EP1198623A1 - Method for producing a cyanide-free solution of a gold compound that is suitable for galvanic gold baths - Google Patents

Method for producing a cyanide-free solution of a gold compound that is suitable for galvanic gold baths

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Publication number
EP1198623A1
EP1198623A1 EP00929531A EP00929531A EP1198623A1 EP 1198623 A1 EP1198623 A1 EP 1198623A1 EP 00929531 A EP00929531 A EP 00929531A EP 00929531 A EP00929531 A EP 00929531A EP 1198623 A1 EP1198623 A1 EP 1198623A1
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EP
European Patent Office
Prior art keywords
gold
galvanic
solution
baths
cyanide
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
EP00929531A
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German (de)
French (fr)
Other versions
EP1198623B1 (en
Inventor
Gerhard Hoffacker
Renate Franz
Ramona Reitz
Richard Walter
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.)
Hoffacker Gerhard
WC Heraus GmbH and Co KG
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WC Heraus GmbH and Co KG
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Application filed by WC Heraus GmbH and Co KG filed Critical WC Heraus GmbH and Co KG
Publication of EP1198623A1 publication Critical patent/EP1198623A1/en
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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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • the invention relates to a method for producing a cyanide-free gold connection solution suitable for galvanic gold baths, a corresponding gold connection solution and their uses.
  • the problem arises of at least partially eliminating the above-mentioned disadvantages with the aid of a novel method, a novel gold connection solution and corresponding uses.
  • the problem that arises is, in particular, to provide a process for the preparation of a cyanide-free, stable gold connection solution suitable for electroplating gold baths.
  • a cysteine and / or cysteinate is reacted with a tetrachloro-gold acid and / or a tetrachloro-gold salt in a first aqueous medium, in particular in water, in a first step.
  • a tetrachloro-gold acid and / or a tetrachloro-gold salt in a first aqueous medium, in particular in water, in a first step.
  • potassium or sodium cysteinate can be used can be used as tetrachloro gold salt, for example sodium or potassium tetrachloroaurate
  • the precipitate obtained is then separated from the first aqueous medium in a second step; this can be accomplished, for example, by repeated centrifugation and decanting of the supernatant liquid
  • the precipitate obtained is dissolved in a second aqueous medium, for example in water, by adding, for example, a potassium hydroxide solution while simultaneously increasing the pH to 12.0 to 14.0
  • the gold compound solutions obtained in this way are stable for several weeks in the absence of light and air and have excellent properties for galvanic gold baths
  • the molar ratio of cysteine / cysteinate to the tetrachlorogold compound is 3 1 to 10 1.
  • the molar ratio of 3 1 gives the highest yields
  • the reaction is advantageously carried out at a temperature of T ⁇ + 30 ° C., since decomposition phenomena of the gold compound can be observed at a higher temperature
  • HAuCI solution 43.021 g (0.0906 mol) of HAuCI solution are weighed into a second beaker (400 ml) and made up to a volume of 145 ml.
  • a rust-red clear solution is created.
  • the gold chloride solution is added in portions to the amino acid salt solution.
  • the solution Since the reaction is exothermic, the solution must be cooled during the entire addition, so that the temperature is not more than + 20 ° C.
  • This suspension is then allowed to stir for a further 1/2 hours. It has become a little lighter, but still has a yellow tinge. The suspension is then washed chloride-free using the centrifuge.
  • aqueous KOH solution (50%) is added to a pH of 13.5. A golden yellow solution was obtained. Because the solution was still slightly cloudy, it was filtered off using a cellulose filter.
  • the Au content of the solution is 3.16% (Au yield: 97.7%).
  • the Cl content of the solution is 17 ppm. The solution is stable for months.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for producing a cyanide-free solution of a gold compound that is suitable for gold electrodeposition baths. The method includes the steps of reacting at least one of a cysteine and a cysteinate with at least one of tetrachloroauric acid and a tetrachloroaurate in a first aqueous medium, separating a resulting precipitate from the first aqueous medium, and dissolving the precipitate in a second aqueous medium with elevation of the pH to 12.0-14.0.

Description

Verfahren zur Herstellung einer cyanidfreien, für galvanische Gold-Bäder geeigneten Goldverbindungslösung Process for the preparation of a cyanide-free gold connection solution suitable for galvanic gold baths
Die Erfindung betrifft ein Verfahren zur Herstellung einer cyanidfreien, für galvanische Gold- Bäder geeigneten Goldverbindungslösung, eine entsprechende Goldverbindungslösung und deren Verwendungen.The invention relates to a method for producing a cyanide-free gold connection solution suitable for galvanic gold baths, a corresponding gold connection solution and their uses.
Es ist seit langem bekannt, cyanidhaltige Goldverbindungslösungen als Bäder zur galvanischen Abscheidung bei der Vergoldung von Gegenständen zu verwenden. Aufgrund der hohen Toxi- zität der verwendeten Cyanidionen bzw. deren unter Umständen freigesetzten Cyanwas- serstoffsäure ergeben sich erhebliche Sicherheitsprobleme bei der Durchführung der bekannten Verfahren.It has long been known to use cyanide-containing gold compound solutions as plating baths for the gold plating of objects. Due to the high toxicity of the cyanide ions used or their possibly released cyanohydric acid, there are considerable safety problems when carrying out the known processes.
Darüber hinaus sind aus dem Stand der Technik Goldverbindungslösungen für galvanische Bäder bekannt, die mit dem Nachteil behaftet sind, nach einer gewissen Zeit sich zu zersetzen; als typisches Beispiel sei eine Ammoniumdisulfitoaurat-Lösung genannt.In addition, gold connection solutions for galvanic baths are known from the prior art, which have the disadvantage of decomposing after a certain time; An ammonium disulfitoaurate solution is a typical example.
Aus JP 10-317183 A ist u. a. ein Mercaptocarbonsäure-Goldbeschichtungsbad offenbart, das einen oder mehrere Bestandteile aus einem Alkalimetallsalz oder Ammoniumsalz eines Acetyl- cystein-Goldkomplexes, einem Cystein-Goldkomplex, einem Mercaptosuccinsäure- Goldkomplex, einem Goldchlorid und einem schwefelhaltigen Goldkomplex enthält. Nachteilig an diesen Lösungen ist jedoch auch die Tatsache, dass sich diese nach einer gewissen Zeit zersetzen.From JP 10-317183 A u. a. discloses a mercaptocarboxylic acid gold plating bath containing one or more components of an alkali metal salt or ammonium salt of an acetyl-cysteine-gold complex, a cysteine-gold complex, a mercaptosuccinic acid-gold complex, a gold chloride and a sulfur-containing gold complex. However, a disadvantage of these solutions is the fact that they decompose after a certain time.
Aus dem vorgenannten ergibt sich das Problem, mit Hilfe eines neuartigen Verfahrens, einer neuartigen Goldverbindungslösung und entsprechenden Verwendungen die oben genannten Nachteile zumindest teilweise zu beseitigen. Das sich ergebende Problem liegt insbesondere darin, ein Verfahren zur Herstellung einer cyanidfreien, stabilen und für galvanische Gold-Bäder geeigneten Goldverbindungslösung bereitzustellen.From the above, the problem arises of at least partially eliminating the above-mentioned disadvantages with the aid of a novel method, a novel gold connection solution and corresponding uses. The problem that arises is, in particular, to provide a process for the preparation of a cyanide-free, stable gold connection solution suitable for electroplating gold baths.
Dieses Problem wird erfindungsgemäß durch ein Verfahren nach Anspruch 1 , eine Goldverbindungslösung nach Anspruch 7 und durch Verwendungen nach den Ansprüchen 8 bis 11 gelöst.This problem is solved according to the invention by a method according to claim 1, a gold connection solution according to claim 7 and by uses according to claims 8 to 11.
BESTATIGUNGSKOPIE Beim erfindungsgemaßen Verfahren wird in einem ersten Schritt ein Cystein und/oder Cysteinat mit einer Tetrachloro-Goldsaure und/oder einem Tetrachloro-Goldsalz in einem ersten wäßrigen Medium, insbesondere in Wasser, umgesetzt Als Cysteinat können beispielsweise Ka um- oder Natπumcysteinat verwendet werden, wahrend als Tetrachloro-Goldsalz z B Natrium- oder Kahumtetrachloroaurat Verwendung finden könnenCONFIRMATION COPY In the process according to the invention, a cysteine and / or cysteinate is reacted with a tetrachloro-gold acid and / or a tetrachloro-gold salt in a first aqueous medium, in particular in water, in a first step. For example, potassium or sodium cysteinate can be used can be used as tetrachloro gold salt, for example sodium or potassium tetrachloroaurate
Anschließend wird in einem zweiten Schritt der erhaltene Niederschlag vom ersten wäßrigen Medium abgetrennt, dies kann beispielsweise durch mehrmaliges Zentπfugieren und Abdekantieren der überstehenden Flüssigkeit bewerkstelligt werdenThe precipitate obtained is then separated from the first aqueous medium in a second step; this can be accomplished, for example, by repeated centrifugation and decanting of the supernatant liquid
Schließlich wird der erhaltene Niederschlag in einem zweiten wäßrigen Medium, beispielsweise in Wasser, durch Zugabe beispielsweise einer Kahumhydroxid-Losung unter gleichzeitiger Erhöhung des pH-Wertes auf 12,0 bis 14,0 gelostFinally, the precipitate obtained is dissolved in a second aqueous medium, for example in water, by adding, for example, a potassium hydroxide solution while simultaneously increasing the pH to 12.0 to 14.0
Die auf diese Art und Weise erhaltenen Goldverbindungslosungen sind unter Ausschluß von Licht und Luft für mehrere Wochen stabil und weisen ausgezeichnete Eigenschaften für galvanische Goldbader aufThe gold compound solutions obtained in this way are stable for several weeks in the absence of light and air and have excellent properties for galvanic gold baths
In der Praxis haben sich die folgenden Ausgestaltungen bewahrt und somit als vorteilhaft herausgestelltIn practice, the following configurations have been retained and have thus proven to be advantageous
Der abgetrennte Niederschlag wird chlondfrei gewaschenThe separated precipitate is washed free of chlorine
Das Mol-Verhaltnis von Cystein/Cysteinat zur Tetrachlorogold-Verbindung betragt 3 1 bis 10 1 Erfahrungsgemäß ergibt das Mol-Verhaltnis von 3 1 die höchsten AusbeutenThe molar ratio of cysteine / cysteinate to the tetrachlorogold compound is 3 1 to 10 1. Experience has shown that the molar ratio of 3 1 gives the highest yields
Die Umsetzung wird in vorteilhafter Weise bei einer Temperatur von T < +30°C durchgeführt, da bei höherer Temperatur Zersetzungserscheinungen der Gold-Verbindung zu beobachten sind )The reaction is advantageously carried out at a temperature of T <+ 30 ° C., since decomposition phenomena of the gold compound can be observed at a higher temperature)
Weiterhin hat es sich in der Praxis als vorteilhaft herausgestellt, daß beim Losen des Niederschlags der pH-Wert auf 13,5 erhöht (sehr stabile Losungen) und als Cysteinat L- Kahumcysteinat verwendet wirdIt has also proven to be advantageous in practice that when the precipitate is dissolved, the pH increases to 13.5 (very stable solutions) and L-potassium cysteinate is used as the cysteinate
Die nach obigem Verfahren hergestellten Goldverbindungslosungen weisen die entsprechenden Eigenschaften aufThe gold compound solutions produced by the above process have the corresponding properties
Dies gilt naturgemäß auch für die entsprechenden Verwendungen, insbesondere für solche, bei denen die hergestellten Goldverbindungslosungen als Precursor zur Herstellung von goldhaltigen Heterogen-Katalysatoren oder als galvanische Goldbader verwendet werden Das nachfolgende Beispiel dient zur Erläuterung der Erfindung.Naturally, this also applies to the corresponding uses, in particular to those in which the gold compound solutions prepared are used as precursors for the production of gold-containing heterogeneous catalysts or as galvanic gold baths The following example serves to explain the invention.
L-Cystein / HAuCI -Lösung 3:1L-cysteine / HAuCI solution 3: 1
30,557 g (0,272 mol) wäßrige KOH-Lösung (50%) werden abgewogen und in einem Becherglas mit 36 ml VEW (vollentsalztes Wasser) verdünnt. Zu dieser Lösung gibt man portionsweise 32,956 g (0,272 mol) L-Cystein. Eine leicht exotherme Reaktion findet statt. Es entsteht eine klare und farblose Lösung.30.557 g (0.272 mol) aqueous KOH solution (50%) are weighed out and diluted in a beaker with 36 ml VEW (fully demineralized water). 32.956 g (0.272 mol) of L-cysteine are added in portions to this solution. A slightly exothermic reaction takes place. A clear and colorless solution is created.
In ein zweites Becherglas (400 ml) werden 43,021 g (0,0906 mol) HAuCI -Lösung eingewogen und auf ein Volumen von 145 ml ergänzt. Zu der HAuCI -Lösung gibt man wäßrige KOH- Lösung (10%) bis ein pH-Wert von 6,1 erreicht ist (Verbrauch = 162 ml). Es entsteht eine rostrote klare Lösung.43.021 g (0.0906 mol) of HAuCI solution are weighed into a second beaker (400 ml) and made up to a volume of 145 ml. Aqueous KOH solution (10%) is added to the HAuCI solution until a pH of 6.1 is reached (consumption = 162 ml). A rust-red clear solution is created.
Anschließend gibt man portionsweise die Goldchlorid-Lösung zu der Aminosäure-Salzlösung.Then the gold chloride solution is added in portions to the amino acid salt solution.
Der pH-Wert fällt während der gesamten Zugabe ständig ab. Am Anfang liegt eine klare farblose Lösung vor. Nach Zugabe von ca. 20 ml der Goldchlorid-Lösung wird die Lösung trüb. Bei weiterer Zugabe entsteht eine weiße Suspension, welche sich gegen Ende der Zugabe nach pastellgelb verfärbt.The pH value drops continuously during the entire addition. At the beginning there is a clear colorless solution. After adding about 20 ml of the gold chloride solution, the solution becomes cloudy. With further addition, a white suspension is formed, which turns pastel yellow towards the end of the addition.
Da die Reaktion exotherm verläuft, ist die Lösung während der kompletten Zugabe zu kühlen, so daß die Temperatur nicht mehr als + 20 °C beträgt.Since the reaction is exothermic, the solution must be cooled during the entire addition, so that the temperature is not more than + 20 ° C.
Diese Suspension läßt man nun noch 1 Vz Stunden nachrühren. Sie ist etwas heller geworden, hat aber immer noch einen Gelbstich. Die Suspension wird anschließend mit Hilfe der Zentrifuge chloridfrei gewaschen.This suspension is then allowed to stir for a further 1/2 hours. It has become a little lighter, but still has a yellow tinge. The suspension is then washed chloride-free using the centrifuge.
Nachdem die Suspension chloridfrei ist, gibt man wäßrige KOH-Lösung (50%) dazu, bis zu einem pH-Wert von 13,5. Es wurde eine goldgelbe Lösung erhalten. Wegen der noch geringen Trübung der Lösung wurde diese über einen Zellulosefilter abfiltriert.After the suspension is free of chloride, aqueous KOH solution (50%) is added to a pH of 13.5. A golden yellow solution was obtained. Because the solution was still slightly cloudy, it was filtered off using a cellulose filter.
Nun wurde eine goldgelbe klare Lösung erhalten, die in eine Braunglasflasche abgefüllt und fest verschlossen wird.Now a golden yellow clear solution was obtained, which is filled into a brown glass bottle and tightly closed.
Es wurden 551 ,487 g Au-Aminosäure-Lösung erhalten.551.487 g of Au amino acid solution were obtained.
Der Au-Gehalt der Lösung beträgt 3,16% (Au-Ausbeute: 97,7 %). Der Cl-Gehalt der Lösung liegt bei 17 ppm. Die Lösung ist über Monate stabil. The Au content of the solution is 3.16% (Au yield: 97.7%). The Cl content of the solution is 17 ppm. The solution is stable for months.

Claims

Patentansprüche claims
1 Verfahren zur Herstellung einer cyanidfreien, für galvanische Gold-Bäder geeigneten Gold- verbindungslosung, mit1 Process for the production of a cyanide-free gold connection solution suitable for galvanic gold baths, with
a) Umsetzung eines Cysteins und/oder Cysteinats mit einer Tetrachlorogoldsäure und/oder einem Tetrachlorogoldsalz in einem ersten wäßrigen Mediuma) reaction of a cysteine and / or cysteinate with a tetrachloroauric acid and / or a tetrachloroaur salt in a first aqueous medium
b) Abtrennen des erhaltenen Niederschlags vom ersten wäßrigen Medium undb) separating the precipitate obtained from the first aqueous medium and
c) Losen des Niederschlags in einem zweiten wäßrigen Medium bei Erhöhung des pH-Wertes auf 12,0 bis 14,0c) dissolving the precipitate in a second aqueous medium by increasing the pH to 12.0 to 14.0
2 Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß der abgetrennte Niederschlag chlondfrei gewaschen wird2 The method according to claim 1, characterized in that the separated precipitate is washed free of chlorine
3 Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß das Mol- Verhaltnis von Cystein/Cystemat zur Tetrachlorogold-Verbindung 3 1 bis 10 1 beträgt3 Process according to one of claims 1 to 2, characterized in that the molar ratio of cysteine / systemate to the tetrachlorogold compound is 3 1 to 10 1
4 Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Umsetzung bei einer Temperatur T < +30°C durchgeführt wird.4 The method according to any one of claims 1 to 3, characterized in that the reaction is carried out at a temperature T <+ 30 ° C.
5 Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß beim Lösen des Niederschlags der pH-Wert auf 13,5 erhöht wird5 The method according to any one of claims 1 to 4, characterized in that the pH is increased to 13.5 when the precipitate is dissolved
6 Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß als Cysteinat L-Kaliumcysteinat verwendet wird6 The method according to any one of claims 1 to 5, characterized in that L-potassium cysteinate is used as the cysteinate
7 Goldverbindungslösung, hergestellt nach einem Verfahren nach einem der Ansprüche 1 bis 6. Verwendung einer Gold-Verbindungslosung nach Anspruch 7 als Precursor zur Herstellung von goldhaltigen Heterogen-Katalysatoren7 gold connection solution, produced by a method according to any one of claims 1 to 6. Use of a gold compound solution according to claim 7 as a precursor for the production of gold-containing heterogeneous catalysts
Verwendung einer Gold-Verbindungslosung nach Anspruch 7 als galvanisches GoldbadUse of a gold connection solution according to claim 7 as a galvanic gold bath
Verwendung eines Verfahrens nach einem der Ansprüche 1 bis 6 zur Herstellung einer für galvanische Goldbader geeigneten Goldverbindungslosung als Precursor zur Herstellung von goldhaltigen Heterogen-KatalysatorenUse of a method according to one of claims 1 to 6 for the production of a gold compound solution suitable for galvanic gold baths as a precursor for the production of gold-containing heterogeneous catalysts
Verwendung eines Verfahrens nach einem der Ansprüche 1 bis 6 zur Herstellung einer für galvanische Goldbader geeigneten Goldverbindungslosung als galvanisches Gold Use of a method according to one of claims 1 to 6 for producing a gold connection solution suitable for galvanic gold baths as galvanic gold
EP00929531A 1999-06-01 2000-05-16 Method for producing a cyanide-free solution of a gold compound that is suitable for galvanic gold baths Expired - Lifetime EP1198623B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19924895A DE19924895B4 (en) 1999-06-01 1999-06-01 Process for the preparation of a cyanide-free gold connection solution suitable for galvanic gold baths
DE19924895 1999-06-01
PCT/EP2000/004368 WO2000073540A1 (en) 1999-06-01 2000-05-16 Method for producing a cyanide-free solution of a gold compound that is suitable for galvanic gold baths

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EP1198623A1 true EP1198623A1 (en) 2002-04-24
EP1198623B1 EP1198623B1 (en) 2003-03-19

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EP00929531A Expired - Lifetime EP1198623B1 (en) 1999-06-01 2000-05-16 Method for producing a cyanide-free solution of a gold compound that is suitable for galvanic gold baths

Country Status (7)

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US (1) US6733651B1 (en)
EP (1) EP1198623B1 (en)
JP (1) JP2003500550A (en)
AT (1) ATE234949T1 (en)
DE (2) DE19924895B4 (en)
ES (1) ES2193959T3 (en)
WO (1) WO2000073540A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4245893A1 (en) 2022-03-15 2023-09-20 Université de Franche-Comté Gold electroplating solution and its use for electrodepositing gold with an aged appearance

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101724872B (en) * 2008-10-20 2013-05-08 长沙铂鲨环保设备有限公司 Non-cyanide gilding saline solution
JP5694303B2 (en) * 2009-06-01 2015-04-01 ロイヤル・メルボルン・インスティテュート・オブ・テクノロジーＲｏｙａｌ Ｍｅｌｂｏｕｒｎｅ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｔｅｃｈｎｏｌｏｇｙ Electrodeposited nanostructure
DE102009024396A1 (en) * 2009-06-09 2010-12-16 Coventya Spa Cyanide-free electrolyte for electrodeposition of gold or its alloys
WO2014106830A1 (en) * 2013-01-07 2014-07-10 Ramot At Tel-Aviv University Ltd. Jellyfish-derived polymer
DE102013015805A1 (en) 2013-09-24 2015-03-26 Heraeus Precious Metals Gmbh & Co. Kg Process for producing a glossy layer structure
EP2980051B1 (en) 2014-08-01 2019-03-13 Heraeus Deutschland GmbH & Co. KG Creation of a decorative layer on ceramic surfaces

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH622829A5 (en) * 1977-08-29 1981-04-30 Systemes Traitements Surfaces
US5338343A (en) * 1993-07-23 1994-08-16 Technic Incorporated Catalytic electroless gold plating baths
JP3566498B2 (en) * 1997-05-14 2004-09-15 株式会社大和化成研究所 Displacement gold plating bath
JP3671102B2 (en) * 1997-05-16 2005-07-13 株式会社大和化成研究所 Non-cyan electrogold plating bath

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0073540A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4245893A1 (en) 2022-03-15 2023-09-20 Université de Franche-Comté Gold electroplating solution and its use for electrodepositing gold with an aged appearance
WO2023174871A1 (en) 2022-03-15 2023-09-21 Université de Franche-Comté Gold electroplating solution and its use for electrodepositing gold with an aged appearance

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ES2193959T3 (en) 2003-11-16
DE19924895B4 (en) 2004-03-25
JP2003500550A (en) 2003-01-07
ATE234949T1 (en) 2003-04-15
WO2000073540A8 (en) 2001-09-13
DE50001514D1 (en) 2003-04-24
EP1198623B1 (en) 2003-03-19
DE19924895A1 (en) 2001-05-10
WO2000073540A1 (en) 2000-12-07
US6733651B1 (en) 2004-05-11

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