EP0198998A1 - 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

Info

Publication number
EP0198998A1
EP0198998A1 EP86100721A EP86100721A EP0198998A1 EP 0198998 A1 EP0198998 A1 EP 0198998A1 EP 86100721 A EP86100721 A EP 86100721A EP 86100721 A EP86100721 A EP 86100721A EP 0198998 A1 EP0198998 A1 EP 0198998A1
Authority
EP
European Patent Office
Prior art keywords
indium
gold
acid
bath
salt
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.)
Granted
Application number
EP86100721A
Other languages
German (de)
French (fr)
Other versions
EP0198998B1 (en
Inventor
Werner Kuhn
Wolfgang Zilske
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP0198998A1 publication Critical patent/EP0198998A1/en
Application granted granted Critical
Publication of EP0198998B1 publication Critical patent/EP0198998B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—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 / 1 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 e.g. DE-PS 11 11 897
  • the gold-indium alloy coatings that can be deposited from weakly acid baths at pB 3.5 - 5 are characterized by great brittleness and tend to crack, which greatly impairs the 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 content in the coating is only about 1%.
  • the co-deposition of indium from a strongly acidic gold electrolyte is based on Potassium tetracyanoaurate (III) possible. Ductile, but no glossy coatings with indium contents of 2-3% are obtained under the specified conditions. The addition of a nickel or cobalt salt to the electrolyte makes it possible to deposit shiny coatings, which, however, appear relatively strongly gray. A light yellow shade is not achieved. The resistance to creep corrosion is also reduced here.
  • 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 / 1 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 buffer or conductive salts. Mixtures of 10 to 150 g / 1 ammonium sulfate with 10 to 150 g / 1 sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid have proven particularly useful.
  • the bath is preferably operated at pH values between 0.4 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 1N in the color scale according to DIN 8238.
  • the coatings are very ductile and can be isolated as stable foils.
  • silver sulfide i.e. with silver or a silver layer as a base, silver sulfide does not spread on the overlying gold-indium layer.
  • 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 up of the following components:
  • the pH is adjusted to 1.0 and the bath is heated to 60 ° C.
  • 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 2 in 5 minutes.
  • the pH is adjusted to 1.3.
  • 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 / dm 2 in 10 minutes.

Landscapes

  • 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

Hellgelbe, glänzende und duktile Gold-Indium-Legierungsüberzüge, die eine gute Beständigkeit gegenüber Kriechkorrosion durch Silbersulfid aufweisen, erhält man aus galvanischen Bädern, die neben 1 bis 20 g/l Gold in Form von Alkalitetracyanoaurat (III), 0,5-50 g/l Indium in Form eines wasserlöslichen Indiumsalzes, einer Säure und einem Puffer- bzw. Leitsalz noch 0,5 bis 10 mg/1 Selen und/oder Tellur enthalten.Light yellow, shiny and ductile gold-indium alloy coatings, which have good resistance to creep corrosion due to silver sulfide, are obtained from electroplating baths, which in addition to 1 to 20 g / l gold in the form of alkali tetracyanoaurate (III), 0.5-50 g / l Indium in the form of a water-soluble indium salt, an acid and a buffer or conductive salt also contain 0.5 to 10 mg / 1 selenium and / or tellurium.

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/l Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat (III),0,5 bis 50 g/1 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 / 1 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 Goldlegierungs- überzügen eine besonders gute Beständigkeit gegen die Kriechkorrosion von Silbersulfid auf. Die aus schwach sauren Bädern bei pB 3,5 - 5 abscheidbaren Gold-Indium-Legierungs- überzüge (z.B. DE-PS 11 11 897) 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-Gehalt 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 (e.g. DE-PS 11 11 897) that can be deposited from weakly acid baths at pB 3.5 - 5 are characterized by great brittleness and tend to crack, which greatly impairs the 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 content in the coating is only about 1%.

Nach der DE-PS 30 12 999 ist die Mitabscheidung von Indium aus einem stark sauren Goldelektrolyten auf der Basis von Kaliumtetracyanoaurat (III) möglich. Unter den angegebenen Bedingungen werden zwar duktile, aber keine glänzenden Überzüge mit Indiumgehalten von 2 - 3 % erhalten. Durch den Zusatz eines Nickel- oder Kobaltsalzes zum Elektrolyten lassen sich zwar glänzende Überzüge abscheiden, die jedoch relativ stark grau erscheinen. Ein hellgelber Farbton wird nicht erzielt. Außerdem wird auch hier die Beständigkeit gegen Kriechkorrosion vermindert.According to DE-PS 30 12 999, the co-deposition of indium from a strongly acidic gold electrolyte is based on Potassium tetracyanoaurate (III) possible. Ductile, but no glossy coatings with indium contents of 2-3% are obtained under the specified conditions. The addition of a nickel or cobalt salt to the electrolyte makes it possible to deposit shiny coatings, which, however, appear relatively strongly gray. A light yellow shade is not achieved. The 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/1 Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat (III), 0,5 bis 50 g/1 Indium in Form eines wasserlöslichen Indiumsalzes, einer Säure und einem Puffer- bzw. Leitsalz, das hellgelbe, glänzende und duktile Überzüge liefert, ohne daß die Kriechkorrosionsbeständigkeit gegenüber Silbersulfid beeinträchtigt wird.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 / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III) , 0.5 to 50 g / 1 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 without the creep corrosion resistance to silver sulfide being impaired.

Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß es zusätzlich 0,5 bis 10 mg/1 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 / 1 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/1 Ammoniumsulfat mit 10 bis 150 g/1 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 buffer or conductive salts. Mixtures of 10 to 150 g / 1 ammonium sulfate with 10 to 150 g / 1 sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid have proven particularly useful.

Vorzugsweise betreibt man das Bad bei pH-Werten zwischen 0,4 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 0.4 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 1N 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 1N 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.It was also surprising that the current yield of the baths, taking into account the indium content, is almost 100%, while without selenium or tellurium addition only current yields between 10-20% are obtained, depending on the bath temperature, current density and gold content.

Die Überzüge sind trotz des hohen Indiumgehaltes sehr duktil und können als stabile Folien isoliert werden.Despite the high indium content, the coatings are very ductile and can be isolated as stable 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-Indium-Schicht Silbersulfid nicht aus.They are also resistant to creep corrosion from silver sulfide, i.e. with silver or a silver layer as a base, silver sulfide does not spread on the overlying gold-indium layer.

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:

  • 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.
A bath is made by dissolving the following components:
  • 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 each of ammonium sulfate and hydroxyethanesulfonic acid Na salt and 3.2 mg of selenic acid are added and dissolved.

Nach Zusatz von 13,8 g Kaliumtetracyanoaurat (III), 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 (III), dilute to 1 liter and adjust the pH to 1.1 with sulfuric acid or ammonia solution. An approx. 5 µm thick, pale yellow gold alloy layer is then deposited on a cathode made of polished copper sheet in the bath heated to 55 ° C. at a current density of 2 A / dm 2 in 14 min. The coating contains 9.8% In. The copper base is dissolved with 3: 1 diluted nitric acid and a ductile gold foil remains that does not break even when it is bent.

Beispiel 2Example 2

Entsprechend Beispiel 1 wird ein Bad aus folgenden Bestandteilen angesetzt:

Figure imgb0001
According to Example 1, a bath is made up of the following components:
Figure imgb0001

Der pH-Wert wird auf 1,0 eingestellt und das Bad auf 60° C erwärmt. Auf einem glanzvernickelten Kupferblech wird bei einer Stromdichte von 3 A/dm2 in 5 min eine 2,8 µm dicke glänzende Goldlegierungsschicht abgeschieden, die 11 Gew.% Indium enthält.The pH is adjusted to 1.0 and the bath is heated to 60 ° C. 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 2 in 5 minutes.

Beispiel 3Example 3

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

Figure imgb0002
In accordance with the approach in Example 1, a bath is produced from the following components:
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.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 / dm 2 in 10 minutes.

Claims (5)

1. Bad zur galvanischen Abscheidung von Gold-Indium-Legierungsüberzügen bei pH-Werten kleiner als 3, bestehend aus i bis 20 g/1 Gold in Form von Alkali- und/oder Ammoniumtetracyanoaurat (III), 0,5 bis 50 g/1 Indium in Form eines wasserlöslichen Indiumsalzes, einer Säure und einem Puffer- bzw. Leitsalz,
dadurch gekennzeichnet,
daß es zusätzlich 0,5 bis 10 mg/l Selen und/oder Tellur in Form von seleniger bzw. telluriger Säure und/oder Alkaliselenit bzw. -tellurit enthält.1. Bath for the electrodeposition of gold-indium alloy coatings at pH values less than 3, consisting of i to 20 g / 1 gold in the form of alkali and / or ammonium tetracyanoaurate (III), 0.5 to 50 g / 1 Indium in the form of a water-soluble indium salt, an acid and a buffer or conductive salt,
characterized,
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 tellurite. 2. Bad nach Anspruch 1,
dadurch gekennzeichnet,
daß es das Indium in Form von Indiumsulfat und als Säure Schwefelsäure enthält.2. Bath according to claim 1,
characterized,
that it contains the indium in the form of indium sulfate and sulfuric acid as an acid. 3. Bad nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
daß als Puffer- bzw. Leitsalze Ammoniumsulfat, Sulfaminsäure, aliphatische und/oder aromatische Sulfonsäuren eingesetzt werden.3. Bath according to claim 1 or 2,
characterized,
that ammonium sulfate, sulfamic acid, aliphatic and / or aromatic sulfonic acids are used as buffer or conductive salts. 4. Bad nach Anspruch 1 bis 3,
dadurch gekennzeichnet,
daß es 10 bis 150 g/1 Ammoniumsulfat und 10 bis 150 g/1 Sulfaminsäure, Toluolsulfonsäure und/oder 2-Hydroxiethansulfonsäure enthält.4. Bath according to claim 1 to 3,
characterized,
that it contains 10 to 150 g / 1 ammonium sulfate and 10 to 150 g / 1 sulfamic acid, toluenesulfonic acid and / or 2-hydroxyethanesulfonic acid. 5. Bad nach Anspruch 1 bis 4,
dadurch gekennzeichnet,
daß es einen pH-Wert von 0,5 bis 2,5 aufweist.5. Bath according to claim 1 to 4,
characterized,
that it has a pH 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
DE3505473A DE3505473C1 (en) 1985-02-16 1985-02-16 Electroplating bath for gold-indium alloy coatings
DE3505473 1985-02-16

Publications (2)

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

Family

ID=6262777

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86100721A Expired EP0198998B1 (en) 1985-02-16 1986-01-21 Bath for the galvanic deposition of a coating of a gold-indium alloy

Country Status (7)

Country Link
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)

Cited By (3)

* Cited by examiner, † Cited by third party
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
US7465385B2 (en) 2005-06-02 2008-12-16 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
US8142637B2 (en) 2005-06-02 2012-03-27 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH418085A (en) * 1964-08-19 1966-07-31 Pilot Pen Co Ltd Electrolyte for the galvanic deposition of gold alloys
EP0037535A2 (en) * 1980-04-03 1981-10-14 Degussa Aktiengesellschaft Plating bath for depositing coatings of gold and gold alloys
FR2538816A1 (en) * 1983-01-04 1984-07-06 Omi Int Corp Aq. gold alloy electroplating baths
EP0119424A1 (en) * 1983-03-16 1984-09-26 Degussa Aktiengesellschaft Process for the deposition of low carat brilliant gold-silver alloy coatings

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH418085A (en) * 1964-08-19 1966-07-31 Pilot Pen Co Ltd Electrolyte for the galvanic deposition of gold alloys
EP0037535A2 (en) * 1980-04-03 1981-10-14 Degussa Aktiengesellschaft Plating bath for depositing coatings of gold and gold alloys
FR2538816A1 (en) * 1983-01-04 1984-07-06 Omi Int Corp Aq. gold alloy electroplating baths
EP0119424A1 (en) * 1983-03-16 1984-09-26 Degussa Aktiengesellschaft Process for the deposition of low carat brilliant gold-silver alloy coatings

Cited By (3)

* Cited by examiner, † Cited by third party
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
US7465385B2 (en) 2005-06-02 2008-12-16 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes
US8142637B2 (en) 2005-06-02 2012-03-27 Rohm And Haas Electronic Materials Llc Gold alloy electrolytes

Also Published As

Publication number Publication date
JPS61190089A (en) 1986-08-23
BR8600414A (en) 1986-10-14
ZA86305B (en) 1986-08-27
US4617096A (en) 1986-10-14
EP0198998B1 (en) 1988-06-29
DE3505473C1 (en) 1986-06-05
HK58091A (en) 1991-08-02
DE3660353D1 (en) 1988-08-04

Similar Documents

Publication Publication Date Title
CH647269A5 (en) Plating FOR DEPOSIT OF PALLADIUM / NICKEL ALLOY.
DE1496843A1 (en) Electrodeposition process
EP0198998B1 (en) Bath for the galvanic deposition of a coating of a gold-indium alloy
EP0195995B1 (en) Process for the electrodeposition of composite tin-graphite or tin-lead graphite layers, and baths used therefor
DE1496917A1 (en) Electrolytic baths and processes for the production of galvanic coatings
DE3012999C2 (en) Bath and process for the galvanic deposition of high-gloss and ductile gold alloy coatings
DE3139815A1 (en) "METHOD FOR MAINTAINING A GOLD COATING WITH IMPROVED CORROSION RESISTANCE ON A SUBSTRATE"
DE2649144A1 (en) METHOD AND BATH FOR ELECTROLYTIC SILVER DEPOSITION
EP0194432B1 (en) Bath for the galvanic deposition of gold-tin alloy coatings
DE2930035A1 (en) AQUEOUS GALVANIC BATH
DE3244092A1 (en) AQUEOUS BATH FOR GALVANIC DEPOSITION OF GOLD AND METHOD FOR GALVANIC DEPOSIT OF HARD GOLD USING ITS USE
EP0018752A1 (en) Electrodeposit of a white gold alloy, its preparation and electroplating bath
DE718252C (en) Process for the production of hydrogen sulfide-resistant galvanic silver coatings
DE2002836A1 (en) Process for the continuous production of wire-shaped material which is coated with a single layer of nickel or a double layer of nickel and gold
DE3108467C2 (en) Use of an acetyleneamine and / or an amino alcohol in a bath for the electrodeposition of a palladium / nickel alloy
EP0126921B1 (en) Bath for the galvanic deposition of gold alloys
CH649318A5 (en) Bad for galvanic separation of palladium / nickel alloy.
DE2511119A1 (en) ADDITIVES FOR ELECTROPLATING
DE2439656C2 (en) Aqueous acid bath for the electrodeposition of a tin-nickel alloy
DE4040526C3 (en) Bath for the galvanic deposition of gold alloys
DE2948999C2 (en) Aqueous, acidic bath for the electrodeposition of gold and method for the electrodeposition of hard gold with its use
DE2333096B2 (en) Electroplated multilayer metal coating and process for its manufacture
DE815882C (en) Process for the production of deposits on metal surfaces by electrolysis
DE3416993A1 (en) ELECTROLYTE CONTAINING AQUEOUS, ACID, NICKEL AND COBALT ION FOR THE GALVANIC DEPOSITION OF HARD, TEMPERATURE-RESISTANT, WHITE GLOSSY ALLOY
DE1086508B (en) Acid galvanic copper bath

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19860121

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB IT LI

17Q First examination report despatched

Effective date: 19870827

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REF Corresponds to:

Ref document number: 3660353

Country of ref document: DE

Date of ref document: 19880804

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19931221

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19940111

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19950121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19950131

BERE Be: lapsed

Owner name: DEGUSSA A.G.

Effective date: 19950131

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19950121

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19961216

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19961217

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970107

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980131

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050121