EP1423557A1 - Bain electrolytique pour le depot electrochimique de l'or et de ses alliages - Google Patents
Bain electrolytique pour le depot electrochimique de l'or et de ses alliagesInfo
- Publication number
- EP1423557A1 EP1423557A1 EP02774881A EP02774881A EP1423557A1 EP 1423557 A1 EP1423557 A1 EP 1423557A1 EP 02774881 A EP02774881 A EP 02774881A EP 02774881 A EP02774881 A EP 02774881A EP 1423557 A1 EP1423557 A1 EP 1423557A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold
- electrolytic bath
- organic compound
- bath according
- electrolytic
- 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
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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
-
- 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
- Electrolytic bath for the electrochemical deposition of gold and its alloys for the electrochemical deposition of gold and its alloys.
- the present invention relates to an electrolytic bath for the electrochemical deposition of gold or its alloys.
- the electrolytic gilding was born in the wake of the invention of the battery by Alisandro Volta. Luigi Brugnatelli, student and collaborator of Volta, professor of chemistry at the University of Pavia, discovered in 1805 the way to gild silver medals using the battery. The procedure he employed is described in particular in a letter addressed to Van Mons of Brussels. Brugnatelli used a solution of chloride of gold in ammonia, in which the object was plunged, and made the latter communicate by a wire of silver or steel with the negative pole of a pile. .
- the rate of deposition of metals in surface treatment is the parameter that it has been and which is still most often requested to optimize (AM Weisberg in Gold Plating Technology, FH Reid and W. Goldie, Electrochemical Publications Limited, Ayr, 1974).
- the most efficient gold baths in terms of electrodeposition rate, keeping the deposition of its excellent properties of gloss, ductility, porosity, hardness, resistance to corrosion and friction, low contact resistance are the baths called "Hard Gold Acid” which are intended for gold deposits hardened by alloying a very small amount of a common metal, most often cobalt or nickel, derived from an acidic electrolyte based on the citric acid / citrate system.
- Improving the rate of electrodeposition is also a demand from the jewelery industry with types of baths ranging from citrate-based electrolytes to phosphate-based electrolytes.
- Hard gold from solutions of amocyanide buffered by the citric acid-potassium citrate system at a pH of between 4 and 5, and containing cobalt as the hardening metal of the deposit. These deposits are accompanied by a codeposition of carbon and nitrogen. There is therefore a contaminant formed during the electrodeposition of gold from such baths. The presence of this contaminant seems to be responsible for relatively strong deposit contact resistance in two different ways.
- the polymers increase the contact resistance of the deposit, not only by forming a film on the surface of the deposit but also by being present within this deposit. The formation of polymers is dependent on the availability of free cyanides in the electrolyte. The amount of polymer included in the deposit is also largely dependent on the cobalt content included.
- cobalt oxides on the surface of the deposit is also responsible for the contact resistance of the cobalt deposits, in particular by formation of a complex with free cyanides.
- Czech patent CS 107 253 1 describes a process for depositing two successive layers of hard, glossy gold using an electrolytic bath containing vanillin as a brightener at a concentration of 0.5 g / L, for an auropotassium cyanide concentration of 8 g / L, which corresponds to a vanillin concentration of the order of 0.1 mol per mol of gold to be deposited.
- the present invention makes it possible, in particular, to improve the electrodeposition rate of gold by allowing the use of gold electrolytes with high current densities, up to
- the invention relates to an electrolytic bath intended for the deposition of gold or gold alloys, this bath containing a well-defined auxiliary agent making it possible to considerably improve the rate of electrodeposition of the gold or of its alloys, while decreasing the contact resistance and allowing the use of high current densities.
- the invention relates to a process for the electrolytic deposition of gold or gold alloys on a substrate, using as an electrolytic bath the bath of the invention.
- the invention relates to a new use of a well-defined family of organic compounds having at least one aldehyde function as an auxiliary for improving the performance of a process for the electrolytic deposition of gold or alloys. gold on a substrate.
- the invention applies to all known processes implementing a step of electroplating gold or gold alloys, as well in the field of decoration as electronics and connectors. It is of particular interest in the case of processes for the electrolytic deposition of gold from a cyanide bath, in particular, from an electrolytic bath containing gold in the form of aurocyanide or auricyanide and especially in the case of gold deposits hardened by a secondary metal, in particular cobalt, iron or nickel.
- the invention relates to an aqueous electrolytic bath for the electrochemical deposition of gold or its alloys comprising at least one soluble gold compound intended to be deposited electrolytically and, optionally to minus a secondary metal compound intended to be codeposited as an alloy with gold, characterized in that it further comprises from 0.3 to 3 moles per mole of gold contained in the electrolytic bath of a compound organic compound comprising one or two aldehyde functions, said organic compound being: - either glyoxal or an organic compound comprising from 3 to 20 carbon atoms and one or two aldehyde functions in the form of:
- An aliphatic group linear, branched, saturated or unsaturated, or
- the invention according to this first aspect relates to an aqueous electrolytic bath for the electrochemical deposition of gold or its alloys.
- a bath intended for the electrolytic deposition of a metal differs from a chemical bath for deposition of the same metal not only by its conditions of implementation (current flow and presence of electrodes in the case of the electrochemical bath) but also by the nature of its constituents.
- a chemical bath will comprise a significant amount of reducing agents and will be characterized by the presence of a high concentration in free cyanides, while in an electrochemical bath we try to eliminate, as much as possible, the presence of free cyanides.
- the orders of magnitude of the deposition rates from a chemical bath and an electrochemical bath have nothing to do, which precludes a priori the use of chemical baths to make continuous deposits on substrates .
- the electrolytic bath can be constituted by any bath conventionally used for the electrodeposition of gold or gold alloys, as soon as it contains in addition a compound organic comprising one or two aldehyde functions as defined above.
- the electrolytic baths of the invention advantageously contain from 1.5 to 2.5 moles of said organic compound comprising one or two aldehyde functions per mole of gold, preferably of the order of 2 moles of said organic compound per mole of gold.
- aldehyde functional organic compound will depend both on the concentration of soluble gold salts in the bath and the molar mass of this aldehyde.
- the electrolytic baths of the invention advantageously contain gold contents which can vary widely but generally are between 1 and 100 g / L (the contents of soluble salts are related to the metal content).
- the content of compounds bearing one or two aldehyde functions can vary in very large proportions.
- the baths of the invention contain, depending on the molar base of the aldehyde, from 0.1 to 50 g / L of at least one organic compound comprising one or two aldehyde functions as defined previously.
- the family of organic compounds that can be used according to the invention as an auxiliary agent in an electrochemical deposition bath of gold or of gold alloys is either glyoxal which has the advantage of containing two aldehyde groups or an organic compound. comprising from 3 to 20 carbon atoms and at least one aldehyde function.
- the family of products that can be used according to the invention also comprises the salts of the above products and in particular the sulphonates, which furthermore have the advantage of having surface-active properties if they are sufficiently long.
- one of the above products will advantageously be chosen from those which are soluble in the medium or at least those which are soluble therein by adding, if appropriate, a surfactant or any other product making it possible to make the bath soluble.
- the organic compound with aldehyde function is glyoxal.
- the organic compounds used according to the invention will be chosen from aldehydes of formula R-CHO in which R is a linear or branched, saturated or unsaturated aliphatic group comprising from 3 to 12 carbon atoms.
- the alkyl chains comprising from 3 to 9 carbon atoms are preferably chosen.
- the organic compound comprises from 4 to 20 carbon atoms and comprises at least one saturated, unsaturated or aromatic ring or is in the form of a salt, in particular a sulphonate, of one of these compounds .
- a compound in which the ring, in particular the aromatic ring, is preferably chosen is chosen. at most two substituent groups.
- the organic compound comprises 4 to 20 carbon atoms and contains at least one saturated, unsaturated or aromatic heterocycle or is in the form of a salt, in particular a sulphonate, of one of these compounds.
- the organic compound used according to the invention will be selected from the group consisting of propionaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, 1-heptaldehyde, caprylic aldehyde, pelargonaldehyde, decanal undecanal, laurylaldehyde, glyoxal, glyoxalic acid, glyoxal-bis (sodium hydrogen sulfite), glyoxal-1,1-dimethyl acetal, acrolein, crotonal, benzaldehyde, phenylacetaldehyde, cuminic aldehyde, cinnamaldehyde, anisaldeh
- These alloy metals are generally selected from cobalt, nickel, iron, indium, cadmium, arsenic, manganese, tin, lead and copper.
- the preferred metals will be cobalt, nickel and iron. However, it is with cobalt that the effect of reducing the contact resistance due to the presence of the aldehyde-functional compound will be the clearest.
- the secondary metal is introduced into the bath in the form of sulphate, carbonate, hydroxide, oxide, acetylacetonate, citrate, gluconate, sulphamate or a mixture of these compounds.
- Brightening agents These brightening agents are all those conventionally used in the field of the electrolytic deposition of gold.
- the bath contains at least 10 g / L of a conductive salt, preferably selected from the group consisting of citrate, phosphate, borate or sulfate salts and mixtures thereof.
- a conductive salt preferably selected from the group consisting of citrate, phosphate, borate or sulfate salts and mixtures thereof.
- buffering agents for stabilizing the pH said buffer preferably being of the acetic, citric, boric, phosphoric or phthalic type.
- wetting agents preferably be of the acetic, citric, boric, phosphoric or phthalic type.
- tolyletriazol or benzotriazol is preferably chosen.
- the invention is particularly applicable to this type of bath, well known to have as disadvantage in the prior art of causing pollution of the electrolytic deposition by formation of polymers.
- the organic compound with aldehyde function according to the invention is found to be introduced particularly advantageously in baths in which the gold is in the form of auri- or aurocyanide but it can also be used in other baths with the effect of improving the performance of the electrolytic deposition. It may, in particular, be introduced into baths where the gold is in the form of aurosulphite, aurothiosulphate or gold chloride.
- the invention relates to a process for electroplating gold or a gold alloy, according to which the electrolysis of an electrolytic bath as defined above is carried out.
- the main advantages of introducing the aldehyde-functional organic compound are to improve the rate of electrodeposition, to decrease the contact resistance and to permit the use of particularly high current densities.
- the improvement of the invention is applicable to all types of electrolytic gold plating processes and for all types of application, whether in decoration, for the preparation of electronic components and connectors.
- the current densities used in the methods of the invention can vary over wide ranges, generally between 0.5 and 120 A / dm 2 . Of course, it will generally be used for applications in the field of decoration, current densities less than 10 A / dm 2 while for so-called "high speed” applications will use current densities of the order of 10 at 120 A / dm 2 , this type of high speed process is generally reserved for the field of electronics and connectors.
- the method of the invention insofar as it allows the use of particularly high current densities up to 120 A / dm 2 finds a particularly advantageous application in electronic applications where it is sought to work with a maximum deposition rate and where desired deposits should be, inter alia, shiny, ductile and non-porous.
- the baths used in this field must operate at the highest current densities possible, which allows in particular the use of auxiliaries used according to the invention.
- the baths of the invention can also be used at lower current speeds and densities and, in particular, in decorating applications.
- the improvement of the invention is applicable to all processes conventionally used for depositing gold or gold alloys.
- insoluble anodes preferably insoluble anodes and preferably platinized titanium, platinum coated with iridium oxide or precious metal such as platinum and a metallized substrate will be placed in cathode.
- the invention relates, according to a third aspect, to the use of an organic compound as defined above in an electrolytic bath intended for the electrolytic deposition of gold or a of its alloys, as an auxiliary agent improving the rate of electrodeposition of the gold or its alloys and / or reducing the contact resistance.
- the preferred bath formulations according to the present invention may be non-restrictively described by the following general composition in which the concentrations of metal derivatives (gold and possibly alloying metals) are referred to the metal: - Gold 1 to 100 g / L
- the substrate to be metallized is prepared by a suitable procedure, according to the nature of the metal.
- cuprous or nickel substrates are electrolytically degreased before, after rinsing with water, the substrate is depassivated in sulfuric acid diluted to 5-20% by volume, the substrate is rinsed with water de-ionized before being introduced into one of the electrolytes of the invention.
- some additives may be added.
- the conducting salt it is possible to use sodium sulphate, but also potassium sulphate or ammonium sulphate or a mixture thereof.
- An acetic, citric, boric, orthophosphoric, or other buffer system effective in the pH range of interest may be used to stabilize the pH of the bath.
- a wetting agent may be added to prevent hydrogen adsorption formed at the cathode during electrolysis and therefore avoid its inclusion in the deposit.
- a cationic, anionic or nonionic wetting agent may be suitable, for example benzotriazol may be used in a small amount.
- This bath deposits more than 99.9% gold, the deposit is bright, ductile, with a contact resistance of 12 mOhm, a low porosity and excellent resistance to corrosion. Its electrodeposition rate is 0.05 to 0.5 ⁇ m / min. it is ideally used in the so-called “fastening” or "dipping” processes.
- EXAMPLE 2 Decorative golden bath
- This bath deposits more than 99.9% gold, the deposit is bright, ductile, with a contact resistance of 5 mOhm, a low porosity and excellent resistance to corrosion. Its electrodeposition rate is 0.1 to 0.7 ⁇ m / min. It is ideally used in so-called “fastening” or “dipping” processes.
- This bath deposits gold at nearly 99.5%, the deposit is bright, ductile, with low contact resistance, low porosity and excellent resistance to corrosion.
- Cobalt acts here not only as a metallic brightener but also as a hardener alloy metal. It allows the deposit to have a good resistance to friction and pass positively test said "British Telecom”. It is ideally used in so-called “continuous” "selective deposition with masking” or “selective deposition” processes.
- the contact resistance is 5 mOhm after thermal aging of 1 hour at 250 ° C. As an indication, it is under the same conditions of 14 mOhm, when the bath does not contain aldehyde (measurement according to ASTM B667-97).
- the deposition rate is 0.5 to 11 ⁇ m / min with aldehyde, 0.4 to 8.5 ⁇ m / min without aldehyde, using a rotary cathode rotating at a speed of 1.5 as a deposition means. m / s or a jet deposit equipment.
- EXAMPLE 5 High-speed gold-nickel bath
- This bath deposits gold to almost 99.5%, the deposit is bright, ductile, with a contact resistance of 7 mOhm, a low porosity and excellent resistance to corrosion, and leads to a speed of
- Nickel acts as a metallic brightener and as a hardener alloy metal. It allows the deposit to present a good resistance to friction and to pass positively the test said "British
- This bath deposits gold at nearly 99.5%, the deposit is bright, ductile, with a contact resistance of 7 mOhm, a low porosity and excellent resistance to corrosion. It leads to a deposition rate of 0.5 to 11 ⁇ m / min.
- Cobalt acts as a metallic brightener and as a hardener alloy metal. It allows the deposit to have a good resistance to friction and pass positively test said "British Telecom". ". It is ideally used in the so-called “continuous”, “selective deposition with masking” or “selective deposition” processes.
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)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0111092A FR2828889B1 (fr) | 2001-08-24 | 2001-08-24 | Bain electrolytique pour le depot electrochimique de l'or et de ses alliages |
FR0111092 | 2001-08-24 | ||
PCT/FR2002/002922 WO2003018880A1 (fr) | 2001-08-24 | 2002-08-22 | Bain electrolytique pour le depot electrochimique de l'or et de ses alliages |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1423557A1 true EP1423557A1 (fr) | 2004-06-02 |
EP1423557B1 EP1423557B1 (fr) | 2004-12-22 |
Family
ID=8866724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02774881A Expired - Lifetime EP1423557B1 (fr) | 2001-08-24 | 2002-08-22 | Bain electrolytique pour le depot electrochimique de l'or et de ses alliages |
Country Status (7)
Country | Link |
---|---|
US (1) | US20040195107A1 (fr) |
EP (1) | EP1423557B1 (fr) |
CN (1) | CN1561407A (fr) |
AT (1) | ATE285489T1 (fr) |
DE (1) | DE60202378T2 (fr) |
FR (1) | FR2828889B1 (fr) |
WO (1) | WO2003018880A1 (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6828898B2 (en) * | 2003-04-03 | 2004-12-07 | Cts Corporation | Fuel tank resistor card having improved corrosion resistance |
US20050092616A1 (en) * | 2003-11-03 | 2005-05-05 | Semitool, Inc. | Baths, methods, and tools for superconformal deposition of conductive materials other than copper |
JP4945193B2 (ja) * | 2006-08-21 | 2012-06-06 | 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. | 硬質金合金めっき液 |
CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
CH710184B1 (fr) * | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
KR101079554B1 (ko) * | 2008-06-11 | 2011-11-04 | 니혼 고쥰도가가쿠 가부시키가이샤 | 전해 금도금액 및 그것을 이용하여 얻어진 금피막 |
EP2312021B1 (fr) | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
JP2011122192A (ja) * | 2009-12-09 | 2011-06-23 | Ne Chemcat Corp | 電解硬質金めっき液及びこれを用いるめっき方法 |
JP5731802B2 (ja) * | 2010-11-25 | 2015-06-10 | ローム・アンド・ハース電子材料株式会社 | 金めっき液 |
CN102586830B (zh) * | 2011-01-10 | 2015-12-09 | 深圳市奥美特科技有限公司 | 金属丝表面镀金或镀钯的设备及方法 |
CN103741180B (zh) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | 无氰光亮电镀金添加剂及其应用 |
KR102670599B1 (ko) * | 2015-06-26 | 2024-05-29 | 이이쟈 가부시키가이샤 | 전해 경질 금 도금액용 치환 방지제 및 그것을 포함하는 전해 경질 금 도금액 |
DE102019202899B3 (de) * | 2019-03-04 | 2019-11-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Wässrige Formulierung zum Herstellen einer Schicht aus Gold und Silber |
CN110344089B (zh) * | 2019-06-26 | 2021-11-09 | 深圳市瑞世兴科技有限公司 | 一种亚硫酸金钠镀液及其电镀方法 |
CN114836794B (zh) * | 2021-06-25 | 2024-01-30 | 深圳市铭轩珠宝首饰有限公司 | 一种金-铜合金电铸工艺及其应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2244434C3 (de) * | 1972-09-06 | 1982-02-25 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen |
SU709719A1 (ru) * | 1977-07-27 | 1980-01-15 | Предприятие П/Я М-5068 | Электролит золочени |
CH662583A5 (fr) * | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc. |
GB8612361D0 (en) * | 1986-05-21 | 1986-06-25 | Engelhard Corp | Gold electroplating bath |
JPS637390A (ja) * | 1986-06-26 | 1988-01-13 | Nippon Engeruharudo Kk | 金−コバルト合金めつき液 |
-
2001
- 2001-08-24 FR FR0111092A patent/FR2828889B1/fr not_active Expired - Fee Related
-
2002
- 2002-08-22 US US10/485,830 patent/US20040195107A1/en not_active Abandoned
- 2002-08-22 WO PCT/FR2002/002922 patent/WO2003018880A1/fr not_active Application Discontinuation
- 2002-08-22 CN CNA028191943A patent/CN1561407A/zh active Pending
- 2002-08-22 EP EP02774881A patent/EP1423557B1/fr not_active Expired - Lifetime
- 2002-08-22 DE DE60202378T patent/DE60202378T2/de not_active Expired - Fee Related
- 2002-08-22 AT AT02774881T patent/ATE285489T1/de not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
See references of WO03018880A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE60202378T2 (de) | 2005-12-08 |
WO2003018880A1 (fr) | 2003-03-06 |
EP1423557B1 (fr) | 2004-12-22 |
CN1561407A (zh) | 2005-01-05 |
FR2828889B1 (fr) | 2004-05-07 |
ATE285489T1 (de) | 2005-01-15 |
DE60202378D1 (de) | 2005-01-27 |
US20040195107A1 (en) | 2004-10-07 |
FR2828889A1 (fr) | 2003-02-28 |
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