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DE1033987B - Bath for the electrolytic deposition of gold-copper alloys - Google Patents

Bath for the electrolytic deposition of gold-copper alloys

Info

Publication number
DE1033987B
DE1033987B DES31496A DES0031496A DE1033987B DE 1033987 B DE1033987 B DE 1033987B DE S31496 A DES31496 A DE S31496A DE S0031496 A DES0031496 A DE S0031496A DE 1033987 B DE1033987 B DE 1033987B
Authority
DE
Germany
Prior art keywords
derivative
gold
salt
acid
bath
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.)
Pending
Application number
DES31496A
Other languages
German (de)
Inventor
Victor Spreter
Jean Mermillod
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of DE1033987B publication Critical patent/DE1033987B/en
Pending 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
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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

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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)

Description

Die Erfindung betrifft ein Bad für die elektrolytische Abscheidung von Gold-Kupfer-Legierungen, welches das Gold als alkalisches Aurocyanid enthält. Die bekannten Bäder dieser Art enthalten das mit dem Gold zu legierende Kupfer vorwiegend als Kupfercyanid. Diese Bäder haben den Nachteil, daß das Verhältnis der Menge des abgeschiedenen Metalls zum Stromverbrauch, kurz gesagt die Stromausbeute, in verhältnismäßig kurzer Zeit sehr stark absinkt, was auch als »Alterung« des Bades bezeichnet wird. Diese Alterung hängt nicht mit der chemischen Beständigkeit der Bäder zusammen, vielmehr beruht sie offenbar auf der Umwandlung des einwertigen Goldes in dreiwertiges Gold durch die Anwesenheit des Kupfercyanids. Da das dreiwertige Gold bei der Elektrolyse nicht oder nur in geringen Mengen zur Abscheidung gelangt, ergibt sich eine Verminderung der Stromausbeute.The invention relates to a bath for the electrolytic deposition of gold-copper alloys, which the Contains gold as an alkaline aurocyanide. The well-known baths of this type contain that to be alloyed with the gold Copper mainly as copper cyanide. These baths have the disadvantage that the ratio of the amount of deposited Metal to power consumption, in short the power yield, very strong in a relatively short time sinks, which is also referred to as "aging" of the bath. This aging is not related to the chemical Stability of the baths together, rather it is based on the transformation of the monovalent gold into trivalent gold due to the presence of copper cyanide. Because the trivalent gold in electrolysis is not deposited or is only deposited in small quantities, the result is a reduction in the current yield.

Gemäß der Erfindung liegt das mit dem Gold zu legierende Kupfer als Salz eines stickstoffhaltigen Derivates der Essigsäure vor. Es zeigt sich überraschenderweise, daß ein Bad dieser Art der obengenannten Alterung nicht unterliegt. Es ist zwar bereits bekannt, in Bädern für die elektrolytische Erzeugung metallischer Überzüge das aufzubringende unedle Metall statt in Form von Cyaniden in Gestalt von Komplexverbindungen der Nitrilotri-, Äthylendiamintetra- oder Propylendiamintetraessigsäure zu verwenden. Hierdurch soll jedoch nur die Giftigkeit der Bäder beseitigt und ihre chemische Beständigkeit erhöht werden, während der durch die vorliegende Erfindung beseitigte Alterungsprozeß bei Mischlösungen aus komplexen Cyaniden unedler Metalle gerade nicht stattfindet.According to the invention, the copper to be alloyed with the gold is a salt of a nitrogen-containing one Derivatives of acetic acid. It turns out, surprisingly, that a bath of this type of the above-mentioned aging not subject. It is already known in baths for the electrolytic production of metallic coatings the base metal to be applied instead of in the form of cyanides in the form of complex compounds of the To use nitrilotriacetic, ethylenediaminetetra- or propylenediaminetetraacetic acid. This is only intended to The toxicity of the baths is eliminated and their chemical resistance increased while being carried out by the The present invention eliminated the aging process in mixed solutions of complex cyanides of base metals is not taking place at the moment.

Das gemäß der Erfindung in dem Bad enthaltene Kupfersalz eines stickstoffhaltigen Derivates der Essigsäure kann in seinem Molekül die GruppierungThe copper salt of a nitrogen-containing derivative of acetic acid contained in the bath according to the invention can in its molecule the grouping

35 — N(CH2COO-)2 35 - N (CH 2 COO-) 2

oder die Gruppierungor the grouping

-NH-CH2COO-NH-CH 2 COO

enthalten. Hier kommen vor allem die Salze der Imidodiessigsäure und ihrer Derivate, z. B. die Äthylendiamino-tetraessigsäure, die Nitrilotriessigsäure, die Anthranildiessigsäure, die Uramildiessigsäure und die Aminomalondiessigsäure in Betracht.contain. The salts of imidodiacetic acid come here in particular and their derivatives, e.g. B. the ethylenediamino-tetraacetic acid, the nitrilotriacetic acid, the Anthranil diacetic acid, uramildiacetic acid and aminomalondiacetic acid into consideration.

Als Ausführungsbeispiel kann ein Bad gemäß der Erfindung, das besonders für die Abscheidung von Überzügen großer Dicke geeignet ist, folgende Zusammensetzung haben:As an embodiment, a bath according to the invention, which is particularly suitable for the deposition of coatings large thickness is suitable, have the following composition:

Gold in Form von Kaliumaurocyanid KAu(CN)2 12 g/l
Cu in Form des Kupfersalzes der Äthylen-Gold in the form of potassium aurocyanide KAu (CN) 2 12 g / l
Cu in the form of the copper salt of the ethylene

diamino-tetraessigsäure 2,5 g/ldiamino-tetraacetic acid 2.5 g / l

Zn in Form des Zinksalzes der Äthylen-Zn in the form of the zinc salt of the ethylene

diamino-tetraessigsäure 2 g/ldiamino-tetraacetic acid 2 g / l

Bad für die elektrolytische Abscheidung von Gold-Kupfer-LegierungenBath for the electrolytic deposition of gold-copper alloys

Anmelder:Applicant:

Victor Spreter und Jean Mermillod,
Genf (Schweiz)Victor Spreter and Jean Mermillod,
Geneva (Switzerland)

Vertreter: Dipl.-Ing. W. Scherrmann, Patentanwalt,
Eßlingen/Neckar, Fabrikstr. 9Representative: Dipl.-Ing. W. Scherrmann, patent attorney,
Eßlingen / Neckar, Fabrikstr. 9

Beanspruchte Priorität:
Schweiz vom 8. Mai 1952Claimed priority:
Switzerland from May 8, 1952

Victor Spreter und Jean Mermillod, Genf (Schweiz),
sind als Erfinder genannt wordenVictor Spreter and Jean Mermillod, Geneva (Switzerland),
have been named as inventors

Ni in Form des Nickelsalzes der Äthylen-Ni in the form of the nickel salt of the ethylene

diamino-tetraessigsäure 2 g/ldiamino-tetraacetic acid 2 g / l

Kaliumsalz der Äthylendiamino-tetraessigsäure 5 g/lPotassium salt of ethylenediaminetetraacetic acid 5 g / l

Man stellt das pH des Bades auf ungefähr 8 ein, und zwar entweder durch Zugabe von Äthylendiamino-tetraessigsäure oder durch Zugabe von Kaliumkarbonat.Man represents the p H of the bath to about 8, and either by the addition of Äthylendiamino-tetraacetic acid or by addition of potassium carbonate.

Wenn man dieses Bad bei einer Temperatur von 6O0C mit einer Anode aus nicht oxydierbarem Stahl und bei einer kathodischen Stromdichte von 2,5 Amp./dm2 verwendet, erhält man die Abscheidung einer stark glänzenden Goldlegierung von einem Gehalt von ungefähr Karat. Die Dicke des Niederschlages beträgt ungefähr Mikron pro Stunde, was einer Stromausbeute von etwa 35% in bezug auf den Stromverbrauch entspricht.When using this bath at a temperature of 6O 0 C with an anode of non-oxidizable steel and at a cathodic current density of 2.5 Amp./dm 2, is obtained the deposition of a highly reflective gold alloy by a content of about carats. The thickness of the deposit is approximately microns per hour, which corresponds to a power efficiency of about 35% in relation to the power consumption.

Claims (9)

Patentansprüche:Patent claims: 1. Bad für die elektrolytische Abscheidung von Gold-Kupfer-Legierungen, welches das Gold als alkalisches Aurocyanid enthält, dadurch gekennzeichnet, daß das mit dem Gold zu legierende Kupfer als Salz eines stickstoffhaltigen Derivates der Essigsäure vorliegt.1. Bath for the electrolytic deposition of gold-copper alloys, which the gold as contains alkaline aurocyanide, characterized in that the copper to be alloyed with the gold is present as a salt of a nitrogen-containing derivative of acetic acid. 2. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat die Gruppierung —N(CH2COO—)2 enthält.2. Bath according to claim 1, characterized in that the derivative contains the group —N (CH 2 COO—) 2 . 809 560/433809 560/433 3. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat die Gruppierung —NH—CH2COO — enthält.3. Bath according to claim 1, characterized in that the derivative contains the grouping —NH — CH 2 COO -. 4. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat ein Salz eines Derivates der Imidodiessigsäure ist.4. Bath according to claim 1, characterized in that the derivative is a salt of a derivative of imidodiacetic acid is. 5. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat ein Salz der Äthylendiamino-tetraessigsäure ist.5. Bath according to claim 1, characterized in that the derivative is a salt of ethylenediamino-tetraacetic acid is. 6. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat ein Salz der Nitrilotriessigsäure ist.6. Bath according to claim 1, characterized in that the derivative is a salt of nitrilotriacetic acid. 7. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat ein Salz der Anthranildiessigsäure ist,7. Bath according to claim 1, characterized in that the derivative is a salt of anthranil diacetic acid, 8. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat ein Salz der Uramildiessigsäure ist.8. Bath according to claim 1, characterized in that the derivative is a salt of uramildiacetic acid. 9. Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Derivat ein Salz der Aminomalondiessigsäure ist.9. Bath according to claim 1, characterized in that the derivative is a salt of aminomalondiacetic acid is. In Betracht gezogene Druckschriften:
Deutsche Patentschrift Nr. 732 102.Considered publications:
German patent specification No. 732 102. 809 560/433 7.58809 560/433 7.58
DES31496A 1952-05-08 1952-12-13 Bath for the electrolytic deposition of gold-copper alloys Pending DE1033987B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH718574X 1952-05-08

Publications (1)

Publication Number Publication Date
DE1033987B true DE1033987B (en) 1958-07-10

Family

ID=4531337

Family Applications (1)

Application Number Title Priority Date Filing Date
DES31496A Pending DE1033987B (en) 1952-05-08 1952-12-13 Bath for the electrolytic deposition of gold-copper alloys

Country Status (5)

Country Link
US (1) US2724687A (en)
CH (1) CH286123A (en)
DE (1) DE1033987B (en)
FR (1) FR1067620A (en)
GB (1) GB718574A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2829979A1 (en) * 1977-07-08 1979-01-18 Systemes Traitements Surfaces ELECTROLYSIS BATH FOR THE DEPOSITION OF GOLD-COPPER-CADMIUM ALLOYS AND ITS APPLICATION IN GALVANO TECHNOLOGY
DE3020765A1 (en) * 1980-05-31 1981-12-10 Degussa Ag, 6000 Frankfurt ALKALINE BATH FOR GALVANIC DEPOSITION OF LOW-CARAINE PINK TO YELLOW-COLORED GOLD ALLOY LAYERS
US8202706B2 (en) 2006-07-13 2012-06-19 Evonik Degussa Gmbh Method of production of L-amino acids

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE801312C (en) * 1949-05-05 1950-11-23 Pforzheimer Elektrizitäts - Gesellschaft m. b. H., Pforzheim Process for the electrolytic deposition of gold and gold alloys
DE1111897B (en) * 1957-08-13 1961-07-27 Sel Rex Corp Bath for the galvanic deposition of shiny gold alloy coatings
BE570261A (en) * 1957-08-13
US3057789A (en) * 1959-02-26 1962-10-09 Paul T Smith Gold plating bath and process
US3149057A (en) * 1959-04-27 1964-09-15 Technic Acid gold plating
US3149058A (en) * 1959-12-31 1964-09-15 Technic Bright gold plating process
US3056733A (en) * 1960-04-23 1962-10-02 Degussa Process for electrolytic deposition of gold-copper-cadmium alloys
USB373094I5 (en) * 1964-08-26
DE1262723B (en) * 1964-12-16 1968-03-07 Philippi & Co K G Galvanic gold or gold alloy bath
US3380898A (en) * 1965-06-18 1968-04-30 Sel Rex Corp Electrolyte and method for electrodepositing a pink gold alloy
US3380814A (en) * 1965-06-18 1968-04-30 Sel Rex Corp Electrolyte and method for coating articles with a gold-copper-antimony alloy and article thereof
US3530049A (en) * 1968-10-02 1970-09-22 Technic Gold and ruthenium plating baths
US3902977A (en) * 1973-12-13 1975-09-02 Engelhard Min & Chem Gold plating solutions and method
US4465564A (en) * 1983-06-27 1984-08-14 American Chemical & Refining Company, Inc. Gold plating bath containing tartrate and carbonate salts
DE69622431T2 (en) 1995-11-03 2003-01-30 Enthone-Omi, Inc. ELECTROPLATING METHODS, COMPOSITIONS AND COATINGS
CH714243B1 (en) * 2006-10-03 2019-04-15 Swatch Group Res & Dev Ltd Electroforming process and part or layer obtained by this method.
CH710184B1 (en) * 2007-09-21 2016-03-31 Aliprandini Laboratoires G Process for obtaining a yellow gold alloy deposit by electroplating without the use of toxic metals or metalloids.
EP2312021B1 (en) * 2009-10-15 2020-03-18 The Swatch Group Research and Development Ltd. Method for obtaining a deposit of a yellow gold alloy by galvanoplasty without using toxic metals

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE732102C (en) * 1937-01-12 1943-02-26 Schallband Syndikat Ag Process for the serial production of sound films with mechanical sound writing

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2660554A (en) * 1950-11-10 1953-11-24 Barnet D Ostrow Bright gold and gold alloy plating baths

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE732102C (en) * 1937-01-12 1943-02-26 Schallband Syndikat Ag Process for the serial production of sound films with mechanical sound writing

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2829979A1 (en) * 1977-07-08 1979-01-18 Systemes Traitements Surfaces ELECTROLYSIS BATH FOR THE DEPOSITION OF GOLD-COPPER-CADMIUM ALLOYS AND ITS APPLICATION IN GALVANO TECHNOLOGY
DE2829979C3 (en) * 1977-07-08 1990-06-21 Systemes Traitements Surfaces AQUEOUS BATH FOR GALVANIC DEPOSITION OF GOLD COPPER CADMIUM ALLOYS
DE3020765A1 (en) * 1980-05-31 1981-12-10 Degussa Ag, 6000 Frankfurt ALKALINE BATH FOR GALVANIC DEPOSITION OF LOW-CARAINE PINK TO YELLOW-COLORED GOLD ALLOY LAYERS
US4358351A (en) * 1980-05-31 1982-11-09 Degussa Aktiengesellschaft Alkaline bath for the electrolytic deposition of low carat yellow colored gold alloy layers
US8202706B2 (en) 2006-07-13 2012-06-19 Evonik Degussa Gmbh Method of production of L-amino acids

Also Published As

Publication number Publication date
US2724687A (en) 1955-11-22
CH286123A (en) 1952-10-15
FR1067620A (en) 1954-06-17
GB718574A (en) 1954-11-17

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