EP0198998B1 - Bath for the galvanic deposition of a coating of a gold-indium alloy - Google Patents

Bath for the galvanic deposition of a coating of a gold-indium alloy Download PDF

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Publication number
EP0198998B1
EP0198998B1 EP86100721A EP86100721A EP0198998B1 EP 0198998 B1 EP0198998 B1 EP 0198998B1 EP 86100721 A EP86100721 A EP 86100721A EP 86100721 A EP86100721 A EP 86100721A EP 0198998 B1 EP0198998 B1 EP 0198998B1
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Prior art keywords
bath
indium
acid
gold
coating
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EP86100721A
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German (de)
French (fr)
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EP0198998A1 (en
Inventor
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-indium alloy coatings at pH values less than 3, consisting of 1 to 20 g / l gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.5 to 50 g / I indium in the form of a water-soluble indium salt, an acid and a buffer or conductive salt.
  • the co-deposition of indium from galvanic gold electrolytes leads to light yellow gold layers, which are mainly used in the decorative industry for the gold plating of watch cases, bracelets, glasses or jewelry.
  • the coatings have a particularly good resistance to creep corrosion of silver sulfide compared to other gold alloy coatings.
  • the gold-indium alloy coatings which can be deposited from weakly acidic baths at pH 3.5-5 (e.g. DE-PS-1 111 897) are extremely brittle and tend to crack, which greatly impairs corrosion resistance. Indium is therefore deposited together with other metals such as nickel or cobalt, which affects the resistance to creep corrosion of silver sulfide.
  • the indium genalt in the coating is only about 1%.
  • baths contain 1 to 20 g / 1 gold in the form of tetracyanoaurate (III), a water-soluble alloy metal salt, an acid and a complexing agent at pH values between 0.4 and - 2.5.
  • This object is achieved in that it additionally contains 0.5 to 10 mg / l selenium and / or tellurium in the form of selenium or telluric acid and / or alkali selenite or tellurium.
  • the bath preferably contains the indium in the form of indium sulfate and sulfuric acid as the acid. Furthermore, it has proven to be advantageous if ammonium sulfate, sulfamic acid, aliphatic and / or aromatic sulfonic acids are used as buffers or conductive salts. Mixtures of 10 to 150 g / l ammonium sulfate with 10 to 150 g / l sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid have proven particularly useful.
  • the bath is preferably operated at pH values between 0.5 and 2.5, temperatures between 20 and 70 ° C. and current densities of 0.2 to 5 A / dm 2 , in particular at temperatures between 50 and 60 ° C. and current densities between 1 and 3 A / dm 2 .
  • the selenium or tellurium compounds contained in the bath not only cause the deposition of high-gloss coatings, but also have an unexpectedly positive effect on other bath and coating properties. This makes it possible to deposit gold-indium alloy coatings with at least 10% by weight indium, which are light yellow and lie between 0 and 1 N in the color scale according to DIN 8238.
  • silver sulfide i.e. in the case of silver or a silver layer as a base, silver sulfide does not spread on the gold layer above.
  • a suitable sulfonic acid has an advantageous effect. Compared to a pure sulfate bath, glossy coatings are obtained in a wider current density range.
  • a bath is made by dissolving the following components:
  • indium sulfate 9.1 g of indium sulfate are dissolved in about 100 ml of water and 12 ml of sulfuric acid (98%) by heating. After dilution to about 500 ml, 50 g of ammonium sulfate and hydroxiethanesulfonic acid Na salt and 3.2 mg of selenic acid are added and dissolved.
  • Example 1 a bath is made up of the following components: The pH is adjusted to 1.0 and the bath is heated to 600C. A 2.8 ⁇ m thick, shiny gold alloy layer containing 11% by weight indium is deposited on a bright nickel-plated copper sheet at a current density of 3 A / dm in 5 minutes.
  • a bath is produced from the following components: The pH is adjusted to 1.3. At a bath temperature of 50 ° C., a 2.7 ⁇ m thick shiny gold alloy layer containing 9.1% indium is deposited on a cathode made of bright nickel-plated copper sheet at a current density of 1 A / dm2 in 10 minutes.

Description

Die Erfindung betrifft ein Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen bei pH-Werten kleiner als 3, bestehend aus 1 bis 20 g/I Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat (III),0,5 bis 50 g/I Indium in Form eines wasserlöslichen Indiumsalzes, einer Säure und einem Puffer- bzw. Leitsalz.The invention relates to a bath for the electrodeposition of gold-indium alloy coatings at pH values less than 3, consisting of 1 to 20 g / l gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.5 to 50 g / I indium in the form of a water-soluble indium salt, an acid and a buffer or conductive salt.

Die Mitabscheidung von Indium aus galvanischen Goldelektrolyten führt zu hellgelben Goldschichten, die vor allem in der dekorativen Industrie bei der Vergoldung von Uhrgehäusen, Armbändern, Brillen oder Schmuck angewendet werden. Die Überzüge weisen neben einer guten allgemeinen Korrosionsbeständigkeit im Vergleich zu anderen Goldlegierungsüberzügen eine besonders gute Beständigkeit gegen die Kriechkorrosion von Silbersulfid auf. Die aus schwach sauren Bädern bei pH 3,5 - 5 abscheidbaren Gold-Indium-Legierungsüberzüge (z. B. DE-PS-1 111 897) zeichnen sich durch große Sprödigkeit aus und neigen zur Rißbildung, wodurch die Korrosionsbeständigkeit stark beeinträchtigt wird. Indium wird deshalb mit anderen Metallen wie Nickel oder Kobalt zusammen abgeschieden, was die Beständigkeit gegen die Kriechkorrosion von Silbersulfid beeinträchtigt. Der Indium-Genalt im Überzug liegt nur bei ca. 1%.The co-deposition of indium from galvanic gold electrolytes leads to light yellow gold layers, which are mainly used in the decorative industry for the gold plating of watch cases, bracelets, glasses or jewelry. In addition to good general corrosion resistance, the coatings have a particularly good resistance to creep corrosion of silver sulfide compared to other gold alloy coatings. The gold-indium alloy coatings which can be deposited from weakly acidic baths at pH 3.5-5 (e.g. DE-PS-1 111 897) are extremely brittle and tend to crack, which greatly impairs corrosion resistance. Indium is therefore deposited together with other metals such as nickel or cobalt, which affects the resistance to creep corrosion of silver sulfide. The indium genalt in the coating is only about 1%.

Nach der DE-PS-3 012 999 ist die Mitabscheidung von Indium aus einem stark sauren Goldelektrolyten auf der Basis von Kaliumtetracyanoaurat (III) möglich. Unter den angegebenen Bedingungen werden duktile, glänzenden Überzüge mit Indiumgehalten von 2-3 % erhalten. Auch hier ist aber die Beständigkeit gegen Kriechkorrosion vermindert.According to DE-PS-3 012 999, the co-deposition of indium from a strongly acidic gold electrolyte based on potassium tetracyanoaurate (III) is possible. Ductile, glossy coatings with indium contents of 2-3% are obtained under the specified conditions. However, resistance to creep corrosion is also reduced here.

Diese Bäder enthalten 1 bis 20 g/1 Gold in Form von Tetracyanoaurat (III), ein wasserlösliches Legierungsmetallsalz, eine Säure und einen Komplexbildner bei pH-Werten zwischen 0,4 und - 2.5.These baths contain 1 to 20 g / 1 gold in the form of tetracyanoaurate (III), a water-soluble alloy metal salt, an acid and a complexing agent at pH values between 0.4 and - 2.5.

Es war daher Aufgabe der vorliegenden Erfindung, ein Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen bei pH-Werten kleiner als 3 zu entwickeln, bestehend aus 1 bis 20 g/I Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat (III), 0,5 bis 50 g/I Indium in Form eines wasserlöslichen Indiumsalzes, einer Säure und einem Puffer- bzw. Leitsalz, das hellgelbe, glänzende und duktile Überzüge liefert und gleichzeitig beständig gegen Kriechkorrosion gegenüber Silbersulfid ist.It was therefore an object of the present invention to develop a bath for the electrodeposition of gold-indium alloy coatings at pH values less than 3, consisting of 1 to 20 g / l of gold in the form of alkali and / or ammonium tetracyanoaurate (III) , 0.5 to 50 g / l indium in the form of a water-soluble indium salt, an acid and a buffer or conductive salt, which provides light yellow, shiny and ductile coatings and at the same time is resistant to creep corrosion against silver sulfide.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß es zusätzlich 0,5 bis 10 mg/I Selen und/oder Tellur in Form von seleniger bzw. telluriger Säure und/oder Alkaliselenit bzw. -tellurit enthält.This object is achieved in that it additionally contains 0.5 to 10 mg / l selenium and / or tellurium in the form of selenium or telluric acid and / or alkali selenite or tellurium.

Vorzugsweise enthält das Bad das Indium in Form von Indiumsulfat und als Säure Schwefelsäure. Weiterhin hat es sich als vorteilhaft erwiesen, wenn als Puffer bzw. Leitsalze Ammoniumsulfat, Sulfaminsäure, aliphatische und/oder aromatische Sulfonsäuren eingesetzt werden. Besonders bewährt haben sich Gemische aus 10 bis 150 g/I Ammoniumsulfat mit 10 bis 150 g/I Sulfaminsäure, Toluolsulfonsäure und/oder 2-Hydroxiethansulfonsäure.The bath preferably contains the indium in the form of indium sulfate and sulfuric acid as the acid. Furthermore, it has proven to be advantageous if ammonium sulfate, sulfamic acid, aliphatic and / or aromatic sulfonic acids are used as buffers or conductive salts. Mixtures of 10 to 150 g / l ammonium sulfate with 10 to 150 g / l sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid have proven particularly useful.

Vorzugsweise betreibt man das Bad bei pH-Werten zwischen 0,5 und 2,5, Temperaturen zwischen 20 und 70° C und Stromdichten von 0,2 bis 5 A/dm2, insbesondere bei Temperaturen zwischen 50 und 60° C und Stromdichten zwischen 1 und 3 A/dm2.The bath is preferably operated at pH values between 0.5 and 2.5, temperatures between 20 and 70 ° C. and current densities of 0.2 to 5 A / dm 2 , in particular at temperatures between 50 and 60 ° C. and current densities between 1 and 3 A / dm 2 .

Die im Bad enthaltenen Selen- oder Tellurverbindungen bewirken nicht nur die Abscheidung hochglänzender Überzüge, sondern wirken sich auch in nicht zu erwartendem Maße positiv auf andere Bad- und Überzugseigenschaften aus. So wird es möglich, Gold- Indium-Legierungsüberzuge mit mindestens 10 Gew. -% Indium abzuscheiden, die hellgelb sind und in der Farbskala nach DIN 8238 zwischen 0 und 1 N liegen.The selenium or tellurium compounds contained in the bath not only cause the deposition of high-gloss coatings, but also have an unexpectedly positive effect on other bath and coating properties. This makes it possible to deposit gold-indium alloy coatings with at least 10% by weight indium, which are light yellow and lie between 0 and 1 N in the color scale according to DIN 8238.

Überraschend war ferner, daß die Stromausbeute der Bäder unter Berücksichtigung des Indiumanteils nahezu 100 % beträgt, während ohne Selen- oder Tellur-Zusatz-nur Stromausbeuten zwischen 10-20 %, je nach Badtemperatur, Stromdichte und Goldgehalt erhalten werden. Die Überzüge sind trotz des hohen Indiumgehaltes sent duktil und können als s Folien isoliert werden;Was also surprising that the current efficiency of the baths under consideration of the Indiuman t is Eils almost 100%, while selenium tellurium additional only be obtained current efficiencies between 10-20%, depending on the bath temperature, current density and gold content or no. Despite the high indium content, the coatings are ductile and can be isolated as foils;

Außerdem sind sie gegen die Kriechkorrosion von Silbersulfid beständig, d.h. bei Silber oder einer Silberschicht als Unterlage breitet sich auf der darüberliegenden Gold-lnatum-Schicht Silbersulfid nicht aus.They are also resistant to creep corrosion from silver sulfide, i.e. in the case of silver or a silver layer as a base, silver sulfide does not spread on the gold layer above.

Zusätzlich wirkt sich die Verwendung einer geeigneten Sulfonsäure vorteilhaft aus. Im Vergleich zu einem reinen Sulfatbad werden glänzende Überzüge in einem breiteren Stromdichtebereich erhalten.In addition, the use of a suitable sulfonic acid has an advantageous effect. Compared to a pure sulfate bath, glossy coatings are obtained in a wider current density range.

Die Erfindung soll anhand der folgenden Beispiele näher erläutert werden:The invention is illustrated by the following examples:

Beispiel 1example 1

Ein Bad wird durch Auflösen folgender Bestandteile hergestellt:A bath is made by dissolving the following components:

9,1 g Indiumsulfat werden in ca. 100 ml Wasser und 12 ml Schwefelsäure (98 %-ig) durch Erhitzen gelöst. Nach Verdünnung auf ca. 500 ml werden je 50 g Ammoniumsulfat und Hydroxiethansulfonsäure-Na-Salz sowie 3,2 mg selenige Säure zugegeben und gelöst.9.1 g of indium sulfate are dissolved in about 100 ml of water and 12 ml of sulfuric acid (98%) by heating. After dilution to about 500 ml, 50 g of ammonium sulfate and hydroxiethanesulfonic acid Na salt and 3.2 mg of selenic acid are added and dissolved.

Nach Zusatz von 13,8 g Kaliumtetracyanoaurat (111), wird auf 1 Liter verdünnt und der pH-Wert mit Schwefelsäure oder Ammoniaklösung auf 1,1 eingestellt. Auf einer Kathode aus poliertem Kupferblech wird nun in dem auf 55° C erwärmten Bad bei einer Stromdichte von 2 A/dm2 in 14 min eine ca. 5 µm dicke glänzende, blaßgelbe Goldlegierungsschicht abgeschieden. Der Überzug enthält 9,8 % In. Die Kupferunterlage wird mit 3 : 1 verdünnter Salpetersäure aufgelöst und es bleibt eine duktile Goldfolie zurück, die auch beim Knicken nicht bricht.After adding 13.8 g of potassium tetracyanoaurate (111), dilute to 1 liter and adjust the pH to 1.1 with sulfuric acid or ammonia solution. On a cathode made of polished copper sheet, an approx. 5 µm thick shiny, pale yellow is now in the bath heated to 55 ° C at a current density of 2 A / dm 2 in 14 minutes Gold alloy layer deposited. The coating contains 9.8% In. The copper base is dissolved with 3: 1 diluted nitric acid and a ductile gold foil remains, which does not break even when it is bent.

Beispiel 2Example 2

Entsprechend Beispiel 1 wird ein Bad aus folgenden Bestandteilen angesetzt:

Figure imgb0001
Der pH-Wert wird auf 1,0 eingestellt und das Bad auf 600C erwärmt. Auf einem glanzvernickelten Kupferblech wird bei einer Stromdichte von 3 A/dm in 5 min eine 2,8 µm dicke glänzende Goldlegierungsschicht abgeschieden, die 11 Gew.-% Indium enthält.According to Example 1, a bath is made up of the following components:
Figure imgb0001
 The pH is adjusted to 1.0 and the bath is heated to 600C. A 2.8 µm thick, shiny gold alloy layer containing 11% by weight indium is deposited on a bright nickel-plated copper sheet at a current density of 3 A / dm in 5 minutes.

Beispiel 3Example 3

Entsprechend der Ansatzweise im Beispiel 1 wird ein Bad aus folgenden Bestandteilen hergestellt:

Figure imgb0002
Der pH-Wert wird auf 1,3 eingestellt. Bei einer Badtemperatur von 50° C wird auf einer Kathode aus glanzvernickeltem Kupferblech bei einer Stromdichte von 1 A/dm2 in 10 min eine 2,7 um dicke glänzende Goldlegierungsschicht abgeschieden, die 9,1 % Indium enthält.In accordance with the approach in Example 1, a bath is produced from the following components:
Figure imgb0002
 The pH is adjusted to 1.3. At a bath temperature of 50 ° C., a 2.7 μm thick shiny gold alloy layer containing 9.1% indium is deposited on a cathode made of bright nickel-plated copper sheet at a current density of 1 A / dm2 in 10 minutes.

Claims (5)

1. A bath for the electrodeposition of gold-indium alloy coatings at pH values below 3 consisting of 1 to 20 g/I gold in the form of alkali and/or ammonium tetracyanoaurate (III), 0.5 to 50 g/I indium in the form of a water-soluble indium salt, an acid and a buffer or conducting salt, characterized in that it also contains 0.5 to 10 g/I selenium and/or tellurium in the form of selenous or tellurous acid and/or alkali selenite or tellurite.
2. A bath as claimed in claim 1, characterized in that it contains the indium in the form of indium sulfate and sulfuric acid as the acid.
3. A bath as claimed in claim 1 or 2, characterized in that it contains ammonium sulfate, sulfamic acid, aliphatic and/or aromatic sulfonic acids as buffer or conducting salts.
4. A bath as claimed in claims 1 to 3, characterized in that it contains 10 to 150 g/I ammonium sulfate and 10 to 150 g/I sulfamic acid, toluenesulfonic acid and/or 2-hydroxyethanesulfonic acid.
5. A bath as claimed in claims 1 to 4, characterized in that it has a pH value of 0.5 to 2.5.
EP86100721A 1985-02-16 1986-01-21 Bath for the galvanic deposition of a coating of a gold-indium alloy Expired EP0198998B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3505473 1985-02-06
DE3505473A DE3505473C1 (en) 1985-02-16 1985-02-16 Electroplating bath for gold-indium alloy coatings

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EP0198998A1 EP0198998A1 (en) 1986-10-29
EP0198998B1 true EP0198998B1 (en) 1988-06-29

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US (1) US4617096A (en)
EP (1) EP0198998B1 (en)
JP (1) JPS61190089A (en)
BR (1) BR8600414A (en)
DE (2) DE3505473C1 (en)
HK (1) HK58091A (en)
ZA (1) ZA86305B (en)

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Publication number Priority date Publication date Assignee Title
US4916235A (en) * 1986-11-26 1990-04-10 University Of Dayton Resin systems derived from benzocyclobutene-maleimide compounds
GB8903818D0 (en) * 1989-02-20 1989-04-05 Engelhard Corp Electrolytic deposition of gold-containing alloys
CH680370A5 (en) * 1989-12-19 1992-08-14 H E Finishing Sa
US6805786B2 (en) * 2002-09-24 2004-10-19 Northrop Grumman Corporation Precious alloyed metal solder plating process
SG127854A1 (en) 2005-06-02 2006-12-29 Rohm & Haas Elect Mat Improved gold electrolytes
US20090104463A1 (en) 2006-06-02 2009-04-23 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
JP5497261B2 (en) 2006-12-15 2014-05-21 ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． Indium composition
US8585885B2 (en) * 2007-08-28 2013-11-19 Rohm And Haas Electronic Materials Llc Electrochemically deposited indium composites
EP2123799B1 (en) * 2008-04-22 2015-04-22 Rohm and Haas Electronic Materials LLC Method of replenishing indium ions in indium electroplating compositions
US8840770B2 (en) * 2010-09-09 2014-09-23 International Business Machines Corporation Method and chemistry for selenium electrodeposition
US9145616B2 (en) * 2012-02-29 2015-09-29 Rohm and Haas Elcetronic Materials LLC Method of preventing silver tarnishing
EP3550057A3 (en) * 2018-04-03 2019-11-13 Supro GmbH Multilayer surface coating

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
DE1111897B (en) * 1957-08-13 1961-07-27 Sel Rex Corp Bath for the galvanic deposition of shiny gold alloy coatings
CH418085A (en) * 1964-08-19 1966-07-31 Pilot Pen Co Ltd Electrolyte for the galvanic deposition of gold alloys
US3990954A (en) * 1973-12-17 1976-11-09 Oxy Metal Industries Corporation Sulfite gold plating bath and process
JPS52108342A (en) * 1976-03-09 1977-09-10 Citizen Watch Co Ltd Gold alloy electroplating method
JPS53149132A (en) * 1977-06-01 1978-12-26 Citizen Watch Co Ltd Golddpalladiummcopper alloy plating liquid
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
DE3347594A1 (en) * 1983-01-04 1984-07-12 Omi International Corp., Warren, Mich. Bath for electrodepositing a wear-resistant gold alloy and process for depositing a wear-resistant gold alloy using said bath
DE3309397A1 (en) * 1983-03-16 1984-09-20 Degussa Ag, 6000 Frankfurt ELECTROLYTIC BATH FOR DEPOSITING LOW-CARAE, GLOSSY GOLD-SILVER ALLOY COATINGS

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DE3505473C1 (en) 1986-06-05
EP0198998A1 (en) 1986-10-29
ZA86305B (en) 1986-08-27
JPS61190089A (en) 1986-08-23
HK58091A (en) 1991-08-02
BR8600414A (en) 1986-10-14
US4617096A (en) 1986-10-14
DE3660353D1 (en) 1988-08-04

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