EP0037534A2 - Plating bath and its use for depositing very lustrous coatings of white gold - Google Patents

Plating bath and its use for depositing very lustrous coatings of white gold Download PDF

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Publication number
EP0037534A2
EP0037534A2 EP81102315A EP81102315A EP0037534A2 EP 0037534 A2 EP0037534 A2 EP 0037534A2 EP 81102315 A EP81102315 A EP 81102315A EP 81102315 A EP81102315 A EP 81102315A EP 0037534 A2 EP0037534 A2 EP 0037534A2
Authority
EP
European Patent Office
Prior art keywords
gold
sulfite
coatings
white gold
cadmium
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
EP81102315A
Other languages
German (de)
French (fr)
Other versions
EP0037534A3 (en
EP0037534B1 (en
Inventor
Eberhard Ing.Grad. Bitzer
Wilhelm Aichinger
Gerhard Ing.Grad. Steinhilber
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
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Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP0037534A2 publication Critical patent/EP0037534A2/en
Publication of EP0037534A3 publication Critical patent/EP0037534A3/en
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Publication of EP0037534B1 publication Critical patent/EP0037534B1/en
Expired legal-status Critical Current

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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 galvanic bath for the deposition of high-gloss white gold coatings with 2 - 10 g / 1 gold in the form of a sulfite complex, 2 - 40 g / 1 alkali sulfite, 2 - 40 g / 1 of a complexing agent, 1 - 10 g / 1 nickel and 1 - 20 g / 1 cadmium each in the form of water-soluble salts.
  • white gold electroplating is often required. It's white Gold baths known that contain the gold as a sulfite complex and also alkali sulfite and ethylenediaminetetraacetic acid. Copper, nickel and / or cadmium are usually used as alloy metals. B. phosphonic acid (DE-OS 23 34 813). These baths can be used to deposit thick, ductile white gold coatings with a gold content of around 75%.
  • the bath contains 0.5-10 g / 1 orotic acid and / or its derivatives and / or salts.
  • Uracil-4-carboxylic acid is referred to as orotic acid.
  • the baths according to the invention are preferably operated at a pH between 9 and 11, a temperature between 50 and 70 ° C. and a current density between 0.5 and 2 A / dm 2 .

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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

Bekannte Weißgoldbäder auf der Basis 2 - 10 g/l Gold als Sulfitokomplex, 2 - 40 g/l Alkalisulfit, 2 - 40 g/l eines Komplexbildners, 1 - 10 g/l Nickel und 1 - 20 g/l Kadmium jeweils in Form wasserlöslicher Salze sind empfindlich gegen Verunreinigungen durch Schwermetalle und Cyanide. Diese Empfindlichkeit läßt sich beheben durch Zusatz von 0,5 - 10 g/l Orotsäure und/oder deren Derivate und/oder deren Salze.Known white gold baths based on 2 - 10 g / l gold as a sulfite complex, 2 - 40 g / l alkali sulfite, 2 - 40 g / l of a complexing agent, 1 - 10 g / l nickel and 1 - 20 g / l cadmium each in the form Water-soluble salts are sensitive to contamination by heavy metals and cyanides. This sensitivity can be eliminated by adding 0.5-10 g / l orotic acid and / or its derivatives and / or its salts.

Description

Die Erfindung betrifft ein galvanisches Bad zur Abscheidung hochglänzender Weißgoldüberzüge mit 2 - 10 g/1 Gold in Form eines Sulfitokomplexes, 2 - 40 g/1 Alkalisulfit, 2 - 40 g/1 eines Komplexbildners, 1 - 10 g/1 Nickel und 1 - 20 g/1 Kadmium jeweils in Form wasserlöslicher Salze.The invention relates to a galvanic bath for the deposition of high-gloss white gold coatings with 2 - 10 g / 1 gold in the form of a sulfite complex, 2 - 40 g / 1 alkali sulfite, 2 - 40 g / 1 of a complexing agent, 1 - 10 g / 1 nickel and 1 - 20 g / 1 cadmium each in the form of water-soluble salts.

Zur korrosionsfesten Beschichtung von Gebrauchsgegenständen aus Metall, wie z. B. Brillengestelle, Uhrengehäuse, Armbänder oder Feuerzeuge, werden oft galvanische Überzüge aus Weißgold benötigt. Es sind Weißgoldbäder bekannt, die das Gold als Sulfitokomplex enthalten und außerdem Alkalisulfit und Äthylendiamintetraessigsäure. Als Legierungsmetalle werden gewöhnlich Kupfer, Nickel und/oder Kadmium verwendet, als Glanzmittel z. B. Phosphonsäure (DE-OS 23 34 813). Mit diesen Bädern lassen sich dicke, duktile Weißgoldüberzüge mit einem Goldgehalt von rund 75 % abscheiden. Nachteilig ist jedoch, daß beim Betrieb solcher Bäder geringe Verunreinigungen von Schwermetallen,wie Blei oder Eisen und Cyanidionen bzw. komplexe Cyanide,in manchen Fällen zu Störungen führen können, die sich ungünstig auf den Glanz der Überzüge auswirken.For the corrosion-resistant coating of metal utensils, such as. B. eyeglass frames, watch cases, bracelets or lighters, white gold electroplating is often required. It's white Gold baths known that contain the gold as a sulfite complex and also alkali sulfite and ethylenediaminetetraacetic acid. Copper, nickel and / or cadmium are usually used as alloy metals. B. phosphonic acid (DE-OS 23 34 813). These baths can be used to deposit thick, ductile white gold coatings with a gold content of around 75%. However, it is disadvantageous that, in the operation of such baths, minor contamination of heavy metals, such as lead or iron and cyanide ions or complex cyanides, can in some cases lead to faults which have an unfavorable effect on the gloss of the coatings.

Es war daher Aufgabe der vorliegenden Erfindung, ein galvanisches Bad zur Abscheidung hochglänzender Weißgoldüberzüge zu schaffen mit 2 - 10 g Gold in Form eines Sulfitkomplexes, 2 - 40 g/1 Alkalisulfit, 2 - 40 g/1 eines Komplexbildners, 1 - 10 g/1 Nickel und 1 - 20 g/1 Kadmium jeweils in Form wasserlöslicher Salze, das nicht empfindlich gegen Schwermetalle und Cyanidverunreinigungen ist.It was therefore the object of the present invention to provide a galvanic bath for the deposition of high-gloss white gold coatings with 2-10 g gold in the form of a sulfite complex, 2-40 g / 1 alkali sulfite, 2-40 g / 1 of a complexing agent, 1-10 g / 1 nickel and 1 - 20 g / 1 cadmium in the form of water-soluble salts, which are not sensitive to heavy metals and cyanide impurities.

Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, daß das Bad 0,5 - 10 g/1 Orotsäure und/oder deren Derivate und/oder Salze enthält. Als Orotsäure bezeichnet man die Uracil-4-carbonsäure.This object was achieved in that the bath contains 0.5-10 g / 1 orotic acid and / or its derivatives and / or salts. Uracil-4-carboxylic acid is referred to as orotic acid.

Die erfindungsgemäßen Bäder werden vorzugsweise bei einem pH-Wert zwischen 9 und 11, einer Temperatur zwischen 50 und 700 C und einer Stromdichte zwischen 0,5 und 2 A/dm2 betrieben.The baths according to the invention are preferably operated at a pH between 9 and 11, a temperature between 50 and 70 ° C. and a current density between 0.5 and 2 A / dm 2 .

Das folgende Beispiel soll die Vorteile der erfindungsgemäßen Bäder näher erläutern. In 1 Liter Wasser werden 5 g Gold in Form seines Sulfitokomplexes, 10 g Dinatriumsulfit, 15 g Tetranatriumäthylendiamintetraacetat, 4 g Nickelsulfat und 12 g Kadmiumsulfat gelöst. Aus diesem Bad erthält man bei einem pH-Wert von etwa 10 bei 700 C und einer Stromdichte von 1 A/dm 2 weiße, seidenmatte Überzüge, die etwa 80 % Gold und 20 % Kadmium neben Spuren von Nickel enthalten. Gibt man zu diesem Elektrolyten 2 g 1-Hydroxyäthyliden-1,1-diphosphonsäure zu, so erhält man zwar hochglänzende Überzüge, der Glanz verschwindet jedoch wieder, wenn man geringe Mengen Eisen dem Bad als Verunreinigung zusetzt.The following example is intended to explain the advantages of the baths according to the invention in more detail. In 1 liter of water are 5 g of gold in the form of its sulfite complex, 10 g Dissolved disodium sulfite, 15 g tetrasodium ethylenediaminetetraacetate, 4 g nickel sulfate and 12 g cadmium sulfate. From this bath is erthält at a pH value of about 10 at 70 0 C and a current density of 1 A / dm 2 white, semi-gloss coatings containing about 80% gold and 20% cadmium in addition contain traces of nickel. If 2 g of 1-hydroxyethylidene-1,1-diphosphonic acid are added to this electrolyte, high-gloss coatings are obtained, but the gloss disappears when small amounts of iron are added to the bath as an impurity.

Fügt man dem Elektrolyten aus 5 g Gold als Sulfitokomplex, 10 g Dinatriumsulfit, 15 g Tetranatrium- äthylendiamintetraacetat, 4 g Nickelsulfat und 12 g Kadmiumsulfat 6 g Orotsäure zu, so erhält man bei einem pH-Wert von 10, einer Temperatur von 70 C und einer Stromdichte von 1 A/dm2 ebenfalls hochglänzende, weiße Schichten, die bis zu einer Schichtdicke von über 30 um absolut rißfrei aufwachsen und einen ausgezeichneten Glanz aufweisen. Diese Bäder sind weitgehend umempfindlich gegen Verunreinigungen durch Schwermetalle und insbesondere Cyanide. Man erhält mit diesen Bädern Goldüberzüge mit 66 bis 75 % Gold, Rest Kadmium, je nach Stromdichte, wobei höhere Stromdichten einen höheren Kadmiumgehalt im Überzug bewirken.If you add 5 g of gold as a sulfite complex, 10 g of disodium sulfite, 15 g of tetrasodium ethylenediaminetetraacetate, 4 g of nickel sulfate and 12 g of cadmium sulfate, 6 g of orotic acid are added to the electrolyte at a pH of 10, a temperature of 70 ° C. and a current density of 1 A / dm 2 also high-gloss, white layers that grow up to a layer thickness of more than 30 µm absolutely crack-free and have an excellent gloss. These baths are largely insensitive to contamination by heavy metals and especially cyanides. With these baths one obtains gold coatings with 66 to 75% gold, the rest cadmium, depending on the current density, whereby higher current densities cause a higher cadmium content in the coating.

Claims (2)

1. Galvanisches Bad zur Abscheidung hochglänzender Weißgoldüberzüge mit 2 - 10 g/l Gold in Form eines Sulfitkomplexes, 2 - 40 g/1 Alkalisulfit, 2 - 40 g/1 eines Komplexbildners, 1 - 10 g/1 Nickel und 1 - 20g/1 Kadmium jeweils in Form wasserlöslicher Salze, dadurch gekennzeichnet, daß es 0,5 - 10 g/1 Orotsäure und/oder deren Derivate und/oder Salze enthält.1. Galvanic bath for the deposition of high-gloss white gold coatings with 2 - 10 g / l gold in the form of a sulfite complex, 2 - 40 g / 1 alkali sulfite, 2 - 40 g / 1 a complexing agent, 1 - 10 g / 1 nickel and 1 - 20 g / 1 cadmium each in the form of water-soluble salts, characterized in that it contains 0.5 - 10 g / 1 orotic acid and / or its derivatives and / or salts. 2. Galvanisches Bad nach Anspruch 1, dadurch gekennzeichnet, daß es bei einem pH-Wert zwischen 9 und 11, Temperaturen zwischen 10 und 700 C und Stromdichten von 0,5 bis 2 A/dm2 betrieben wird.2. Galvanic bath according to claim 1, characterized in that it is operated at a pH between 9 and 11, temperatures between 10 and 70 0 C and current densities of 0.5 to 2 A / dm 2 .
EP81102315A 1980-04-03 1981-03-27 Plating bath and its use for depositing very lustrous coatings of white gold Expired EP0037534B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3013030 1980-04-03
DE3013030A DE3013030C2 (en) 1980-04-03 1980-04-03 Galvanic bath and process for the deposition of high-gloss white gold coatings

Publications (3)

Publication Number Publication Date
EP0037534A2 true EP0037534A2 (en) 1981-10-14
EP0037534A3 EP0037534A3 (en) 1981-11-04
EP0037534B1 EP0037534B1 (en) 1983-09-07

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US (1) US4374006A (en)
EP (1) EP0037534B1 (en)
DE (1) DE3013030C2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2306508A (en) * 1995-11-03 1997-05-07 Enthone Omi Gold-iron alloy electroplating processes compositions and deposits

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE220736T1 (en) 1995-11-03 2002-08-15 Enthone Omi Inc ELECTROPLATTING METHODS, COMPOSITIONS AND COATINGS
CN1360643A (en) * 1999-07-14 2002-07-24 大阪市 Spectacle frame surface treatment method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1232597A (en) * 1959-01-13 1960-10-10 Deinert & Co Galvanic bath for depositing nickel or other metals
CH455434A (en) * 1963-08-15 1968-07-15 Werner Fluehmann Galvanische A Process for the production of white gold coatings

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3475292A (en) * 1966-02-10 1969-10-28 Technic Gold plating bath and process
ZA734253B (en) * 1972-07-10 1975-02-26 Degussa Electrolytic bath
US3981782A (en) * 1972-07-28 1976-09-21 Johnson Matthey & Co., Limited Electroplating of gold and gold compounds therefor
US4012294A (en) * 1972-08-10 1977-03-15 Oxy Metal Industries Corporation Gold sulfite baths containing organophosphorous compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1232597A (en) * 1959-01-13 1960-10-10 Deinert & Co Galvanic bath for depositing nickel or other metals
CH455434A (en) * 1963-08-15 1968-07-15 Werner Fluehmann Galvanische A Process for the production of white gold coatings

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2306508A (en) * 1995-11-03 1997-05-07 Enthone Omi Gold-iron alloy electroplating processes compositions and deposits
GB2306508B (en) * 1995-11-03 1999-04-28 Enthone Omi Electroplating processes compositions and deposits

Also Published As

Publication number Publication date
DE3013030C2 (en) 1984-02-09
US4374006A (en) 1983-02-15
EP0037534A3 (en) 1981-11-04
EP0037534B1 (en) 1983-09-07
DE3013030A1 (en) 1981-10-15

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