EP0194432A1 - Bath for the galvanic deposition of gold-tin alloy coatings - Google Patents

Bath for the galvanic deposition of gold-tin alloy coatings Download PDF

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Publication number
EP0194432A1
EP0194432A1 EP86101083A EP86101083A EP0194432A1 EP 0194432 A1 EP0194432 A1 EP 0194432A1 EP 86101083 A EP86101083 A EP 86101083A EP 86101083 A EP86101083 A EP 86101083A EP 0194432 A1 EP0194432 A1 EP 0194432A1
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Prior art keywords
tin
gold
bath
oxalic acid
acid
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EP86101083A
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German (de)
French (fr)
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EP0194432B1 (en
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Werner Kuhn
Wolfgang Zilske
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Evonik Operations GmbH
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Degussa GmbH
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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
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold

Definitions

  • the invention relates to a bath for the electrodeposition of gold / tin alloy coatings at pH values less than 3, consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 Tin in the form of a water-soluble tin salt, optionally 0.005 to 1 g / 1 of a further alloy metal in the form of a water-soluble salt, an acid and a buffer or conductive salt.
  • the galvanic co-deposition of tin from gold baths is of interest for decorative and technical applications.
  • decorative industrial gold are / tin - alloy baths for producing color gold coatings, especially white gold layers used, and in electrical engineering, the good corrosion resistance and solderability provides the tin in conjunction with Gold advantages over other alloy layers.
  • Tin in combination with gold can only be separated from weakly acid baths, at pH values from 3.5 to 6, if it is divalent.
  • the electrolytes contain the gold in the form of potassium dicyano-aurate (I), KAutCN) 2 _
  • Such electrolytes are known from DE-OS 1 960 047 and DE-AS 25 23 510.
  • these baths are not stable since divalent tin is oxidized relatively easily to tetravalent, which is no longer deposited under the given conditions.
  • Protective substances such as complexing agents, sulfonic acids or soluble tin anodes cannot adequately prevent oxidation.
  • DE-OS 26 58 003 and DE-PS 30 12 999 the co-deposition of tin from strongly acidic gold electrolytes at pH values less than 3 is known, which the gold in the form of the tetracyanoaurate (III) complex Au (CN) 4 included. In these baths, the tin is separated from the divalent and tetravalent oxidation stage.
  • DE-OS 26 58 003 describes a galvanic bath which contains 1 to 30 g / 1 gold as a gold (III) cyanide complex and 1 to 150 g / 1 tin as a halogen stannate (IV) complex Adjustment of the pH value and to stabilize the complex of hydrogen halide acids, which lead to considerable corrosion damage to the galvanic systems. In addition, poisonous halogen is developed at the anode during electrolysis, which escapes in gaseous form under the given working conditions.
  • a bath for the electrodeposition of gold / tin alloy layers at pH values less than 3 consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 tin in the form of a water-soluble tin salt, optionally
  • the bath contains the tin in the form of a tin (IV) oxalato complex.
  • V or preferably it contains the complex in the form of potassium oxalatostannate (IV).
  • oxalato tin (IV) acid can also be used, for example.
  • oxalic acid or oxalic acid and ammonium sulfate are used as buffer or conductive salts. 10 to 50 g / 1 oxalic acid or mixtures of 10 to 50 g / l oxalic acid and 10 to 100 g / 1 ammonium sulfate are preferably used.
  • the bath can additionally contain 0.005 to 1 g / l of a further alloy metal in the form of a water-soluble nickel or cobalt salt.
  • the pH of the bath is advantageously adjusted to 0.5 to 2.5 using sulfuric acid or oxalic acid.
  • the bath is normally used at temperatures between 20 and 60 ° C, preferably at 40 to 55 ° C, and current densities of 0.2 to 5 A / dm 2 , preferably 1 to 4 A / dm 2 .
  • Oxalato tin (IV) acid is produced, for example, by dissolving tin in oxalic acid with the addition of hydrogen peroxide, potassium oxalate stannate (IV) by reacting tin (IV) chloride with potassium oxalate. Thanks to the use of tin in grade 4 and in a complex bond, the bath is stable against oxidation. No tin acid is excreted.
  • these gold / tin alloy baths with oxalato complexes without special gloss additives, such as salts of semi-metals such as selenium or tellurium or organic compounds provide shiny coatings over a wide current density range with high current yields of approx. 90%.
  • the additional co-deposition of cobalt or nickel can influence the color and the technological properties, such as hardness and mechanical abrasion resistance, of the coatings.
  • the current yield then drops to values of 40 to 50%.
  • the very low content of non-metallic impurities in the coatings is also surprising. At less than 0.1%, it is far below that of comparable gold alloy coatings.
  • the coatings are also high hardness despite very ductile (HV 0th 015 230).
  • the elongation at break measured at 10 ⁇ m thick layers on a copper foil is around 20% in the order of that of fine gold layers.

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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

Zur galvanischen Abscheidung glänzender Gold/Zinn-Legierungsschichten werden Bäder mit pH-Werten kleiner 3 eingesetzt, die 1 bis 20 g/l Gold in Form von Tetracyanoaurat (III) 0,1 bis 10 g/l Zinn, eine Säure und ein Leitsalz enthalten, wobei das Zinn in Form eines Zinn(lV)-Oxalato-Komplexes vorliegt.For the electrodeposition of shiny gold / tin alloy layers, baths with pH values less than 3 are used, which contain 1 to 20 g / l gold in the form of tetracyanoaurate (III) 0.1 to 10 g / l tin, an acid and a conductive salt , the tin being in the form of a tin (IV) oxalato complex.

Description

Die Erfindung betrifft ein Bad zur galvanischen Abscheidung von Gold/Zinn-Legierungsüberzügen bei pH-Werten kleiner als 3, bestehend aus 1 bis 20 g/1 Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat (III), 0.1 bis 10 g/1 Zinn in Form eines wasserlöslichen Zinnsalzes, gegebenenfalls 0.005 bis 1 g/1 eines weiteren Legierungsmetalls in Form eines wasserlöslichen Salzes, einer Säure und einem Puffer- oder Leitsalz.The invention relates to a bath for the electrodeposition of gold / tin alloy coatings at pH values less than 3, consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 Tin in the form of a water-soluble tin salt, optionally 0.005 to 1 g / 1 of a further alloy metal in the form of a water-soluble salt, an acid and a buffer or conductive salt.

Die galvanische Mitabscheidung von Zinn aus Goldbädern ist für dekorative und technische Anwendungen von Interesse. In der dekorativen Industrie werden Gold/ Zinn-Legierungsbäder zur Erzeugung von Farbgoldüberzügen, vor allem Weißgoldschichten, eingesetzt und in der Elektrotechnik bietet die gute Korrosionsbeständigkeit und Lötbarkeit des Zinns in Verbindung mit Gold Vorteile gegenüber anderen Legierungsschichten.The galvanic co-deposition of tin from gold baths is of interest for decorative and technical applications. In decorative industrial gold are / tin - alloy baths for producing color gold coatings, especially white gold layers used, and in electrical engineering, the good corrosion resistance and solderability provides the tin in conjunction with Gold advantages over other alloy layers.

Die gemeinsame Abscheidung von Zinn und Gold ist aus alkalischen und sauren Elektrolyten möglich. In der US-PS 1 905 105 wird ein alkalischer Elektrolyt, der Kaliumdicyanoaurat(I) und Zinn als Hydroxostannat(IV) enthält, beschrieben. Gold/Zinn-Legierungsüberzüge aus Bädern dieses Typs können jedoch nicht metallisch glänzend abgeschieden werden.The combined deposition of tin and gold is possible from alkaline and acidic electrolytes. US Pat. No. 1,905,105 describes an alkaline electrolyte which contains potassium dicyanoaurate (I) and tin as hydroxostannate (IV). However, gold / tin alloy coatings from baths of this type cannot be deposited with a metallic sheen.

Aus schwach sauren Bädern, bei pH-Werten von 3.5 bis 6, kann Zinn in Verbindung mit Gold nur abgeschieden werden, wenn es zweiwertig vorliegt. Die Elektrolyte enthalten das Gold dabei in Form von Kaliumdicyanoau- rat(I), KAutCN)2_ Bekannt sind solche Elektrolyte aus der DE-OS 1 960 047 und der DE-AS 25 23 510. Diese Bäder sind allerdings nicht stabil, da das zweiwertige Zinn relativ leicht zum vierwertigen oxidiert wird, das unter den gegebenen Bedingungen nicht mehr mitabgeschieden wird. Auch Schutzsubstanzen, wie Komplexbildner, Sulfonsäuren oder lösliche Zinnanoden können die Oxidation nicht ausreichend verhindern.Tin in combination with gold can only be separated from weakly acid baths, at pH values from 3.5 to 6, if it is divalent. The electrolytes contain the gold in the form of potassium dicyano-aurate (I), KAutCN) 2 _ Such electrolytes are known from DE-OS 1 960 047 and DE-AS 25 23 510. However, these baths are not stable since divalent tin is oxidized relatively easily to tetravalent, which is no longer deposited under the given conditions. Protective substances such as complexing agents, sulfonic acids or soluble tin anodes cannot adequately prevent oxidation.

Aus der DE-OS 26 58 003 und der DE-PS 30 12 999 ist die Mitabscheidung von Zinn aus stark sauren Goldelektrolyten bei pH-Werten kleiner als 3 bekannt, die das Gold in Form des Tetracyanoaurat(III)-Komplexes Au(CN)4 enthalten. In diesen Bädern wird das Zinn aus der zweiwertigen und vierwertigen Oxidationsstufe abgeschieden.
In der DE-OS 26 58 003 wird ein galvanisches Bad beschrieben, das 1 bis 30 g/1 Gold als Gold(III)-Cyanid- komplex und 1 bis 150 g/1 Zinn als Halogenstannat(IV)-Komplex enthält, wobei zur Einstellung des pH-Wertes und zur Stabilisierung des Komplexes Halogenwasserstoffsäuren verwendet werden, die zu erheblichen Korrosionsschäden an den galvanischen Anlagen führen. Außerdem wird während der Elektrolyse an der Anode giftiges Halogen entwickelt, das unter den gegebenen Arbeitsbedingungen gasförmig entweicht.From DE-OS 26 58 003 and DE-PS 30 12 999 the co-deposition of tin from strongly acidic gold electrolytes at pH values less than 3 is known, which the gold in the form of the tetracyanoaurate (III) complex Au (CN) 4 included. In these baths, the tin is separated from the divalent and tetravalent oxidation stage.
DE-OS 26 58 003 describes a galvanic bath which contains 1 to 30 g / 1 gold as a gold (III) cyanide complex and 1 to 150 g / 1 tin as a halogen stannate (IV) complex Adjustment of the pH value and to stabilize the complex of hydrogen halide acids, which lead to considerable corrosion damage to the galvanic systems. In addition, poisonous halogen is developed at the anode during electrolysis, which escapes in gaseous form under the given working conditions.

Es war daher Aufgabe der vorliegenden Erfindung, ein Bad zur galvanischen Abscheidung von Gold/Zinn-Legierungsschichten bei pH-Werten kleiner als 3 zu entwickeln, bestehend aus 1 bis 20 g/1 Gold in Form von Alkali- und/ oder Ammoniumtetracyanoaurat(III), 0.1 bis 10 g/1 Zinn in Form eines wasserlöslichen Zinnsalzes, gegebenenfalls 0.005 bis 1 g/1 eines weiteren Legierungsmetalls in Form eines wasserlöslichen Salzes, einer Säure und einem Puffer- oder Leitsalz, das das Zinn als stabiles Komplexsalz der Oxidationszahl IV enthält, halogenidfrei ist und glänzende Legierungsschichten liefert.It was therefore an object of the present invention to develop a bath for the electrodeposition of gold / tin alloy layers at pH values less than 3, consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 tin in the form of a water-soluble tin salt, optionally 0.005 to 1 g / 1 of another alloy metal in the form of a water-soluble salt, an acid and a buffer or conductive salt, which the tin as a stable complex salt contains the oxidation number IV, is halide-free and provides shiny alloy layers.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Bad das Zinn in Form eines Zinn(IV)-Oxalato-Komplexes enthält. V
orzugsweise enthält es den Komplex in Form von Kalium- oxalatostannat(IV). Daneben kann beispielsweise auch Oxalatozinn(IV)-säure eingesetzt werden. Weiterhin hat es sich als vorteilhaft erwiesen, wenn als Puffer- bzw. Leitsalze Oxalsäure oder Oxalsäure und Ammoniumsulfat verwendet werden. Vorzugsweise werden 10 bis 50 g/1 Oxalsäure oder Gemische aus 10 bis 50 g/l Oxalsäure und 10 bis 100 g/1 Ammoniumsulfat eingesetzt.
Das Bad kann zusätzlich 0.005 bis 1 g/1 eines weiteren Legierungsmetalls in Form eines wasserlöslichen Nickel-oder Kobaltsalzes enthalten. Vorteilhafterweise wird der pH-Wert des Bades auf 0.5 bis 2.5 mit Schwefelsäure oder Oxalsäure eingestellt.The object is achieved in that the bath contains the tin in the form of a tin (IV) oxalato complex. V
or preferably it contains the complex in the form of potassium oxalatostannate (IV). In addition, oxalato tin (IV) acid can also be used, for example. Furthermore, it has proven to be advantageous if oxalic acid or oxalic acid and ammonium sulfate are used as buffer or conductive salts. 10 to 50 g / 1 oxalic acid or mixtures of 10 to 50 g / l oxalic acid and 10 to 100 g / 1 ammonium sulfate are preferably used.
The bath can additionally contain 0.005 to 1 g / l of a further alloy metal in the form of a water-soluble nickel or cobalt salt. The pH of the bath is advantageously adjusted to 0.5 to 2.5 using sulfuric acid or oxalic acid.

Das Bad wird normalerweise bei Temperaturen zwischen 20 und 60°C, bevorzugt bei 40 bis 55°C,und Stromdichten von 0.2 bis 5 A/dm2, bevorzugt 1 bis 4 A/dm2 eingesetzt. Oxalatozinn(IV)-Säure wird z.B. durch Auflösen von Zinn in Oxalsäure unter Zusatz von Wasserstoffperoxid, Kaliumoxalatostannat(IV) durch Umsetzung von Zinn(IV)-Chlorid mit Kaliumoxalat hergestellt. Durch die Verwendung des Zinns in der Wertigkeitsstufe 4 und in komplexer Bindung ist das Bad gegen Oxidation stabil. Es wird auch keine Zinnsäure ausgeschieden.The bath is normally used at temperatures between 20 and 60 ° C, preferably at 40 to 55 ° C, and current densities of 0.2 to 5 A / dm 2 , preferably 1 to 4 A / dm 2 . Oxalato tin (IV) acid is produced, for example, by dissolving tin in oxalic acid with the addition of hydrogen peroxide, potassium oxalate stannate (IV) by reacting tin (IV) chloride with potassium oxalate. Thanks to the use of tin in grade 4 and in a complex bond, the bath is stable against oxidation. No tin acid is excreted.

Überraschenderweise liefern diese Gold/Zinn-Legierungsbäder mit Oxalatokomplexen ohne besondere Glanzzusätze, wie Salze von Halbmetallen z.B. Selen oder Tellur oder organische Verbindungen, über einen breiten Stromdichtebereich mit hohen Stromausbeuten von ca. 90 % glänzende Überzüge.
Durch die zusätzliche Mitabscheidung von Kobalt oder Nickel können die Farbe und die technologischen Eigenschaften, wie Härte und mechanische Abriebbeständigkeit, der Überzüge beeinflußt werden. Die Stromausbeute sinkt dann allerdings auf Werte von 40 bis 50 % ab. Überraschend ist auch der sehr niedrige Gehalt an nichtmetallischen Verunreinigungen in den Überzügen. Mit weniger als 0.1 % liegt er weit unter dem vergleichbarer Goldlegierungsüberzüge. Die Überzüge sind außerdem trotz hoher Härte (HV 0.015 ca. 230) sehr duktil. Die an 10 µm dicken Schichten auf einer Kupferfolie gemessene Bruchdehnung liegt mit ca. 20 % in der Größenordnung der von Feingoldschichten.Surprisingly, these gold / tin alloy baths with oxalato complexes without special gloss additives, such as salts of semi-metals such as selenium or tellurium or organic compounds, provide shiny coatings over a wide current density range with high current yields of approx. 90%.
The additional co-deposition of cobalt or nickel can influence the color and the technological properties, such as hardness and mechanical abrasion resistance, of the coatings. The current yield then drops to values of 40 to 50%. The very low content of non-metallic impurities in the coatings is also surprising. At less than 0.1%, it is far below that of comparable gold alloy coatings. The coatings are also high hardness despite very ductile (HV 0th 015 230). The elongation at break measured at 10 µm thick layers on a copper foil is around 20% in the order of that of fine gold layers.

Die Erfindung soll anhand der folgenden Beispiele näher erläutert werden.

  • 1. Ein galvanisches Gold/Zinn-Bad wird durch Auflösen folgender Bestandteile hergestellt:
    • 30 g Oxalsäure und 50 g Ammoniumsulfat werden in ca. 900 ml Wasser aufgelöst. Anschließend werden 1.5 g Kaliumoxolatostannat(IV) und 13.8 g Kaliumtetracyano- aurat(III) hinzugefügt. Danach wird der pH-Wert mit Schwefelsäure auf 0.6 eingestellt und das Badvolumen auf 1 Liter aufgefüllt.
    • In dem auf 55oC erwärmten Bad wird nun auf einer Kathode aus poliertem und glanzvernickeltem Kupfer bei 2 A/dm2 in 10 Minuten eine ca. 3.5 um dicke glänzende Goldlegierungsschicht abgeschieden. Der Überzug hat etwa den Farbton 2N nach DIN 8238. Die Analyse auf Zinn ergibt einen Gehalt von 0.74 %. Nach dem Auflösen der Kupferunterlage in Salpetersäure 1 : 3 bleibt eine knickfeste Goldfolie zurück.
  • 2. Entsprechend Beispiel 1 wird ein Bad aus folgenden Bestandteilen angesetzt:
    • 50 g/l Oxalsäure
    • 2 g/1 Zinn als Oxalato zinn(IV)-Säure
    • 20.7 g/1 Kaliumtetracyanoaurat(III)
    • Der pH-Wert wird mit Schwefelsäure auf 1.0 eingestellt. In dem auf 40°C erwärmten Bad wird auf einer glanzvernickelten Kathode aus poliertem Kupferblech bei einer Stromdichte von 1 A/dm2 in 10 Minuten eine 1.5 pm dicke, glänzende Goldschicht abgeschieden, die 0.4 % Zinn enthält.
  • 3. Entsprechend Beispiel 1 wird ein Bad aus folgenden Bestandteilen angesetzt:
    • 50 g/1 Oxalsäure
    • 50 g/1 Ammoniumsulfat
    • 1 g/1 Zinn als Kaliumoxalatostannat(IV)
    • 13.8 g/1 Kaliumtetracyanoaurat(III)
    • Zusätzlich werden 0.1 g/1 Kobalt in Form von Kobaltsulfat im Bad gelöst. Der pH-Wert wird mit Schwefelsäure auf 0.8 eingestellt.
    • Bei einer Badtemperatur von 55°C und einer Stromdichte von 3 A/dm2 wird auf einer glanzvernickelten Kathode aus poliertem Messingblech in 10 Minuten eine ca. 3 µm dicke glänzende Goldschicht mit einem Farbton zwischen 2 und 3N abgeschieden. Sie enthält 0.98 % Zinn und 0.3 % Kobalt.

    Die Bäder sind in allen Fällen über längere Zeit stabil.
The invention is illustrated by the following examples.
  • 1. A galvanic gold / tin bath is made by dissolving the following components:
    • 30 g oxalic acid and 50 g ammonium sulfate are dissolved in approx. 900 ml water. Then 1.5 g of potassium oxolatostannate (IV) and 13.8 g of potassium tetracyanourate (III) are added. The pH is then adjusted to 0.6 with sulfuric acid and the bath volume is made up to 1 liter.
    • In the bath, heated to 55 o C, an approx. 3.5 µm shiny gold alloy layer is deposited on a cathode made of polished and nickel-plated copper at 2 A / dm2 in 10 minutes. The Coating has approximately the color 2N according to DIN 8238. The analysis for tin shows a content of 0.74%. After dissolving the copper base in nitric acid 1: 3, a kink-proof gold foil remains.
  • 2. According to example 1, a bath is made up of the following components:
    • 50 g / l oxalic acid
    • 2 g / 1 tin as oxalato tin (IV) acid
    • 20.7 g / 1 potassium tetracyanoaurate (III)
    • The pH is adjusted to 1.0 with sulfuric acid. In the bath, heated to 40 ° C, a 1.5 pm thick, shiny gold layer containing 0.4% tin is deposited on a bright nickel-plated cathode made of polished copper sheet at a current density of 1 A / dm 2 in 10 minutes.
  • 3. According to example 1, a bath is made up of the following components:
    • 50 g / 1 oxalic acid
    • 50 g / 1 ammonium sulfate
    • 1 g / 1 tin as potassium oxalatostannate (IV)
    • 13.8 g / 1 potassium tetracyanoaurate (III)
    • In addition, 0.1 g / 1 cobalt in the form of cobalt sulfate is dissolved in the bath. The pH is adjusted to 0.8 with sulfuric acid.
    • At a bath temperature of 55 ° C and a current density of 3 A / dm2, an approx. 3 µm thick shiny gold layer with a color between 2 and 3N is deposited on a shiny nickel-plated cathode made of polished brass sheet. It contains 0.98% tin and 0.3% cobalt.

    In all cases, the baths are stable over a long period of time.

Claims (6)

1) Bad zur galvanischen Abscheidung von Gold/Zinn-Legierungsüberzügen bei pH-Werten kleiner als 3, bestehend aus 1 bis 20 g/1 Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat(III), 0.1 bis 10 g/1 Zinn in Form eines wasserlöslichen Zinnsalzes, gegebenenfalls 0.005 bis 1 g/1 eines weiteren Legierungsmetalls in Form eines wasserlöslichen Salzes, einer Säure und einem Puffer- oder Leitsalz, dadurch gekennzeichnet, daß es das Zinn in Form eines Zinn(IV)-Oxalato-Komplexes enthält.1) Bath for the electrodeposition of gold / tin alloy coatings at pH values less than 3, consisting of 1 to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.1 to 10 g / 1 tin in Form of a water-soluble tin salt, optionally 0.005 to 1 g / 1 of a further alloy metal in the form of a water-soluble salt, an acid and a buffer or conductive salt, characterized in that it contains the tin in the form of a tin (IV) oxalato complex. 2) Bad nach Anspruch 1, dadurch gekennzeichnet, daß es den Zinn-Komplex in Form von Kaliumoxalato- stannat(IV) enthält.2) Bath according to claim 1, characterized in that it contains the tin complex in the form of potassium oxalato stannate (IV). 3) Bad nach Anspruch 1 und 2, dadurch gekennzeichnet, daß als Leit- und Puffersalz Oxalsäure oder Oxalsäure und Ammoniumsulfat verwendet werden.3) Bath according to claim 1 and 2, characterized in that oxalic acid or oxalic acid and ammonium sulfate are used as the conductive and buffer salt. 4) Bad nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß es 10 bis 50 g/1 Oxalsäure oder 10 bis 50 g/1 Oxalsäure und 10 bis 100 g/1 Ammoniumsulfat enthält.4) Bath according to claim 1 to 3, characterized in that it contains 10 to 50 g / 1 oxalic acid or 10 to 50 g / 1 oxalic acid and 10 to 100 g / 1 ammonium sulfate. 5) Bad nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß es noch 0.005 bis 1 g/1 Kobalt oder Nickel in Form eines wasserlöslichen Salzes enthält.5) Bath according to claim 1 to 4, characterized in that it also contains 0.005 to 1 g / 1 cobalt or nickel in the form of a water-soluble salt. 6) Bad nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß es einen pH-Wert von 0.5 bis 2.5 aufweist und die Einstellung des pH-Wertes mit Schwefelsäure oder Oxalsäure erfolgt.6) Bath according to claim 1 to 5, characterized in that it has a pH of 0.5 to 2.5 and the adjustment of the pH is carried out with sulfuric acid or oxalic acid.
EP86101083A 1985-03-15 1986-01-28 Bath for the galvanic deposition of gold-tin alloy coatings Expired EP0194432B1 (en)

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Application Number Priority Date Filing Date Title
DE3509367 1985-03-15
DE3509367A DE3509367C1 (en) 1985-03-15 1985-03-15 Bath and process for electrodeposition of gold / tin alloy coatings

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EP0194432A1 true EP0194432A1 (en) 1986-09-17
EP0194432B1 EP0194432B1 (en) 1988-06-15

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US (1) US4634505A (en)
EP (1) EP0194432B1 (en)
JP (1) JPH0684553B2 (en)
BR (1) BR8601029A (en)
DE (2) DE3509367C1 (en)
HK (1) HK58191A (en)
ZA (1) ZA86309B (en)

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CH680370A5 (en) * 1989-12-19 1992-08-14 H E Finishing Sa
DE4406434C1 (en) * 1994-02-28 1995-08-10 Heraeus Gmbh W C Bright gold@-tin@ alloy electroplating bath
US20060237324A1 (en) * 2003-05-21 2006-10-26 Fred Hayward Pulse plating process for deposition of gold-tin alloy
JP2007537358A (en) * 2004-05-11 2007-12-20 テクニック・インコーポレイテッド Electroplating solution for gold-tin eutectic alloy
WO2006078549A1 (en) * 2005-01-21 2006-07-27 Technic, Inc. Pulse plating process for deposition of gold-tin alloy
CN114759182B (en) * 2022-05-25 2023-04-07 昆明理工大学 Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery

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GB1442325A (en) * 1972-07-26 1976-07-14 Oxy Metal Finishing Corp Electroplating with gold and gold alloys
DE3012999C2 (en) * 1980-04-03 1984-02-16 Degussa Ag, 6000 Frankfurt Bath and process for the galvanic deposition of high-gloss and ductile gold alloy coatings

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US4013523A (en) * 1975-12-24 1977-03-22 Oxy Metal Industries Corporation Tin-gold electroplating bath and process
FR2538816A1 (en) * 1983-01-04 1984-07-06 Omi Int Corp Aq. gold alloy electroplating baths
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Also Published As

Publication number Publication date
EP0194432B1 (en) 1988-06-15
JPS61223194A (en) 1986-10-03
HK58191A (en) 1991-08-02
ZA86309B (en) 1986-08-27
DE3660313D1 (en) 1988-07-21
US4634505A (en) 1987-01-06
BR8601029A (en) 1986-11-25
DE3509367C1 (en) 1986-08-14
JPH0684553B2 (en) 1994-10-26

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