EP2103717A1 - Pyrophosphate-based bath for depositing tin alloy layers - Google Patents

Pyrophosphate-based bath for depositing tin alloy layers Download PDF

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Publication number
EP2103717A1
EP2103717A1 EP08003786A EP08003786A EP2103717A1 EP 2103717 A1 EP2103717 A1 EP 2103717A1 EP 08003786 A EP08003786 A EP 08003786A EP 08003786 A EP08003786 A EP 08003786A EP 2103717 A1 EP2103717 A1 EP 2103717A1
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EP
European Patent Office
Prior art keywords
carbamoyl
pyridinium chloride
pyrophosphate
benzyl
aqueous cyanide
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.)
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EP08003786A
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German (de)
French (fr)
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EP2103717B1 (en
Inventor
Philip Hartmann
Lars Kohlmann
Heiko Brunner
Klaus Dieter Schulz
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to ES08003786T priority Critical patent/ES2340973T3/en
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to PL08003786T priority patent/PL2103717T3/en
Priority to AT08003786T priority patent/ATE465283T1/en
Priority to DE502008000573T priority patent/DE502008000573D1/en
Priority to PT08003786T priority patent/PT2103717E/en
Priority to EP08003786A priority patent/EP2103717B1/en
Priority to BRPI0907497-0A priority patent/BRPI0907497A2/en
Priority to CN2009801015016A priority patent/CN101918618B/en
Priority to KR1020107018440A priority patent/KR101540615B1/en
Priority to PCT/EP2009/000802 priority patent/WO2009109271A2/en
Priority to US12/864,180 priority patent/US8647491B2/en
Priority to JP2010547984A priority patent/JP5688841B2/en
Priority to CA2716115A priority patent/CA2716115A1/en
Priority to TW098104123A priority patent/TWI439580B/en
Publication of EP2103717A1 publication Critical patent/EP2103717A1/en
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Publication of EP2103717B1 publication Critical patent/EP2103717B1/en
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the present invention relates to an aqueous cyanide-free bath and a process for the cyanide-free deposition of tin alloys, in particular tin-copper alloys containing N-methylpyrrolidone as organic brightener.
  • the invention enables the cyanide-free deposition of homogeneous, shiny tin alloy layers, in particular tin-copper alloy layers, the alloy ratio of which can be selectively adjusted depending on the metal salt ratio used within the electrolyte.
  • Tin alloys and especially copper-tin alloys, have come into focus as an alternative to nickel deposits. Electrodeposited nickel layers are commonly used for both decorative and functional applications.
  • nickel layers are problematic due to their sensitizing properties, especially in the case of direct skin contact. For this reason, alternatives are of the highest interest.
  • Cyanide-containing copper-tin alloy baths are industrially established. Due to stricter regulations and the high toxicity and problematic and expensive disposal of these cyanide-containing baths, there is a growing demand for cyanide-free copper-tin electrolytes.
  • JP 10-102278 A a pyrophosphate-based copper-tin alloy bath which contains as an additive a reaction product of an amine and an epihalodrin derivative (molar ratio 1: 1), an aldehyde derivative and, optionally, depending on the application, surfactants.
  • the US 6416571 B1 also describes a pyrophosphate-based bath which also contains as additives a reaction product of an amine and an epihalohydrin derivative (molar ratio 1: 1), a cationic surfactant, optionally further surface-active surfactants and an antioxidant.
  • a disadvantage of the abovementioned baths is that no uniform alloy layers are obtained, especially in the case of drum galvanizations, so that the products do not have a uniform coloring and gloss.
  • a pyrophosphate-containing copper-tin alloy bath containing as an additive a reaction product of an amine derivative, more preferably piperazine, an epihalohydrin derivative, especially epichlorohydrin, and a glycidyl ether.
  • an amine derivative more preferably piperazine
  • an epihalohydrin derivative especially epichlorohydrin
  • a glycidyl ether for the preparation of this reaction product, a mixture consisting of epichlorohydrin and the glycidyl ether is added slowly under precise temperature control to an aqueous solution of piperazine, wherein the temperature from 65 to 80 ° C must be maintained.
  • a disadvantage of this additive is the difficult to control reaction, especially at high temperatures, since such reaction products tend at too high reaction and / or storage temperatures for post-reaction and thus formation of high molecular weight and thus partially water-insoluble and ineffective polymers.
  • a way out of this dilemma can be achieved only by a reaction in very high dilution ( ⁇ 1 wt .-%). It comes with such low concentration additive solutions with repeated replenishment to an adverse solution buildup of the electrolyte. This can lead to fluctuating deposits with longer use of electrolyte.
  • this electrolyte exhibits weaknesses in rack plating applications.
  • the quality of the deposited layers which often show a haze, very much depends on the nature of the movement of goods during the electrolysis.
  • the copper-tin coatings obtained in this way also often have pores, which is problematic especially in decorative coatings.
  • the invention is therefore based on the object to develop a galvanic bath for tin alloys, which allows the production of optically attractive tin alloy layers.
  • a more homogeneous tin-alloy metal distribution and an optimal tin-metal ratio should be set.
  • a uniform layer thickness with high gloss and the uniformity of the distribution of the alloy components in the coating should be maintained over a wide current density range.
  • the electrolytic bath according to the invention may further comprise an acid (iii) and / or a pyrophosphate source (iv).
  • the component (iii) of the aqueous cyanide-free electrolyte bath according to the invention is any acid which can be used in known electrolyte baths.
  • they are organic sulfonic acids, orthophosphoric acid, sulfuric acid and boric acid.
  • the aqueous cyanide-free electrolyte bath according to the invention preferably also contains additives which are selected from antioxidants and / or further organic brighteners.
  • Preferred organic brighteners here are morpholine, 2-morpholineethanesulfonic acid, hexamethylenetetramine, 3- (4-morpholino) -1,2-propanediol, 1,4-diazabicyclo [2.2.2] octane, 1-benzyl-3-carbamoyl-pyridinium chloride , 1- (2'-Chloro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-methoxy-benzyl) - 3-carbamoyl-pyridinium chloride, 1- (2'-carboxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-carbamoyl-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3 'Chloro-benzy
  • the additives according to the invention can be used with N-methylpyrrolidone alone or as a mixture of a plurality of different brightener systems of the abovementioned representatives in a concentration of 0.0001 to 20 g / l and more preferably of 0.001 to 1 g / l.
  • the tin ion source and the source of another alloying element may be pyrophosphates.
  • the tin ion source and the source of another alloying element are also pyrophosphate sources within the meaning of the aforementioned component (iv) of the electrolytic bath according to the invention.
  • the pyrophosphate concentration of the source for another alloying element is 0.5 to 50 g / l, and preferably 1 to 5 g / l.
  • the bath according to the invention may contain copper pyrophosphate in an amount of 0.5 to 50 g / l, preferably 1 to 5 g / l or zinc pyrophosphate in these amounts.
  • the concentration is generally 0.5 to 100 g / l, with concentrations of 10 to 40 g / l being particularly preferred.
  • tin and metal pyrophosphates In addition to the above-mentioned tin and metal pyrophosphates, other water-soluble tin and metal salts, such as tin sulfate, tin methanesulfonate, copper sulfate, copper methanesulfonate, or the corresponding Zinc salts are used, which can be umkomplexiert by the addition of suitable alkali metal pyrophosphates within the electrolyte into the corresponding pyrophosphates.
  • the concentration ratio of pyrophosphate to tin / metal should be 3 to 80, more preferably 5 to 50.
  • Pyrophosphate sources according to component (iv) are particularly preferably the sodium, potassium and ammonium pyrophosphates in concentrations of 50 to 500 g / l, more preferably from 100 to 400 g / l.
  • the aforementioned antioxidants include hydroxylated aromatic compounds, e.g. Catechol, resorcinol, pyrocatechol, hydroquinone, pyrogallol, ⁇ - or ⁇ -naphthol, phloroglucin and sugar-based systems such as e.g. Ascorbic acid, sorbitol in concentrations of 0.1 to 1 g / l.
  • hydroxylated aromatic compounds e.g. Catechol, resorcinol, pyrocatechol, hydroquinone, pyrogallol, ⁇ - or ⁇ -naphthol, phloroglucin
  • sugar-based systems such as e.g. Ascorbic acid, sorbitol in concentrations of 0.1 to 1 g / l.
  • organic sulfonic acids both mono- and polyalkylsulfonic acids, e.g. Methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid and salts thereof and their hydroxylated derivatives are used. Particularly preferred is the use of methanesulfonic acid in a concentration of 0.01 to 1 g / l.
  • the baths according to the invention have a pH of 3 to 9, more preferably 6 to 8.
  • N-methylpyrrolidone a significant improvement in the deposited layers can be achieved with regard to gloss and freedom from pores, preferably in a concentration of 0.1 to 50 g / l, more preferably 0.1 to 4 g / l.
  • the baths according to the invention can be prepared by conventional methods, for example by adding the specific amounts of the above-described components to water.
  • the amount of bases, acids and acids Buffer components such as sodium pyrophosphate, methanesulfonic acid and / or boric acid should preferably be chosen so that the bath reaches the pH range of at least 6 to 8.
  • the baths according to the invention deposit a bright, even and ductile copper-tin alloy layer at any customary temperature of about 15 to 50 ° C, preferably 20 ° C to 40 ° C, more preferably 25 ° C to 30 ° C from. At these temperatures, the baths according to the invention are stable and effective over a wide current density range of 0.01 to 2 A / dm 2 , more preferably 0.25 to 0.75 A / dm 2 .
  • the baths of the invention may be operated in a continuous or intermittent manner, and from time to time the components of the bath will have to be supplemented.
  • the components of the bath may be added singly or in combination. Furthermore, they can be varied over a wide range, depending on the consumption and present concentration of the individual components.
  • An advantage of the baths according to the invention compared to the electrolyte of WO 2004/005528 is the good reproducibility and long-term stability of the formulations according to the invention in comparison to the reaction products of piperazine with epichlorohydrin and glycidyl ether.
  • the aqueous baths according to the invention can generally be used for all types of substrates on which tin alloys can be deposited.
  • substrates on which tin alloys can be deposited.
  • useful substrates include copper-zinc alloys, chemically copper or chemically nickel-coated ABS plastic surfaces, mild steel, stainless steel, spring steel, chrome steel, chromium-molybdenum steel, copper and tin.
  • Another object is therefore a process for the electrodeposition of copper-tin alloys on conventional substrates, wherein the inventive Bath is used.
  • the substrate to be coated is introduced into the electrolyte bath.
  • the deposition of the coatings at a current density of 0.25 to 0.75 A / dm 2 and at a temperature of 15 to 50 ° C, preferably 25 to 30 ° C.
  • the method according to the invention can be carried out in the application for mass parts, for example as a drum electroplating method and for depositing on larger workpieces as a rack electroplating method.
  • anodes are used which may be soluble, such as copper anodes, tin anodes or suitable copper-tin alloy anodes, which simultaneously serve as copper and / or tin ion source, so that the deposited on the cathode copper and / or tin by dissolution is substituted by copper and / or tin at the anode.
  • insoluble anodes e.g., platinized titanium mixed oxide anodes
  • the copper and tin ions withdrawn from the electrolyte must be re-added in some other way, e.g. by addition of the corresponding soluble metal salts.
  • galvanic deposition it is also possible to operate the process according to the invention under nitrogen or argon injection, with goods movement or without movement, without resulting in any disadvantages for the coatings obtained.
  • the tin (II) ions can be used with the separation of the electrode spaces or with the use of membrane anodes, whereby a significant stabilization of the electrolyte can be achieved.
  • the current source used are commercial DC converters or pulse rectifiers.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.1 g / l 1- (pentafluorobenzyl) -3-carbamoyl pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 20 ml / l N-methylpyrrolidone 0.06 g / l 1-benzyl-3-acetyl-pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high glossy, light veil deposit in the low current density range was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.03 g / l 1- (4-methoxy-benzyl) -3-carbamoyl pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A brilliant deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.03 g / l 1,1 '- (xylenyl) -3', 3-bis-carbamoyl-bis-pyridinium dichloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1 A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.12 g / l 1- (4'-Carboxy-benzyl) -3-carbamoyl pyridinium chloride
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 ml / l 1- (Benzyl) -3-carbamoylpyridinium chloride 35% solution
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 g / l morpholine
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 5 g / l 2-morpholino-ethane sulfonic acid
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.
  • An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 g / l 3- (4-morpholino) -1,2-propanediol
  • the anode used is a titanium mixed oxide electrode.
  • the cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Abstract

An aqueous cyanide-free electrolyte bath comprises tin ion source and source for another alloy element; and N-methyl pyrrolidone. An independent claim is included for a process for electroplating of glossy and uniform tin alloy coatings comprising introducing substrate to be coated into aqueous cyanide-free electrolyte bath, and plating the tin alloy coating on the substrate.

Description

Gebiet der ErfindungField of the invention

Die vorliegende Erfindung betrifft ein wässriges cyanid-freies Bad und ein Verfahren zur cyanid-freien Abscheidung von Zinn-Legierungen, insbesondere Zinn-Kupfer-Legierungen, das N-Methylpyrrolidon als organischen Glanzbildner enthält.The present invention relates to an aqueous cyanide-free bath and a process for the cyanide-free deposition of tin alloys, in particular tin-copper alloys containing N-methylpyrrolidone as organic brightener.

Die Erfindung ermöglicht die cyanid-freie Abscheidung von homogenen, glänzenden Zinn-Legierungsschichten, insbesondere Zinn-Kupfer-Legierungsschichten, deren Legierungsverhältnis je nach eingesetztem Metallsalzverhältnis innerhalb des Elektrolyten gezielt eingestellt werden kann.The invention enables the cyanide-free deposition of homogeneous, shiny tin alloy layers, in particular tin-copper alloy layers, the alloy ratio of which can be selectively adjusted depending on the metal salt ratio used within the electrolyte.

Stand der TechnikState of the art

Zinn-Legierungen und insbesondere Kupfer-Zinn-Legierungen sind als Alternative zu Nickelabscheidungen in den Fokus des Interesses gekommen. Galvanisch abgeschiedene Nickelschichten werden üblicherweise sowohl für dekorative als auch funktionale Anwendungen eingesetzt.Tin alloys, and especially copper-tin alloys, have come into focus as an alternative to nickel deposits. Electrodeposited nickel layers are commonly used for both decorative and functional applications.

Trotz ihrer guten Eigenschaften sind Nickelschichten auf Grund ihrer sensibilisierenden Eigenschaften gerade bei direktem Hautkontakt gesundheitlich problematisch. Aus diesem Grund sind Alternativen von höchstem Interesse.Despite their good properties, nickel layers are problematic due to their sensitizing properties, especially in the case of direct skin contact. For this reason, alternatives are of the highest interest.

Neben den im Elektronik-Sektor etablierten aber ökologisch problematischen Zinn-Blei-Legierungen, sind in den letzten Jahren vor allem Kupfer-Zinn-Legierungen als Ersatz ins Auge gefasst worden. Kapitel 13 (S. 155 bis 163) der Schrift "The Electrodeposition of Tin and ist Alloys" von Manfred Jordan (Eugen G. Leuze Publ., 1st Ed., 1995 ) gibt einen Überblick über die bekannten Bad-Typen für Kupfer-Zinn-Legierungsabscheidungen.In addition to the established in the electronics sector but ecologically problematic tin-lead alloys, especially copper-tin alloys have been considered as a replacement in recent years. Chapter 13 (pages 155 to 163) of the work "The Electrodeposition of Tin and Alloys" by Manfred Jordan (Eugen G. Leuze Publ., 1st ed., 1995 ) gives an overview of the known bath types for copper-tin alloy deposits.

Industriell etabliert sind cyanid-haltige Kupfer-Zinn-Legierungsbäder. Aufgrund strenger werdender Regularien und der hohen Toxizität und problematischen und teuren Entsorgung dieser cyanid-haltigen Bäder besteht ein wachsender Bedarf an cyanid-freien Kupfer-Zinn-Elektrolyten.Cyanide-containing copper-tin alloy baths are industrially established. Due to stricter regulations and the high toxicity and problematic and expensive disposal of these cyanide-containing baths, there is a growing demand for cyanide-free copper-tin electrolytes.

Zu diesem Zweck sind vereinzelt cyanid-freie pyrophosphat-haltige Elektrolyte entwickelt worden. So beschreibt die JP 10-102278 A ein Kupfer-Zinn-Legierungsbad auf Pyrophosphat-Basis, das als Additiv ein Reaktionsprodukt eines Amins und eines Epihalodrin-Derivates (Molverhältnis 1:1), ein Aldehyd-Derivat und gegebenenfalls je nach Anwendung Tenside enthält. Die US 6416571 B1 beschreibt ebenfalls ein Pyrophosphat-basierendes Bad, welches ebenfalls als Additive ein Reaktionsprodukt eines Amins und eines Epihalohydrin-Derivates (Molverhältnis 1:1), ein kationisches Tensid, gegebenenfalls weitere oberflächenaktive Tenside und ein Antioxidationsmittel enthält.For this purpose, isolated cyanide-free pyrophosphate-containing electrolytes have been developed. That's how it describes JP 10-102278 A a pyrophosphate-based copper-tin alloy bath which contains as an additive a reaction product of an amine and an epihalodrin derivative (molar ratio 1: 1), an aldehyde derivative and, optionally, depending on the application, surfactants. The US 6416571 B1 also describes a pyrophosphate-based bath which also contains as additives a reaction product of an amine and an epihalohydrin derivative (molar ratio 1: 1), a cationic surfactant, optionally further surface-active surfactants and an antioxidant.

Nachteilig bei den oben genannten Bädern ist, dass gerade bei Trommelgalvanisierungen keine einheitlichen Legierungsschichten erhalten werden, so dass die Produkte keine einheitliche Farbgebung und Glanz aufweisen.A disadvantage of the abovementioned baths is that no uniform alloy layers are obtained, especially in the case of drum galvanizations, so that the products do not have a uniform coloring and gloss.

Zur Lösung dieses Problems wird in der WO 2004/005528 ein pyrophosphathaltiges Kupfer-Zinn-Legierungsbad vorgeschlagen, das als Additiv ein Reaktionsprodukt eines Amin-Derivates, besonders bevorzugt Piperazin, eines Epihalohydrin-Derivates, vor allem Epichlorhydrin, und eines Glycidylethers enthält. Zur Herstellung dieses Reaktionsproduktes wird ein Gemisch bestehend aus Epichlorhydrin und dem Glycidylether langsam unter genauer Temperaturkontrolle zu einer wässrigen Lösung des Piperazin gegeben, wobei die Temperatur von 65 bis 80°C eingehalten werden muss. Nachteilig bei diesem Additiv ist die schwierig zu kontrollierende Reaktionsführung gerade bei hohen Temperaturen, da derartige Reaktionsprodukte bei zu hohen Reaktions- und/oder Lagertemperaturen zur Nachreaktion und somit Bildung hochmolekularer und somit teilweise wasserunlöslicher und unwirksamer Polymere neigen. Ein Ausweg aus diesem Dilemma kann nur durch eine Reaktionsführung in sehr hoher Verdünnung (< 1 Gew.-%) erreicht werden. Dabei kommt es bei derartig gering konzentrierten Additiv-Lösungen bei mehrmaligem Nachdosieren zu einem nachteiligen Lösungsaufbau des Elektrolyten. Dadurch kann es bei längerem Elektrolytgebrauch zu schwankenden Abscheidungen kommen.To solve this problem is in the WO 2004/005528 proposed a pyrophosphate-containing copper-tin alloy bath containing as an additive a reaction product of an amine derivative, more preferably piperazine, an epihalohydrin derivative, especially epichlorohydrin, and a glycidyl ether. For the preparation of this reaction product, a mixture consisting of epichlorohydrin and the glycidyl ether is added slowly under precise temperature control to an aqueous solution of piperazine, wherein the temperature from 65 to 80 ° C must be maintained. A disadvantage of this additive is the difficult to control reaction, especially at high temperatures, since such reaction products tend at too high reaction and / or storage temperatures for post-reaction and thus formation of high molecular weight and thus partially water-insoluble and ineffective polymers. A way out of this dilemma can be achieved only by a reaction in very high dilution (<1 wt .-%). It comes with such low concentration additive solutions with repeated replenishment to an adverse solution buildup of the electrolyte. This can lead to fluctuating deposits with longer use of electrolyte.

Ferner zeigt dieser Elektrolyt Schwächen bei Anwendungen in der Gestellgalvanisierung. So ist die Qualität der abgeschiedenen Schichten, die oftmals einen Schleier zeigen, sehr stark von der Art der Warenbewegung während der Elektrolyse abhängig. Die auf diese Weise erhaltenen Kupfer-Zinn-Überzüge weisen zudem oftmals Poren auf, was gerade bei dekorativen Überzügen problematisch ist.Further, this electrolyte exhibits weaknesses in rack plating applications. Thus, the quality of the deposited layers, which often show a haze, very much depends on the nature of the movement of goods during the electrolysis. The copper-tin coatings obtained in this way also often have pores, which is problematic especially in decorative coatings.

Zusammenfassung der ErfindungSummary of the invention

Der Erfindung liegt deshalb die Aufgabe zugrunde, ein galvanisches Bad für Zinn-Legierungen zu entwickeln, welches die Herstellung von optisch ansprechenden Zinn-Legierungsschichten ermöglicht.The invention is therefore based on the object to develop a galvanic bath for tin alloys, which allows the production of optically attractive tin alloy layers.

Dabei soll zusätzlich eine homogenere Zinn-Legierungsmetallverteilung und ein optimales Zinn-Metall-Verhältnis eingestellt werden. Außerdem sollen eine einheitliche Schichtdicke mit hohem Glanz und die Gleichmäßigkeit der Verteilung der Legierungskomponenten im Überzug über einen weiten Stromdichtebereich aufrechterhalten werden.In addition, a more homogeneous tin-alloy metal distribution and an optimal tin-metal ratio should be set. In addition, a uniform layer thickness with high gloss and the uniformity of the distribution of the alloy components in the coating should be maintained over a wide current density range.

Gegenstand der Erfindung ist ein wässriges cyanid-freies Elektrolytbad zur Abscheidung von Zinn-Legierungsschichten auf Substratoberflächen, umfassend

  1. (i) eine Zinn-Ionenquelle und eine Quelle für ein weiteres Legierungselement sowie
  2. (ii) N-Methylpyrrolidon.
The invention relates to an aqueous cyanide-free electrolyte bath for the deposition of tin alloy layers on substrate surfaces, comprising
  1. (i) a tin ion source and a source of another alloying element as well
  2. (ii) N-methylpyrrolidone.

Beschreibung bevorzugter Ausführungsformen der ErfindungDescription of preferred embodiments of the invention

Neben den vorgenannten Komponenten (i) und (ii) kann das erfindungsgemäße Elektrolytbad weiterhin eine Säure (iii) und/oder eine Pyrophosphat-Quelle (iv) umfassen.In addition to the aforementioned components (i) and (ii), the electrolytic bath according to the invention may further comprise an acid (iii) and / or a pyrophosphate source (iv).

Bei der Komponente (iii) des erfindungsgemäßen wässrigen cyanid-freien Elektrolytbads handelt es sich um eine beliebige Säure, wie sie in bekannten Elektrolytbädern eingesetzt werden kann. Vorzugsweise handelt es sich um organische Sulfonsäuren, Orthophosphorsäure, Schwefelsäure und Borsäure.The component (iii) of the aqueous cyanide-free electrolyte bath according to the invention is any acid which can be used in known electrolyte baths. Preferably, they are organic sulfonic acids, orthophosphoric acid, sulfuric acid and boric acid.

Das erfindungsgemäße wässrige cyanid-freie Elektrolytbad enthält vorzugsweise weiterhin Zusätze, die aus Antioxidationsmitteln und/oder weiteren organischen Glanzbildnern ausgewählt sind.The aqueous cyanide-free electrolyte bath according to the invention preferably also contains additives which are selected from antioxidants and / or further organic brighteners.

Bevorzugte organische Glanzbildner sind hierbei Morpholin, 2-Morpholinethansulfonsäure, Hexamethylentetramin, 3-(4-Morpholino)-1,2-propandiol, 1,4-Diazabicyclo-[2.2.2]-octan, 1-Benzyl-3-carbamoyl-pyridiniumchlorid, 1-(2'-Chloro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Fluoro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Methoxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Carboxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Carbamoyl-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Chloro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Fluoro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Methoxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Carboxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Carbamoyl-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Chloro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Fluoro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Methoxybenzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Carboxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Carbamoyl-benzyl)-3-carbamoyl-pyridinium-chlorid, (1'-Methyl-naphthyl)-3-carbamoyl-pyridinium-chlorid, 1-(1'methyl-naphthyl)-3-carbamoyl-pyridinium-bromid, 1-(1'-Methyl-naphthyl)-3-carbamoyl-pyridinium-fluorid, 1,1'-(Xylenyl)-3,3'-bis-carbamoyl-bis-pyridinium-dibromid, 1,1',1"-(Mesitylenyl)-3,3',3"-tris-carbamoyl-tri-pyridinium-trichlorid, sowie die korrespondierenden Bromide, Fluoride, Iodide und Pseudohalogenide (z.B. Triflate, Tosylate) der oben aufgeführten Verbindungen sowie quatemisierte N,N-Bis-[dialkylamino-alkyl]-harnstoffe, wobei benzylierte Derivate besonders geeignet sind.Preferred organic brighteners here are morpholine, 2-morpholineethanesulfonic acid, hexamethylenetetramine, 3- (4-morpholino) -1,2-propanediol, 1,4-diazabicyclo [2.2.2] octane, 1-benzyl-3-carbamoyl-pyridinium chloride , 1- (2'-Chloro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-methoxy-benzyl) - 3-carbamoyl-pyridinium chloride, 1- (2'-carboxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-carbamoyl-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3 'Chloro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-methoxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-carboxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-carbamoyl-benzyl) -3-carbamoyl-pyridinium chloride, 1- (4'-chlorobenzyl ) -3-carbamoyl-pyridinium chloride, 1- (4'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (4'-methoxybenzyl) -3-carbamoyl-pyridinium chloride, 1- (4 '-carboxy-benzyl) -3-carbamoyl pyridinium chloride, 1- (4'-carbamoyl-benzyl) -3-carbamoyl-pyridinium chloride, (1'-methyl-naphthyl) -3-carbamoyl-pyridinium chloride, 1- (1'-methyl-naphthyl) -3-carbamoyl pyridinium bromide, 1- (1'-methyl-naphthyl) -3-carbamoyl-pyridinium-fluoride, 1,1 '- (xylenyl) -3,3'-bis-carbamoyl-bis-pyridinium-dibromide, 1,1 ', 1 "- (Mesitylenyl) -3,3', 3" -tris-carbamoyl-tri-pyridinium-trichloride, and the corresponding bromides, fluorides, iodides and pseudohalides (eg triflates, tosylates) of the compounds listed above and quaternized N , N-bis [dialkylamino-alkyl] -ureas, with benzylated derivatives being particularly suitable.

Die erfindungsgemäßen Additive können mit N-Methylpyrrolidon alleine oder als Gemisch mehrerer unterschiedlicher Glanzbildnersysteme der oben genannten Vertreter in einer Konzentration von 0,0001 bis 20 g/l und besonders bevorzugt von 0,001 bis 1 g/l eingesetzt werden.The additives according to the invention can be used with N-methylpyrrolidone alone or as a mixture of a plurality of different brightener systems of the abovementioned representatives in a concentration of 0.0001 to 20 g / l and more preferably of 0.001 to 1 g / l.

Die Zinn-Ionenquelle und die Quelle für ein weiteres Legierungselement können Pyrophosphate sein. Insoweit sind die Zinn-Ionenquelle und die Quelle für ein weiteres Legierungselement auch Pyrophosphat-Quellen im Sinne der vorgenannten Komponente (iv) des erfindungsgemäßen Elektrolytbads.The tin ion source and the source of another alloying element may be pyrophosphates. In that regard, the tin ion source and the source of another alloying element are also pyrophosphate sources within the meaning of the aforementioned component (iv) of the electrolytic bath according to the invention.

In einem solchen Fall beträgt die Pyrophosphatkonzentration der Quelle für ein weiteres Legierungselement 0,5 bis 50 g/l und vorzugsweise 1 bis 5 g/l. Beispielsweise kann das erfindungsgemäße Bad Kupferpyrophosphat in einer Menge von 0,5 bis 50 g/l, vorzugsweise 1 bis 5 g/l oder Zinkpyrophosphat in diesen Mengen enthalten.In such a case, the pyrophosphate concentration of the source for another alloying element is 0.5 to 50 g / l, and preferably 1 to 5 g / l. For example, the bath according to the invention may contain copper pyrophosphate in an amount of 0.5 to 50 g / l, preferably 1 to 5 g / l or zinc pyrophosphate in these amounts.

Wenn als Zinn-Ionenquelle Zinnpyrophosphat in dem erfindungsgemäßen Elektrolytbad eingesetzt wird, beträgt die Konzentration im Allgemeinen 0,5 bis 100 g/l, wobei Konzentrationen von 10 bis 40 g/l besonders bevorzugt sind.When tin pyrophosphate is used as the tin ion source in the electrolytic bath of the present invention, the concentration is generally 0.5 to 100 g / l, with concentrations of 10 to 40 g / l being particularly preferred.

Neben den oben erwähnten Zinn- und Metallpyrophosphaten können auch anderweitige wasserlösliche Zinn- und Metallsalze, wie z.B. Zinnsulfat, Zinnmethansulfonat, Kupfersulfat, Kupfermethansulfonat, oder die entsprechenden Zinksalze eingesetzt werden, die durch Zusatz geeigneter Alkalimetallpyrophosphate innerhalb des Elektrolyten in die entsprechenden Pyrophosphate umkomplexiert werden können. Dabei sollte das Konzentrationsverhältnis Pyrophosphat zu Zinn/Metall bei 3 bis 80, besonders bevorzugt bei 5 bis 50 liegen.In addition to the above-mentioned tin and metal pyrophosphates, other water-soluble tin and metal salts, such as tin sulfate, tin methanesulfonate, copper sulfate, copper methanesulfonate, or the corresponding Zinc salts are used, which can be umkomplexiert by the addition of suitable alkali metal pyrophosphates within the electrolyte into the corresponding pyrophosphates. The concentration ratio of pyrophosphate to tin / metal should be 3 to 80, more preferably 5 to 50.

Pyrophosphat-Quellen gemäß Komponente (iv) sind besonders bevorzugt die Natrium-, Kalium- und Ammoniumpyrophosphate in Konzentrationen von 50 bis 500 g/l, besonders bevorzugt von 100 bis 400 g/l.Pyrophosphate sources according to component (iv) are particularly preferably the sodium, potassium and ammonium pyrophosphates in concentrations of 50 to 500 g / l, more preferably from 100 to 400 g / l.

Die vorgenannten Antioxidationsmittel beinhalten hydroxylierte aromatische Verbindungen wie z.B. Catechol, Resorcin, Brenzkatechin, Hydrochinon, Pyrogallol, α- oder β-Naphthol, Phloroglucin und zuckerbasierte Systeme wie z.B. Ascorbinsäure, Sorbitol in Konzentrationen von 0,1 bis 1 g/l.The aforementioned antioxidants include hydroxylated aromatic compounds, e.g. Catechol, resorcinol, pyrocatechol, hydroquinone, pyrogallol, α- or β-naphthol, phloroglucin and sugar-based systems such as e.g. Ascorbic acid, sorbitol in concentrations of 0.1 to 1 g / l.

Als organische Sulfonsäuren können sowohl Mono- als auch Polyalkylsulfonsäuren wie z.B. Methansulfonsäure, Methandisulfonsäure, Ethansulfonsäure, Propansulfonsäure, 2-Propansulfonsäure, Butansulfonsäure, 2-Butansulfonsäure, Pentansulfonsäure, Hexansulfonsäure, Decansulfonsäure, Dodecansulfonsäure sowie deren Salze und deren hydroxylierte Derivate eingesetzt werden. Besonders bevorzugt ist die Verwendung von Methansulfonsäure in einer Konzentration von 0,01 bis 1 g/l.As organic sulfonic acids, both mono- and polyalkylsulfonic acids, e.g. Methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid and salts thereof and their hydroxylated derivatives are used. Particularly preferred is the use of methanesulfonic acid in a concentration of 0.01 to 1 g / l.

Die erfindungsgemäßen Bäder weisen einen pH-Wert von 3 bis 9, besonders bevorzugt 6 bis 8 auf.The baths according to the invention have a pH of 3 to 9, more preferably 6 to 8.

Überraschend und unerwarteter Weise konnte gefunden werden, dass durch Zusatz von N-Methylpyrrolidon eine signifikante Verbesserung der abgeschiedenen Schichten hinsichtlich Glanz und Porenfreiheit erreicht werden kann, vorzugsweise in einer Konzentration von 0,1 bis 50 g/l, besonders bevorzugt 0,1 bis 4 g/l.Surprisingly and unexpectedly it could be found that by adding N-methylpyrrolidone a significant improvement in the deposited layers can be achieved with regard to gloss and freedom from pores, preferably in a concentration of 0.1 to 50 g / l, more preferably 0.1 to 4 g / l.

Die erfindungsgemäßen Bäder können mit gebräuchlichen Verfahren hergestellt werden, beispielsweise durch Zugabe der spezifischen Mengen der vorstehend beschriebenen Komponenten zu Wasser. Die Menge der Basen-, Säure- und Pufferkomponenten, wie z.B. Natriumpyrophosphat, Methansulfonsäure und/oder Borsäure, sollte vorzugsweise so gewählt werden, dass das Bad den pH-Bereich von mindestens 6 bis 8 zu erreicht.The baths according to the invention can be prepared by conventional methods, for example by adding the specific amounts of the above-described components to water. The amount of bases, acids and acids Buffer components such as sodium pyrophosphate, methanesulfonic acid and / or boric acid should preferably be chosen so that the bath reaches the pH range of at least 6 to 8.

Die erfindungsgemäßen Bäder scheiden eine blanke, ebene und duktile Kupfer-Zinn-Legierungsschicht bei jeder gebräuchlichen Temperatur von etwa 15 bis 50°C, vorzugsweise 20°C bis 40°C, besonders bevorzugt 25°C bis 30°C, ab. Bei diesen Temperaturen sind die erfindungsgemäßen Bäder stabil und über einen weiten Stromdichtebereich von 0,01 bis 2 A/dm2, besonders bevorzugt 0,25 bis 0,75 A/dm2, wirkungsvoll.The baths according to the invention deposit a bright, even and ductile copper-tin alloy layer at any customary temperature of about 15 to 50 ° C, preferably 20 ° C to 40 ° C, more preferably 25 ° C to 30 ° C from. At these temperatures, the baths according to the invention are stable and effective over a wide current density range of 0.01 to 2 A / dm 2 , more preferably 0.25 to 0.75 A / dm 2 .

Die erfindungsgemäßen Bäder können auf eine kontinuierliche oder intermittierende Weise betrieben werden, und von Zeit zu Zeit wird man die Komponenten des Bades ergänzen müssen. Die Komponenten des Bades können einzeln oder in Kombination zugesetzt werden. Ferner können sie über einen weiten Bereich variiert werden, abhängig vom Verbrauch und vorliegenden Konzentration der Einzelkomponenten.The baths of the invention may be operated in a continuous or intermittent manner, and from time to time the components of the bath will have to be supplemented. The components of the bath may be added singly or in combination. Furthermore, they can be varied over a wide range, depending on the consumption and present concentration of the individual components.

Ein Vorteil der erfindungsgemäßen Bäder im Vergleich zum Elektrolyten der WO 2004/005528 ist die gute Reproduzierbarkeit und Langzeitstabilität der erfindungsgemäßen Formulierungen im Vergleich zu den Umsetzungsprodukten des Piperazin mit Epichlorhydrin und Glycidylether.An advantage of the baths according to the invention compared to the electrolyte of WO 2004/005528 is the good reproducibility and long-term stability of the formulations according to the invention in comparison to the reaction products of piperazine with epichlorohydrin and glycidyl ether.

Die erfindungsgemäßen wässrigen Bäder können im allgemeinen für alle Arten von Substraten verwendet werden, auf welchen Zinn-Legierungen abgeschieden werden können. Beispiele zweckdienlicher Substrate schließen Kupfer-Zink-Legierungen, mit chemisch Kupfer oder chemisch Nickel beschichtete ABS-Kunststoffoberflächen, Weichstahl, Edelstahl, Federstahl, Chromstahl, Chrom-Molybdänstahl, Kupfer und Zinn ein.The aqueous baths according to the invention can generally be used for all types of substrates on which tin alloys can be deposited. Examples of useful substrates include copper-zinc alloys, chemically copper or chemically nickel-coated ABS plastic surfaces, mild steel, stainless steel, spring steel, chrome steel, chromium-molybdenum steel, copper and tin.

Ein weiterer Gegenstand ist daher ein Verfahren zur galvanischen Abscheidung von Kupfer-Zinn-Legierungen auf üblichen Substraten, wobei das erfindungsgemäße Bad verwendet wird. Dabei wird das zu beschichtende Substrat in das Elektrolytbad eingebracht.Another object is therefore a process for the electrodeposition of copper-tin alloys on conventional substrates, wherein the inventive Bath is used. In this case, the substrate to be coated is introduced into the electrolyte bath.

Vorzugsweise erfolgt bei dem erfindungsgemäßen Verfahren die Abscheidung der Überzüge bei einer Stromdichte von 0,25 bis 0,75 A/dm2 sowie bei einer Temperatur von 15 bis 50°C, vorzugsweise 25 bis 30°C.Preferably, in the inventive method, the deposition of the coatings at a current density of 0.25 to 0.75 A / dm 2 and at a temperature of 15 to 50 ° C, preferably 25 to 30 ° C.

Das erfindungsgemäße Verfahren kann bei der Anwendung für Massenteile beispielsweise als Trommelgalvanisierverfahren und zur Abscheidung auf größeren Werkstücken als Gestellgalvanisierverfahren durchgeführt werden. Dabei werden Anoden verwendet, die löslich sein können, wie beispielsweise Kupferanoden, Zinnanoden oder geeignete Kupfer-Zinn-Legierungsanoden, die gleichzeitig als Kupfer und/oder Zinn-Ionen-Quelle dienen, damit das auf der Kathode abgeschiedenen Kupfer und/oder Zinn durch Auflösen von Kupfer und/oder Zinn an der Anode substituiert wird.The method according to the invention can be carried out in the application for mass parts, for example as a drum electroplating method and for depositing on larger workpieces as a rack electroplating method. In this case, anodes are used which may be soluble, such as copper anodes, tin anodes or suitable copper-tin alloy anodes, which simultaneously serve as copper and / or tin ion source, so that the deposited on the cathode copper and / or tin by dissolution is substituted by copper and / or tin at the anode.

Andererseits können auch unlösliche Anoden (z.B. platinierte Titanmischoxid-Anoden) eingesetzt werden, wobei die dem Elektrolyten entzogenen Kupfer- und Zinn-Ionen auf andere Weise wieder zugesetzt werden müssen, z.B. durch Zusatz der entsprechenden löslichen Metallsalze. Wie bei der galvanischen Abscheidung möglich, kann auch das erfindungsgemäße Verfahren unter Stickstoff- oder Argoneinblasung, mit Warenbewegung oder ohne Bewegung, betrieben werden, ohne dass sich hierfür irgendwelche Nachteile für die erhaltenen Überzüge ergeben. Zur Vermeidung bzw. Reduzierung von Oxidationen der zugesetzten Additive bzw. der Zinn(II)-Ionen kann mit der Trennung der Elektrodenräume oder mit der Verwendung von Membrananoden gearbeitet werden, wodurch eine erhebliche Stabilisierung des Elektrolyten erreicht werden kann.On the other hand, insoluble anodes (e.g., platinized titanium mixed oxide anodes) may also be employed, and the copper and tin ions withdrawn from the electrolyte must be re-added in some other way, e.g. by addition of the corresponding soluble metal salts. As in the case of galvanic deposition, it is also possible to operate the process according to the invention under nitrogen or argon injection, with goods movement or without movement, without resulting in any disadvantages for the coatings obtained. To avoid or reduce oxidations of the added additives or the tin (II) ions can be used with the separation of the electrode spaces or with the use of membrane anodes, whereby a significant stabilization of the electrolyte can be achieved.

Als Stromquelle dienen handelsübliche Gleichstromrichter oder Pulsgleichrichter.The current source used are commercial DC converters or pulse rectifiers.

Beispiele:Examples: Anwendungsbeispiel 1:Application Example 1

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 0,1 g/l 1-(Pentafluorbenzyl)-3-carbamoyl-pyridinium-chlorid An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.1 g / l 1- (pentafluorobenzyl) -3-carbamoyl pyridinium chloride

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Anwendungsbeispiel 2:Application Example 2:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 20 ml/l N-Methylpyrrolidon 0,06 g/l 1-Benzyl-3-acetyl-pyridinium-chlorid An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 20 ml / l N-methylpyrrolidone 0.06 g / l 1-benzyl-3-acetyl-pyridinium chloride

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung mit leichtem Schleier im niedrigen Stromdichtebereich erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high glossy, light veil deposit in the low current density range was obtained.

Anwendungsbeispiel 3:Application Example 3

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 0,03 g/l 1-(4-Methoxy-benzyl)-3-carbamoyl-pyridinium-chlorid An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.03 g / l 1- (4-methoxy-benzyl) -3-carbamoyl pyridinium chloride

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A brilliant deposit was obtained.

Anwendungsbeispiel 4:Application Example 4:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 0,03 g/l 1,1'-(Xylenyl)-3',3-bis-carbamoyl-bis-pyridinium-dichlorid An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.03 g / l 1,1 '- (xylenyl) -3', 3-bis-carbamoyl-bis-pyridinium dichloride

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1 A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1 A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Anwendungsbeispiel 5:Application Example 5:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 0,12 g/l 1-(4'-Carboxy-benzyl)-3-carbamoyl-pyridinium-chlorid An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 0.12 g / l 1- (4'-Carboxy-benzyl) -3-carbamoyl pyridinium chloride

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Anwendungsbeispiel 6:Application Example 6:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 3 ml/l 1-(Benzyl)-3-carbamoyl-pyridinium-chlorid 35%-ige Lösung An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 ml / l 1- (Benzyl) -3-carbamoylpyridinium chloride 35% solution

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Anwendungsbeispiel 7:Application Example 7:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 3 g/l Morpholin An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 g / l morpholine

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Anwendungsbeispiel 8 :Application Example 8:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 5 g/l 2-Morpholino-ethansulfonsäure An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 5 g / l 2-morpholino-ethane sulfonic acid

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Anwendungsbeispiel 9 :Application Example 9:

Es wird ein Elektrolyt mit folgender Zusammensetzung verwendet: 300 g/l Tetrakaliumpyrophosphat 10 g/l Kupferpyrophosphat 30 g/l Zinnpyrophosphat 50 g/l Borsäure 32,4 ml/l Phosphorsäure 85%-ig 40 ml/l N-Methylpyrrolidon 3 g/l 3-(4-Morpholino)-1,2-propandiol An electrolyte with the following composition is used: 300 g / l tetrapotassiumpyrophosphate 10 g / l copper pyrophosphate 30 g / l pyrophosphate 50 g / l boric acid 32.4 ml / l 85% phosphoric acid 40 ml / l N-methylpyrrolidone 3 g / l 3- (4-morpholino) -1,2-propanediol

250 ml des Elektrolyten mit einem pH-Wert von 7 werden in eine Hullzelle gefüllt. Als Anode dient eine Titan-Mischoxid-Elektrode. Das Kathodenblech wird 10 min bei 1A beschichtet. Nach beendeter Beschichtung wird das Blech abgespült und unter Pressluft getrocknet. Es wurde eine hoch glänzende Abscheidung erhalten.250 ml of the electrolyte with a pH of 7 are filled into a Hull cell. The anode used is a titanium mixed oxide electrode. The cathode sheet is coated at 1A for 10 minutes. After completion of the coating, the sheet is rinsed and dried under compressed air. A high gloss deposit was obtained.

Claims (22)

Wässriges cyanid-freies Elektrolytbad zur Abscheidung von Zinn-Legierungsschichten auf Substratoberflächen, umfassend (i) eine Zinn-lonenquelle und eine Quelle für ein weiteres Legierungselement, dadurch gekennzeichnet, dass sie weiterhin (ii) N-Methylpyrrolidon enthält. An aqueous cyanide-free electrolyte bath for depositing tin alloy layers on substrate surfaces, comprising (i) a tin ion source and a source of another alloying element, characterized by further comprising (ii) contains N-methylpyrrolidone. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, weiterhin umfassend eine Säure (iii) und/oder eine Pyrophosphat-Quelle (iv).An aqueous cyanide-free electrolyte bath according to claim 1, further comprising an acid (iii) and / or a pyrophosphate source (iv). Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, worin die Säure Orthophosphorsäure, Schwefelsäure oder Methansulfonsäure ist.An aqueous cyanide-free electrolytic bath according to claim 1, wherein the acid is orthophosphoric acid, sulfuric acid or methanesulfonic acid. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, worin die Zinn-Ionenquelle Zinnpyrophosphat ist.An aqueous cyanide-free electrolyte bath according to claim 1, wherein the tin ion source is tin pyrophosphate. Wässriges cyanid-freies Elektrolytbad nach Anspruch 4, enthaltend Zinnpyrophosphat in einer Menge von 0,5 bis 100 g/l.An aqueous cyanide-free electrolyte bath according to claim 4, containing tin pyrophosphate in an amount of 0.5 to 100 g / l. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, worin die Quelle für ein weiteres Legierungselement Kupferpyrophosphat ist.An aqueous cyanide-free electrolyte bath according to claim 1, wherein the source of another alloying element is copper pyrophosphate. Wässriges cyanid-freies Elektrolytbad nach Anspruch 5 oder 6, enthaltend Zinnpyrophosphat in einer Menge von 10 bis 40 g/l und Kupferpyrophosphat in einer Menge von 1 bis 5 g/l.An aqueous cyanide-free electrolytic bath according to claim 5 or 6, containing tin pyrophosphate in an amount of 10 to 40 g / l and copper pyrophosphate in an amount of 1 to 5 g / l. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, worin die Pyrophosphatquelle aus der Gruppe, bestehend aus Natrium-, Kalium- und Ammoniumpyrophosphaten, ausgewählt ist.An aqueous cyanide-free electrolyte bath according to claim 1, wherein the pyrophosphate source is selected from the group consisting of sodium, potassium and ammonium pyrophosphates. Wässriges cyanid-freies Elektrolytbad nach Anspruch 8, enthaltend die Pyrophosphate in einer Konzentration von 50 bis 500 g/l.An aqueous cyanide-free electrolyte bath according to claim 8, containing the pyrophosphates in a concentration of 50 to 500 g / l. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, worin das Konzentrationsverhältnis von Pyrophosphat zu Zinn/Legierungselement 3 bis 80 beträgt.An aqueous cyanide-free electrolytic bath according to claim 1, wherein the concentration ratio of pyrophosphate to tin / alloying element is 3 to 80. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, enthaltend N-Methylpyrrolidon in einer Konzentration von 0,1 bis 50 g/l.An aqueous cyanide-free electrolyte bath according to claim 1, containing N-methylpyrrolidone in a concentration of 0.1 to 50 g / l. Wässriges cyanid-freies Elektrolytbad nach Anspruch 11, enthaltend N-Methylpyrrolidon in einer Konzentration von 0,1 bis 4 g/l.An aqueous cyanide-free electrolyte bath according to claim 11, containing N-methylpyrrolidone in a concentration of 0.1 to 4 g / l. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1 mit einem pH-Wert von 3 bis 9.An aqueous cyanide-free electrolyte bath according to claim 1 having a pH of 3 to 9. Wässriges cyanid-freies Elektrolytbad nach Anspruch 1, weiterhin umfassend ein Antioxidationsmittel und/oder einen weiteren organischen Glanzbildner.An aqueous cyanide-free electrolyte bath according to claim 1, further comprising an antioxidant and / or another organic brightener. Wässriges cyanid-freies Elektrolytbad nach Anspruch 14, worin der weitere organische Glanzbildner aus der Gruppe, bestehend aus Morpholin, 2-Morpholinethansulfonsäure, Hexamethylentetramin, 3-(4-Morpholino)-1,2-propandiol, 1,4-Diazabicyclo-[2.2.2]-octan, 1-Benzyl-3-carbamoyl-pyridiniumchlorid, 1-(2'-Chloro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Fluoro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Methoxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Carboxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(2'-Carbamoyl-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Chloro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Fluoro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Methoxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Carboxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(3'-Carbamoyl-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Chloro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Fluoro-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Methoxy-benzyl)-3-carbamoyl-pyridinium-chlorid, 1-(4'-Carbamoyl-benzyl)-3-carbamoyl-pyridinium-chlorid, (1'-Methyl-naphthyl)-3-carbamoyl-pyridinium-chlorid, 1-(1'methyl-naphthyl)-3-carbamoyl-pyridinium-bromid, 1,1'-(Xylenyl)-3,3'-bis-carbamoyl-bis-pyridinium-dibromid, 1,1',1"-(Mesitylenyl)-3,3',3"-tris-carbamoyl-tri-pyridinium-trichlorid, den korrespondierenden Bromiden, Fluoriden, Iodiden und Pseudohalogeniden der vorgenannten Verbindungen und quaternisierten N,N-Bis-[dialkylamino-alkyl]-harnstoffen ausgewählt ist.The aqueous cyanide-free electrolyte bath of claim 14, wherein the further organic brightener is selected from the group consisting of morpholine, 2-morpholineethanesulfonic acid, hexamethylenetetramine, 3- (4-morpholino) -1,2-propanediol, 1,4-diazabicyclo [2.2 .2] octane, 1-benzyl-3-carbamoyl-pyridinium chloride, 1- (2'-chlorobenzyl) -3-carbamoyl-pyridinium chloride, 1- (2'-fluoro-benzyl) -3-carbamoyl- pyridinium chloride, 1- (2'-methoxybenzyl) -3-carbamoylpyridinium chloride, 1- (2'-carboxybenzyl) -3-carbamoylpyridinium chloride, 1- (2'-carbamoyl) benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-chlorobenzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1 - (3'-methoxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-carboxy-benzyl) -3-carbamoyl-pyridinium chloride, 1- (3'-carbamoyl-benzyl) -3- carbamoyl-pyridinium chloride, 1- (4'-chlorobenzyl) -3-carbamoyl-pyridinium chloride, 1- (4'-fluoro-benzyl) -3-carbamoyl-pyridinium chloride, 1- (4'- methoxy-benzyl) -3-carbamoyl pyridinium chloride, 1- (4'-carbamoyl-benzyl) -3-carbamoyl-pyridinium chloride, (1'-methyl-naphthyl) -3-carbamoyl-pyridinium chloride, 1- (1'-methyl-naphthyl) -3-carbamoyl pyridinium bromide, 1,1 '- (xylenyl) -3,3'-bis-carbamoyl-bis-pyridinium-dibromide, 1,1', 1 "- (mesitylenyl) -3,3 ', 3" -tris- carbamoyl-tri-pyridinium trichloride, the corresponding bromides, fluorides, iodides and pseudohalides of the aforementioned compounds and quaternized N, N-bis- [dialkylamino-alkyl] -ureas. Verfahren zur galvanischen Abscheidung von glänzenden und ebenen Zinn-Legierungsüberzügen, umfassend das Einbringen eines zu beschichtenden Substrats in ein wässriges cyanid-freies Elektrolytbad nach den Ansprüchen 1 bis 15 und Abscheiden des Zinnlegierungsüberzugs auf dem Substrat.A method of electrodepositing bright and even tin alloy plating, comprising introducing a substrate to be coated into an aqueous cyanide-free electrolyte bath according to claims 1 to 15 and depositing the tin alloy coating on the substrate. Verfahren nach Anspruch 16, worin das Bad bei einer Stromdichte von 0,01 bis 2 A/dm2 betrieben wird.The method of claim 16, wherein the bath is operated at a current density of 0.01 to 2 A / dm 2 . Verfahren nach Anspruch 17, worin das Bad bei einer Stromdichte von 0,25 bis 0,75 A/dm2 betrieben wird.The method of claim 17, wherein the bath is operated at a current density of 0.25 to 0.75 A / dm 2 . Verfahren nach Anspruch 16, worin das Bad bei einer Temperatur von 15 bis 50°C betrieben wird.The process of claim 16, wherein the bath is operated at a temperature of 15 to 50 ° C. Verfahren nach Anspruch 19, worin das Bad bei einer Temperatur von 25 bis 30°C betrieben wird.The process of claim 19, wherein the bath is operated at a temperature of 25 to 30 ° C. Verfahren nach den Ansprüchen 16 bis 20, worin die Überzüge auf einem leitenden Substrat unter Anwendung eines Gestellgalvanisierungsverfahren abgeschieden werden.The method of claims 16 to 20, wherein the coatings are deposited on a conductive substrate using a rack plating process. Verfahren nach den Ansprüchen 16 bis 21, worin als Anoden Membrananoden verwendet werden.Process according to claims 16 to 21, wherein as anodes membrane anodes are used.
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DE502008000573T DE502008000573D1 (en) 2008-02-29 2008-02-29 Pyrophosphate-based bath for the deposition of tin alloy layers
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EP08003786A EP2103717B1 (en) 2008-02-29 2008-02-29 Pyrophosphate-based bath for depositing tin alloy layers
ES08003786T ES2340973T3 (en) 2008-02-29 2008-02-29 PIROPHOSPHATE BASED BATHROOM FOR THE DEPOSITION OF TIN ALLOY LAYERS.
CN2009801015016A CN101918618B (en) 2008-02-29 2009-02-05 Pyrophosphate-based bath for plating on tin alloy layers
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US12/864,180 US8647491B2 (en) 2008-02-29 2009-02-05 Pyrophosphate-based bath for plating of tin alloy layers
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