriummethansulfonat, aber auch Sulfate und andere als Leitsalz geeignete Verbindungen zum Einsatz in der erfindungsgemäßen Elektrolytzusammensetzung.In addition to potassium methanesulfonate, other methanesulfonates such as, for example, sodium methanesulfonate, but also sulfates and other compounds suitable as electrolyte salt are suitable for use in the electrolyte composition according to the invention.
Die erfindungsgemäße Elektrolytzusammensetzung kann eine Silberkonzentration zwischen 10 bis 50 g/I, bevorzugt zwischen 20 und 40 g/I, noch bevorzugter zwischen 25 und 35 g/I aufweisen.The electrolyte composition of the invention may have a silver concentration between 10 to 50 g / l, preferably between 20 and 40 g / l, more preferably between 25 and 35 g / l.
Als Silberionenquelle weist die erfindungsgemäße Elektrolytzusammensetzung wenigstens ein Silbersalz einer Sulfonsäure auf.As the silver ion source, the electrolyte composition of the present invention has at least one silver salt of a sulfonic acid.
Darüber hinaus können als weitere Silberionenquellen anorganische Silbersalze ausgewählt aus der Gruppe bestehend aus Silberoxid, Silbernitrat und Silbersulfat in der Elektrolytzusammensetzung enthalten sein.In addition, other silver ion sources may include inorganic silver salts selected from the group consisting of silver oxide, silver nitrate and silver sulfate in the electrolyte composition.
Zur Abscheidung von Silberlegierungsschichten kann die erfindungsgemäße Elektrolytzusammensetzung entsprechende Quellen für Legierungsmetallionen aufweisen. Vorzugsweise werden entsprechende Legierungsmetalle in Form ihrer Sulfonsäuresalze, Oxide, Nitrate oder Sulfate eingesetzt.For depositing silver alloy layers, the electrolyte composition of the present invention may have corresponding sources of alloy metal ions. Preferably, corresponding alloying metals are used in the form of their sulfonic acid salts, oxides, nitrates or sulfates.
Als Netzmittel kann die erfindungsgemäße Elektrolytzusammensetzung beispielsweise ein Naphthalinsulfonsäure-Formaldehyd-Polykondensatz und/oder ein sulfopropyliertes polyalkoxyliertes Naphthol aufweisen. Darüber hinaus kann die Elektrolytzusammensetzung weitere Netzmittel oder Oberflächenaktive Substanzen aufweisen.As a wetting agent, the electrolyte composition according to the invention may for example comprise a naphthalenesulfonic acid-formaldehyde polycondensate and / or a sulfopropylated polyalkoxylated naphthol. In addition, the electrolyte composition may comprise other wetting agents or surfactants.
Der pH-Wert der erfindungsgemäßen Elektrolytzusammensetzung liegt zwischen pH 8 und pH 14, bevorzugt zwischen pH 9,0 und pH 12,5, noch bevorzugter zwischen pH 9,5 und pH 12,0.The pH of the electrolyte composition of the invention is between pH 8 and pH 14, preferably between pH 9.0 and pH 12.5, more preferably between pH 9.5 and pH 12.0.
Hinsichtlich des Verfahrens wird die Aufgabe durch ein Verfahren zur Abscheidung einer Silber- oder Silberlegierungsschicht auf einem Substrat gelöst, wobei das zu beschichtende Substrat bei einer eingestellten Stromdichte zwischen 0,1 und 1 A/dm2, bevorzugt 0,3 bis 0,8 A/dm2 mit der erfindungsgemäßen Elektrolytzusammensetzung kontaktiert wird.With regard to the method, the object is achieved by a method for depositing a silver or silver alloy layer on a substrate , wherein the substrate to be coated at a set current density between 0.1 and 1 A / dm 2 , preferably 0.3 to 0.8 A. / dm 2 is contacted with the electrolyte composition according to the invention.
Mit der erfindungsgemäßen Elektrolytzusammensetzung und dem erfindungsgemäßen Verfahren ist die Abscheidung von glänzenden, duktilen Silber- oder Silberlegierungsschichten in einem breiten Einsatzbereich möglich. So lassen sich beispielsweise Schichten für Anwendungen im Bereich der Schmuck-, Elektronik- oder Automobilindustrie mit Hilfe der erfindungsgemäßen Elektrolytzusammensetzung abscheiden.With the electrolyte composition according to the invention and the process according to the invention, the deposition of lustrous, ductile silver or silver alloy layers in a wide range of applications is possible. For example, layers for applications in the jewelery, electronics or automotive industry can be deposited with the aid of the electrolyte composition according to the invention.
Das erfindungsgemäße Verfahren und die erfindungsgemäße Elektrolytzusammensetzung sind insbesondere anwendbar für geeignete Substrate wie vergoldete, vernickelte und weitere, nicht zur Sudabscheidung neigende Bleche.The inventive method and the electrolyte composition of the invention are particularly applicable to suitable substrates such as gold-plated, nickel-plated and other, not prone to sedimentation sheets.
Ein vergoldetes Messingblech wurde bei einer eingestellten Stromdichte von 0,5 A/dm2 für 15 Minuten mit einer Elektrolytzusammensetzung kontaktiert, welche die nachfolgende Zusammensetzung aufwies:
- • 30 g/L Ag als Silbermethansulfonat (Ag-MSA)
- • 150 g/L Kaliummethansulfonat
- • 80 g/L 5,5-Dimethylhydantoin
- • 15 g/L Naphthalinsulfonsäure-Formaldehyd-Polykondensat
- • 2,5 g/L sulfopropyliertes polyalkoxyliertes Naphthol, als Kaliumsalz
- 30 g / L Ag as silver methanesulfonate (Ag-MSA)
- • 150 g / L potassium methanesulfonate
- • 80 g / L of 5,5-dimethylhydantoin
- • 15 g / L naphthalenesulfonic acid-formaldehyde polycondensate
- • 2.5 g / L sulfopropylated polyalkoxylated naphthol, as the potassium salt
Es wurde eine gleichmäßige, glänzende Silberschicht von 5 µm abgeschieden.It was deposited a uniform, shiny silver layer of 5 microns.
Claims (7)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06021174A EP1918426A1 (en) | 2006-10-09 | 2006-10-09 | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
JP2009531764A JP5439181B2 (en) | 2006-10-09 | 2007-10-09 | Cyanide-free electrolyte composition and method for depositing a silver or silver alloy layer on a substrate |
EP07818853.9A EP2089561B1 (en) | 2006-10-09 | 2007-10-09 | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
US12/445,049 US9212427B2 (en) | 2006-10-09 | 2007-10-09 | Cyanide-free electrolyte composition, and method for the deposition of silver or silver alloy layers on substrates |
CN2007800454144A CN101627150B (en) | 2006-10-09 | 2007-10-09 | Cyanide-free electrolyte composition, and method for the deposition of silver or silver alloy layers on substrates |
PCT/EP2007/008780 WO2008043528A2 (en) | 2006-10-09 | 2007-10-09 | Cyanide-free electrolyte composition, and method for the deposition of silver or silver alloy layers on substrates |
KR1020097009568A KR101409701B1 (en) | 2006-10-09 | 2007-10-09 | Cyanide-free electrolyte composition, and method for the deposition of silver or silver alloy layers on substrates |
US14/962,863 US9657402B2 (en) | 2006-10-09 | 2015-12-08 | Cyanide-free electrolyte composition and method for the deposition of silver or silver alloy layers on substrates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP06021174A EP1918426A1 (en) | 2006-10-09 | 2006-10-09 | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
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EP1918426A1 true EP1918426A1 (en) | 2008-05-07 |
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EP06021174A Withdrawn EP1918426A1 (en) | 2006-10-09 | 2006-10-09 | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
EP07818853.9A Active EP2089561B1 (en) | 2006-10-09 | 2007-10-09 | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
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EP07818853.9A Active EP2089561B1 (en) | 2006-10-09 | 2007-10-09 | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
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US (2) | US9212427B2 (en) |
EP (2) | EP1918426A1 (en) |
JP (1) | JP5439181B2 (en) |
KR (1) | KR101409701B1 (en) |
CN (1) | CN101627150B (en) |
WO (1) | WO2008043528A2 (en) |
Cited By (3)
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DE102009029558A1 (en) | 2009-09-17 | 2011-03-31 | Schott Solar Ag | electrolyte composition |
RU2536127C2 (en) * | 2010-03-09 | 2014-12-20 | Общество с ограниченной ответственностью "Санкт-Петербургский Центр "ЭЛМА (Электроникс Менеджмент)" | Acid electrolyte for silvering |
DE102015008686A1 (en) | 2015-07-02 | 2017-01-05 | ORU e.V. | Cyanide-free, aqueous electrolytic composition |
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EP1918426A1 (en) * | 2006-10-09 | 2008-05-07 | Enthone, Inc. | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
EP2431501B1 (en) | 2010-09-21 | 2013-11-20 | Rohm and Haas Electronic Materials LLC | Method of electroplating silver strike over nickel |
US20160032479A1 (en) * | 2013-03-15 | 2016-02-04 | Enthone Inc. | Electrodeposition of silver with fluoropolymer nanoparticles |
CN105420770A (en) * | 2015-11-30 | 2016-03-23 | 苏州市金星工艺镀饰有限公司 | Color-change-preventing cyanide-free silver plating electroplating liquid and electroplating method thereof |
CN105350037A (en) * | 2015-12-17 | 2016-02-24 | 宏正(福建)化学品有限公司 | Alkaline non-cyanide zinc plating nickel alloy plating solution and electroplating process thereof |
CN112469847A (en) * | 2018-08-21 | 2021-03-09 | 优美科电镀技术有限公司 | Electrolyte for cyanide-free deposition of silver |
DE102019106004B4 (en) * | 2019-03-08 | 2023-11-30 | Umicore Galvanotechnik Gmbh | Additive for the cyanide-free deposition of silver |
US11578418B2 (en) * | 2021-03-29 | 2023-02-14 | Rohm And Haas Electronic Materials Llc (Rhem) | Silver electroplating compositions and methods for electroplating silver with low coefficients of friction |
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EP1918426A1 (en) * | 2006-10-09 | 2008-05-07 | Enthone, Inc. | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
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2006
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- 2007-10-09 EP EP07818853.9A patent/EP2089561B1/en active Active
- 2007-10-09 KR KR1020097009568A patent/KR101409701B1/en active IP Right Grant
- 2007-10-09 JP JP2009531764A patent/JP5439181B2/en active Active
- 2007-10-09 WO PCT/EP2007/008780 patent/WO2008043528A2/en active Application Filing
- 2007-10-09 US US12/445,049 patent/US9212427B2/en active Active
- 2007-10-09 CN CN2007800454144A patent/CN101627150B/en active Active
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2015
- 2015-12-08 US US14/962,863 patent/US9657402B2/en active Active
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102009029558A1 (en) | 2009-09-17 | 2011-03-31 | Schott Solar Ag | electrolyte composition |
EP2309035A1 (en) | 2009-09-17 | 2011-04-13 | SCHOTT Solar AG | Electrolyte composition |
CN102021613A (en) * | 2009-09-17 | 2011-04-20 | 肖特太阳能控股公司 | Electrolyte composition |
CN102021613B (en) * | 2009-09-17 | 2015-09-30 | 肖特太阳能控股公司 | Electrolyte composition |
RU2536127C2 (en) * | 2010-03-09 | 2014-12-20 | Общество с ограниченной ответственностью "Санкт-Петербургский Центр "ЭЛМА (Электроникс Менеджмент)" | Acid electrolyte for silvering |
DE102015008686A1 (en) | 2015-07-02 | 2017-01-05 | ORU e.V. | Cyanide-free, aqueous electrolytic composition |
Also Published As
Publication number | Publication date |
---|---|
KR101409701B1 (en) | 2014-06-19 |
JP2010506048A (en) | 2010-02-25 |
US20100044239A1 (en) | 2010-02-25 |
EP2089561A2 (en) | 2009-08-19 |
EP2089561B1 (en) | 2016-03-09 |
JP5439181B2 (en) | 2014-03-12 |
KR20090073220A (en) | 2009-07-02 |
WO2008043528A3 (en) | 2009-04-16 |
CN101627150A (en) | 2010-01-13 |
CN101627150B (en) | 2011-06-22 |
WO2008043528A2 (en) | 2008-04-17 |
US9657402B2 (en) | 2017-05-23 |
US20160122890A1 (en) | 2016-05-05 |
US9212427B2 (en) | 2015-12-15 |
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