EP0149830B2 - Electrolytic bath for the deposition of thin layers of pure gold - Google Patents
Electrolytic bath for the deposition of thin layers of pure gold Download PDFInfo
- Publication number
- EP0149830B2 EP0149830B2 EP19840115879 EP84115879A EP0149830B2 EP 0149830 B2 EP0149830 B2 EP 0149830B2 EP 19840115879 EP19840115879 EP 19840115879 EP 84115879 A EP84115879 A EP 84115879A EP 0149830 B2 EP0149830 B2 EP 0149830B2
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- EP
- European Patent Office
- Prior art keywords
- acid
- methylene
- phosphonic
- bath
- complexing agent
- 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.)
- Expired - Lifetime
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- 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 present invention relates to an electrolytic bath for depositing thin layers (of the order of at least 0.5 ⁇ ) of pure gold on passive surfaces (for example stainless steel, Ti, Mo, alloys based on Cr and of Ni).
- passive surfaces for example stainless steel, Ti, Mo, alloys based on Cr and of Ni.
- the baths used for the galvanic deposition of gold are generally prepared from solutions of potassium aurocyanide KAu (CN) 2 , to which various salts, acids or alkaline products are added, according to the methods, to improve the electrical conductivity of the bath and the crystallization conditions of the metal.
- the aurocyanide is only stable up to a pH of around 3 and, below this value, it decomposes into insoluble yellow CN gold cyanide and hydrocyanic acid HCN.
- very low pH baths is especially essential to deposit a thin layer of adherent pure gold on objects whose surface is highly passive, that is to say, for example stainless steel, alloys containing a high proportion of chromium and nickel, in titanium, in molybdenum, or on surfaces having previously undergone a galvanic chromium plating, a chemical nickel plating or a coating of molybdenum-manganese alloy.
- compositions as disclosed in the examples of US Pat. No. 4,168,214 are in practice unusable for obtaining electrolytic baths having a pH of less than about 0.4.
- these baths have the drawback, in particular with regard to environmental protection, of containing alkaline cyanides.
- the object of this invention therefore consists in providing an electrolytic bath on the deposit of thin layers (of the order of ⁇ C, 5, ⁇ ) of pure gold (24cts) on passive surfaces, which adhere perfectly to said passive surfaces and can be used as a bonding layer for the subsequent deposition of thicker layers of a gold alloy, this bath having a pH of at most 0.4.
- the electrolytic bath according to the invention contains from 0.5 to 20 g / I of gold in the form of an auricyanide of an alkali metal, in which the gold is trivalent, and at least an acid present in sufficient concentration for the pH of this bath to be at most 0.4 and is characterized in that the acid is at least one organic acid chosen from the group comprising sufamic acid, monochloroacetic acids, dichlo - racetic and trichloroacetic, malic acid, and 1-hydroxy-1, 1-ethylidene-diphosphoric, hydroxy-methyl-phosphoric and amino-tris (methylene-phosphonic) acids, and mixtures thereof, or else sulfuric acid in combination with at least one organic complexing agent chosen from the alkaline salts of diethylene-triamine-penta- (methylene-phosphonic), ethylene-diamine-tetra (methylene-phosphonic), hexamethylene-diamine-tetra acids - (
- this bath may contain the auricyanide in the form of potassium auricyanide KAu (CN) 4 or sodium auricyanide NaAu (CN) 4 , and its pH is preferably between 0.1 and 0.3.
- the acid concentration being relatively high, it does not prove necessary to add conductive salts, the solution being sufficiently electrically conductive.
- These acids can be used either alone or mixed with each other, in concentrations of 40 to 500 g / l, except for sulfamic acid, the solubility of which in water is limited and which can be present in 100 g / I at saturation, which is reached for a concentration of approximately 150 g / I at room temperature.
- complexing agents as well as other complexing agents such as amino-carbonic acids (see for example DE 3,012,999), cannot be used in large quantities because they risk precipitating.
- other compounds mentioned below can be introduced into the electrolytic bath according to the invention, therefore having a pH of less than 0.4, as complexing agents and without precipitating, in quantities at least greater than 20 g / I.
- These compounds are N-carboxymethyl-aspartic and N, N-bis (carboxymethyl) aspartic acids having the following formulas: or the salts thereof, as well as the compound represented by the following formula, where R is an alkyl or alkylene group having 1 to 5 C atoms, or the salts thereof.
- the baths are generally used at room temperature, with platinum titanium or graphite anodes.
- platinum titanium or graphite anodes For certain applications, in particular for coating particularly passive surfaces, it is possible to raise the working temperature of these baths up to 80 ° C.
- the chemicals which enter into their composition not being volatile, and having a perfect stability at this temperature, there does not follow any loss or any change in the behavior of the bath during electrolysis.
- a stainless steel wafer was treated in the bath, at room temperature, with a current density of 3 Aldm 2 for 5 minutes.
- the pure gold deposit obtained is both perfectly adherent to the substrate and brilliant.
- a stainless steel plate was treated in this bath, at room temperature, with a current density of 4 Aldm 2 for 4 minutes.
- the deposit obtained is both perfectly adherent and shiny.
- a stainless steel plate was treated in this bath, at room temperature, with a current density of 4 Aldm 2 for 3 minutes.
- the deposit obtained is both perfectly adherent and shiny.
- This bath was intentionally polluted with 50 mg / I of iron.
- the addition of 4 g / l of EDTA makes it possible to obtain, under the same electrolysis conditions, a deposit of pure yellow and shiny gold.
- the stainless steel plate treated in this bath at a current density of 5 A / dm 2 for 5 minutes, had an adherent and shiny gold layer of 0.2 to 0.3 ⁇
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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)
- Mechanical Treatment Of Semiconductor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
La présente invention concerne un bain électrolytique pour le dépôt de couches minces (de l'ordre de 0,5 µ au moins) d'or pur sur des surfaces passives (par exemple acier inoxydable, Ti, Mo, alliages à base de Cr et de Ni).The present invention relates to an electrolytic bath for depositing thin layers (of the order of at least 0.5 μ) of pure gold on passive surfaces (for example stainless steel, Ti, Mo, alloys based on Cr and of Ni).
Les bains utilisés pour la déposition galvanique de l'or sont en général préparés à partir de solutions d'auro- cyanure de potassium KAu(CN)2, auxquelles on ajoute différents sels, acides ou produits alcalins, selon les procédés, pour améliorer la conductibilité électrique du bain et les conditions de cristallisation du métal. L'auro- cyanure n'est toutefois stable que jusqu'à un pH d'environ 3 et, au-dessous de cette valeur, il se décompose en cyanure d'or Au CN jaune insoluble et un acide cyanhydrique HCN. Dans la pratique, il est parfois souhaitable de pouvoir déposer de l'or ou un alliage d'or en milieu très acide, donc en utilisant des solutions dont le pH est inférieur à 3. Pour y parvenir, il est nécessaire d'utiliser un sel d'or stable à un pH bas, ce qui est le cas pour l'auricyanure de potassium KAu(CN)4, dans lequel l'or est trivalent.The baths used for the galvanic deposition of gold are generally prepared from solutions of potassium aurocyanide KAu (CN) 2 , to which various salts, acids or alkaline products are added, according to the methods, to improve the electrical conductivity of the bath and the crystallization conditions of the metal. However, the aurocyanide is only stable up to a pH of around 3 and, below this value, it decomposes into insoluble yellow CN gold cyanide and hydrocyanic acid HCN. In practice, it is sometimes desirable to be able to deposit gold or a gold alloy in a very acid medium, therefore using solutions whose pH is less than 3. To achieve this, it is necessary to use a stable gold salt at low pH, which is the case for potassium auricyanide KAu (CN) 4 , in which gold is trivalent.
Ce complexe cyanuré d'or trivalent est déjà mentionné notamment dans le brevet US 4 168 214, qui décrit un bain contenant un cyanure de métal alcalin, un sel tel qu'un nitrate, et dont le pH est ajusté avec de l'acide chlorhydrique à 0,1-1,5.This cyanide complex of trivalent gold is already mentioned in particular in US Pat. No. 4,168,214, which describes a bath containing an alkali metal cyanide, a salt such as a nitrate, and the pH of which is adjusted with hydrochloric acid. at 0.1-1.5.
L'emploi de bains à pH très bas est surtout indispensable pour effectuer la déposition d'une couche mince d'or pur adhérente sur des objects dont la surface est fortement passive, c'est-à-dire par exemple en acier inoxydable, en alliages contenant une forte proportion de chrome et de nickel, en titane, en molybdène, ou sur des surfaces ayant subi préalablement un chromage galvanique, un nickelage chimique ou un revêtement d'alliage molybdène-manganèse.The use of very low pH baths is especially essential to deposit a thin layer of adherent pure gold on objects whose surface is highly passive, that is to say, for example stainless steel, alloys containing a high proportion of chromium and nickel, in titanium, in molybdenum, or on surfaces having previously undergone a galvanic chromium plating, a chemical nickel plating or a coating of molybdenum-manganese alloy.
Toutefois, les compositions telles que divulguées dans les exemples du brevet US 4 168 214 sont en pratique inutilisables pour obtenir des bains électrolytiques ayant un pH inférieur à environ 0,4. De plus ces bains présentent l'inconvénient, notamment à l'égard de la protection de l'environnement, de contenir des cyanures alcalins.However, the compositions as disclosed in the examples of US Pat. No. 4,168,214 are in practice unusable for obtaining electrolytic baths having a pH of less than about 0.4. In addition, these baths have the drawback, in particular with regard to environmental protection, of containing alkaline cyanides.
Le but de cette invention consiste donc à fournir un bain électrolytique sur le dépôt de couches minces (de l'ordre de < C,5,µ) d'or pur (24cts) sur des surfaces passives, qui adhérent parfaitement auxdites surfaces passives et pouvant servir de couche d'accrochage pour le dépôt subséquent de couches plus épaisses d'un alliage d'or, ce bain ayant un pH d'au plus 0,4.The object of this invention therefore consists in providing an electrolytic bath on the deposit of thin layers (of the order of <C, 5, μ) of pure gold (24cts) on passive surfaces, which adhere perfectly to said passive surfaces and can be used as a bonding layer for the subsequent deposition of thicker layers of a gold alloy, this bath having a pH of at most 0.4.
Le bain électrolytique selon l'invention, visant à atteindre le but précité, contient de 0,5 à 20 g/I d'or sous forme d'auricyanure d'un métal alcalin, dans lequel l'or est trivalent, et au moins un acide présent en concentration suffisante pour que le pH de ce bain soit au plus de 0,4 et est caractérisé en ce que l'acide est au moins un acide organique choisi parmi le groupe comprenant l'acide sufamique, les acides monochloracétique, dichlo- racétique et trichloracétique, l'acide malique, et les acides 1-hydroxy-1 ,1-éthylidène-diphosphorique, hydroxy- méthyl-phosphorique et amino-tris(méthylène-phosphonique), et les mélanges de ceux-ci, ou bien l'acide sulfurique en combinaison avec au moins un agent complexant organique choisi parmi les sels alcalins des acides diéthylène-triamine-penta-(méthylène-phosphonique), éthylène-diamine-tétra(méthylène-phosphoni- que), hexaméthylène-diamine-tétra-(méthylène-phosphonique) et éthylène-diamine-tétraacétique, et les mélanges de ceux-ci, l'acide N-carboxyméthyl-aspartique et l'acide N,N-bis(carboxyméthyl) aspartique, ou un sel de ceux-ci, et un composé ayant la formule suivante :
Plus précisément, ce bain peut contenir l'auricyanure sous forme d'auricyanure de potassium KAu(CN)4 ou d'auricyanure de sodium NaAu(CN)4, et son pH est de préférence compris entre 0,1 et 0,3. En outre, la concentration en acide étant relativement élevée, il ne s'avère pas nécessaire de procéder à l'adjonction de sels conducteurs, la solution étant suffisamment conductrice de l'électricité.More specifically, this bath may contain the auricyanide in the form of potassium auricyanide KAu (CN) 4 or sodium auricyanide NaAu (CN) 4 , and its pH is preferably between 0.1 and 0.3. In addition, the acid concentration being relatively high, it does not prove necessary to add conductive salts, the solution being sufficiently electrically conductive.
Ces acides peuvent être utilisés soit seuls, soit mélangés les uns avec les autres, en concentrations de 40 à 500 g/I, sauf pour l'acide sulfamique dont la solubilité dans l'eau est restreinte et qui peut être présent de 100 g/I à la saturation, qui est atteinte pour une concentration d'environ 150 g/I à la température ambiante.These acids can be used either alone or mixed with each other, in concentrations of 40 to 500 g / l, except for sulfamic acid, the solubility of which in water is limited and which can be present in 100 g / I at saturation, which is reached for a concentration of approximately 150 g / I at room temperature.
Lors du traitement de pièces dans le bain précédemment, certains métaux peuvent passer en solution et, comme impuretés, perturber le dépôt d'or pur. On peut y remédier en ajoutant dans le bain d'or très acide des complexants organiques, par exemple des sels de sodium, de potassium, d'ammonium ou d'amines des acides diéthylène-triamine-penta(méthylène-phosphorique), éthylène-diamine-tétra(méthylène-phosphorique) et éthylène-diamine-tétra-acétique (EDTA), qui sont de préférence utilisés en concentrations de 1 à 20 g/I.When treating parts in the bath previously, certain metals may go into solution and, as impurities, disturb the deposition of pure gold. This can be remedied by adding organic complexing agents, for example sodium, potassium, ammonium or amine salts, to the highly acidic gold bath. diethylene-triamine-penta (methylene-phosphoric), ethylene-diamine-tetra (methylene-phosphoric) and ethylene-diamine-tetra-acetic (EDTA), which are preferably used in concentrations of 1 to 20 g / l.
Les exemples de complexants ci-dessus, de même que d'autres complexants tels que des acides amino- carboniques (voir par exemple DE 3 012 999), ne peuvent pas être utilisés en quantités importantes car ils risquent de précipiter. On a par contre trouvé que d'autres composés mentionnés ci-après peuvent être introduits dans le bain électrolytique selon l'invention, ayant donc un pH inférieur à 0,4, en tant qu'agents complexants et sans précipiter, en quantités au moins supérieures à 20 g/I. Ces composés sont les acides N-carboxyméthyl-aspartique et N,N-bis(carboxyméthyl) aspartique ayant les formules suivantes :
Les bains sont utilisés généralement à la température ambiante, avec des anodes en titane platiné ou en graphite. Pour certaines applications, en particulier pour le revêtement de surfaces particulièrement passives, il est possible d'élever la température de travail de ces bains jusqu'à 80 °C. Les produits chimiques qui entrent dans leur composition n'étant pas volatils, et présentant une parfaite stabilité à cette température, il ne s'ensuit aucune perte ni aucun changement dans le comportement du bain lors de l'électrolyse.The baths are generally used at room temperature, with platinum titanium or graphite anodes. For certain applications, in particular for coating particularly passive surfaces, it is possible to raise the working temperature of these baths up to 80 ° C. The chemicals which enter into their composition not being volatile, and having a perfect stability at this temperature, there does not follow any loss or any change in the behavior of the bath during electrolysis.
Les exemples qui suivent illustrent l'invention en donnant notamment plusieurs possibilités de compositions de bains utilisables pratiquement. Dans chacun de ceux-ci, la surface des objets traités dans le bain d'or a été préalablement décapé selon les procédés préparatoires habituels.The examples which follow illustrate the invention by giving in particular several possibilities of practically usable bath compositions. In each of these, the surface of the objects treated in the gold bath was previously pickled according to the usual preparatory processes.
Une plaquette en acier inoxydable a été traitée dans le bain, à température ambiante, avec une densité de courant de 3 Aldm2 pendant 5 minutes. Le dépôt d'or pur obtenu est à la fois parfaitement adhérent au substrat et brillant.A stainless steel wafer was treated in the bath, at room temperature, with a current density of 3 Aldm 2 for 5 minutes. The pure gold deposit obtained is both perfectly adherent to the substrate and brilliant.
Une plaquette en acier inoxydable a été traitée dans ce bain, à température ambiante, avec une densité de courant de 4 Aldm2 pendant 4 minutes. Le dépôt obtenu est à la fois parfaitement adhérent et brillant.A stainless steel plate was treated in this bath, at room temperature, with a current density of 4 Aldm 2 for 4 minutes. The deposit obtained is both perfectly adherent and shiny.
Une plaquette en acier inoxydable a été traitée dans ce bain, à température ambiante, avec une densité de courant de 4 Aldm2 pendant 3 minutes. Le dépôt obtenu est à la fois parfaitement adhérent et brillant.A stainless steel plate was treated in this bath, at room temperature, with a current density of 4 Aldm 2 for 3 minutes. The deposit obtained is both perfectly adherent and shiny.
Ce bain a été intentionnellement pollué par 50 mg/I de fer. Le dépôt obtenu sur une plaquette d'acier inoxydable avec une densité de courant de 3 A/dm2, durant 2 minutes, est alors sombre, brunâtre et terne. L'adjonction de 4 g/I d'EDTA permet d'obtenir, dans les mêmes conditions d'électrolyse, un dépôt d'or pur jaune et brillant.This bath was intentionally polluted with 50 mg / I of iron. The deposit obtained on a stainless steel wafer with a current density of 3 A / dm 2 , for 2 minutes, is then dark, brownish and dull. The addition of 4 g / l of EDTA makes it possible to obtain, under the same electrolysis conditions, a deposit of pure yellow and shiny gold.
La plaquette en acier inoxydable traitée dans ce bain, à une densité de courant de 5 A/dm2 pendant 5 minutes, présentait une couche d'or adhérente et brillante de 0,2 à 0,3 µThe stainless steel plate treated in this bath, at a current density of 5 A / dm 2 for 5 minutes, had an adherent and shiny gold layer of 0.2 to 0.3 µ
Aucun précipité n'a été constaté, alors qu'un bain identique, mais contenant la même quantité d'EDTA, au lieu du complexant mentionné ci-dessus, devient rapidement trouble par suite de la formation d'un précipitéNo precipitate has been found, while an identical bath, but containing the same amount of EDTA, instead of the complexing agent mentioned above, quickly becomes cloudy as a result of the formation of a precipitate.
L'utilisation de ce bain a conduit à des résultats similaires à ceux obtenus avec le bain de l'exemple 5 .The use of this bath led to results similar to those obtained with the bath of Example 5.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH6961/83 | 1983-12-29 | ||
| CH696183A CH665656A5 (en) | 1983-12-29 | 1983-12-29 | ACID GOLD BATH AND USE OF THIS BATH IN ELECTROPLASTY. |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0149830A2 EP0149830A2 (en) | 1985-07-31 |
| EP0149830A3 EP0149830A3 (en) | 1986-10-15 |
| EP0149830B1 EP0149830B1 (en) | 1989-04-05 |
| EP0149830B2 true EP0149830B2 (en) | 1992-05-13 |
Family
ID=4317752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19840115879 Expired - Lifetime EP0149830B2 (en) | 1983-12-29 | 1984-12-20 | Electrolytic bath for the deposition of thin layers of pure gold |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0149830B2 (en) |
| CH (1) | CH665656A5 (en) |
| DE (2) | DE149830T1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3902977A (en) * | 1973-12-13 | 1975-09-02 | Engelhard Min & Chem | Gold plating solutions and method |
| AT353071B (en) * | 1977-10-06 | 1979-10-25 | Oxy Metal Industries Corp | CYANIDE-FREE BASIC SULPHITE BATH FOR ELECTROLYTIC FILLING OF GOLD-ZINC ALLOYS |
| US4168214A (en) * | 1978-06-14 | 1979-09-18 | American Chemical And Refining Company, Inc. | Gold electroplating bath and method of making the same |
| GB2038361B (en) * | 1978-11-11 | 1983-08-17 | Ibm | Trivalent chromium plating bath |
| DE3012999C2 (en) * | 1980-04-03 | 1984-02-16 | Degussa Ag, 6000 Frankfurt | Bath and process for the galvanic deposition of high-gloss and ductile gold alloy coatings |
| DE3021665A1 (en) * | 1980-06-10 | 1981-12-17 | Degussa Ag, 6000 Frankfurt | STRONG ACID GOLD ALLOY BATH |
-
1983
- 1983-12-29 CH CH696183A patent/CH665656A5/en not_active IP Right Cessation
-
1984
- 1984-12-20 EP EP19840115879 patent/EP0149830B2/en not_active Expired - Lifetime
- 1984-12-20 DE DE1984115879 patent/DE149830T1/en active Pending
- 1984-12-20 DE DE8484115879T patent/DE3477588D1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE149830T1 (en) | 1985-10-24 |
| DE3477588D1 (en) | 1989-05-11 |
| EP0149830A3 (en) | 1986-10-15 |
| EP0149830B1 (en) | 1989-04-05 |
| EP0149830A2 (en) | 1985-07-31 |
| CH665656A5 (en) | 1988-05-31 |
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