EP3964610A1 - Bain d'électrodéposition pour revêtements palladium-ruthénium - Google Patents

Bain d'électrodéposition pour revêtements palladium-ruthénium Download PDF

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Publication number
EP3964610A1
EP3964610A1 EP21193782.6A EP21193782A EP3964610A1 EP 3964610 A1 EP3964610 A1 EP 3964610A1 EP 21193782 A EP21193782 A EP 21193782A EP 3964610 A1 EP3964610 A1 EP 3964610A1
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Prior art keywords
weight
coating
electrolyte bath
ions
palladium
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Pending
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EP21193782.6A
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German (de)
English (en)
Inventor
Christian GARHÖFER
Claudia GARHÖFER-ONDREICSKA
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Iwg Ing W Garhoefer GmbH
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Iwg Ing W Garhoefer GmbH
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Publication of EP3964610A1 publication Critical patent/EP3964610A1/fr
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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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • 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
    • 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
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the invention relates to an electrolytic bath for depositing binary palladium-ruthenium alloys, a composition for such an electrolytic bath, the use of such an electrolytic bath, a method for coating with such an electrolytic bath, a coating and an object coated with the coating.
  • palladium coatings are also used in industrial applications, especially in the electronics industry, as a replacement for gold coatings because they are harder and more abrasion-resistant.
  • the object is therefore to provide an electrolyte bath from which a coating can be deposited, which is more cost-effective, in particular compared to pure palladium, and which has high abrasion resistance and good corrosion resistance, the coating being particularly shiny and having a light color, preferably L* ⁇ 82 in the CIELAB color space.
  • an electrolytic bath for the cathodic deposition of a binary Pd/Ru alloy with 30% by weight to 70% by weight Pd and 70% by weight - 30% by weight Ru the electrolytic bath being in the form of an aqueous solution with a pH of 7, 5 to pH 9.0, containing ammonium ions, and containing 0.5 g/l to 5 g/l Pd ions, 2 g/l to 10 g/l rulones, 0.5 g/l to 4 g / l of an amphoteric surfactant as a wetting agent and a glazing agent are included.
  • a binary palladium-ruthenium alloy which is particularly abrasion-resistant and has good corrosion resistance can be deposited from such an electrolyte bath.
  • a coating deposited from the electrolytic bath according to the invention is just as corrosion-resistant as a pure palladium coating of the same layer thickness.
  • a good adhesive strength is achieved.
  • the coating is not very brittle and cracking can be avoided.
  • the inexpensive, abrasion-resistant coating is therefore particularly suitable, for example, for use in the electronics industry, especially for plug connections.
  • the coating is glossy and has a light hue with L* ⁇ 82 in the CIELAB color space. This is particularly advantageous for decorative objects, in particular costume jewellery.
  • the stated amounts correspond to approximately 4.7 mmol to 47 mmol of Pd ions, approximately 0.02 mol/l to 0.1 mol/l of Ru ions and approximately 1.5 mmol/l to 12 mmol/l of the amphoteric surfactant .
  • the pH can preferably be adjusted with ammonia water. This simplifies bath management. It is also possible to adjust the pH with another basic substance. eg. sodium or potassium hydroxide or an amine.
  • An electrolyte bath with 1 g/l to 3 g/l Pd ions is particularly suitable. This corresponds to approx. 9.4 mmol/l to 28.2 mmol/l Pd ions.
  • the Pd ions are present in divalent form, the Pd ions being present in particular from palladium chloride, palladium tetramine sulfate, palladium diaminodinitrite, palladium diaminodichloride.
  • an electrolytic bath containing 4 g/l to 8 g/l of Ru ions is preferred. This corresponds to about 0.04 mol/l to 0.08 mol/l Ru ions.
  • Ru ions are present from complex Ru compounds.
  • the cation is preferably monovalent, with ammonium, lithium, sodium or potassium, for example, being suitable.
  • An electrolyte bath with 1 g/l to 3 g/l Pd ions and 4 g/l to 8 g/l Ru ions is particularly preferred.
  • Amphoteric surfactants that are particularly useful as wetting agents are betaines or sulphobetaines.
  • wetting agents can also be present, in particular alkyl ether sulfonates, alkyl ether phosphates, or preferably fatty alcohol alkoxylates.
  • the glazing agent is advantageously a glazing agent from the group of substituted aromatic N-heterocycles or from a mixture of substituted aromatic N-heterocycles.
  • Examples of connections include in US3458409 , US3972787 , as DE 4412253 disclosed.
  • a stress reducer can be included, in particular saccharin or an organic sulfonate.
  • Conductive salts and/or pH stabilizers can be included in order to simplify bath management, in particular ammonium, sodium or potassium phosphate, sulfate, nitrate, chloride, citrate, tartrate or succinate.
  • the electrolyte bath is in the form of a clear solution, the solution being in particular free of precipitates.
  • concentration of the metal salts, wetting agents, the brightening agent and the additional ingredients can be selected such that the electrolyte solution is clear and remains clear during the implementation of the coating process.
  • the coating obtained is particularly shiny, adherent, free of cracks, and resistant to abrasion and corrosion.
  • a particularly advantageous electrolyte bath comprises 2 g/l Pd ions from palladium diamminodichloride, 8 g/l Ru ions from sodium diaquooctachloronitridodiruthenate, 60 g/l ammonium sulfate, 80 g/l lactic acid, 4 g/l betaine as a wetting agent, 0.2 g/l 1 Fatty alcohol ethoxylate as an additional wetting agent, 2 g/l saccharin as a tension reducer, 4 ml/l of a mixture of substituted aromatic N-heterocycles as a glazing agent, the pH value being adjusted to 8.0 with ammonia water.
  • Exemplary substituted aromatic N-heterocycles that act as brighteners can be found, among others, in US3458409 , US3972787 as DE 4412253 being found.
  • an electrolytic bath as described above for the galvanic coating of an object with an electrically conductive surface, a binary Pd/Ru alloy with 30% by weight to 70% by weight Pd and 70% by weight to 30% by weight Ru being cathodic is deposited.
  • a coating with high abrasion resistance and good corrosion resistance is achieved, which can be produced inexpensively and has an advantageous light color.
  • Bath management with the electrolyte bath is particularly simple.
  • a use of the electrolyte bath is suitable, for example, for an object made of a metal, a metal alloy or a plastic that has been pretreated for electroplating.
  • the bath is particularly suitable for depositing layers with a thickness of 0.1 to 3 ⁇ m, in particular 0.5 to 2 ⁇ m.
  • Also according to the invention is a method for producing a coating using an electrolyte bath as described above. It can be provided that the object to be coated is immersed in the electrolyte bath and a voltage is applied to the electrodes, with a current density of between 0.01 A/dm 2 and 5 A/dm 2 being set. The object is connected as a cathode. The process can be carried out particularly advantageously when the bath is maintained at a temperature of 35°C to 65°C.
  • Anodes that are insoluble in this way are preferably those made from a material selected from the group consisting of platinized titanium and iridium transition metal mixed oxide or combinations of these materials. Platinum-coated titanium anodes are particularly preferred.
  • a current density of 0.05 to 1 A/dm 2 is particularly suitable.
  • a current density of 0.2 to 5 A/dm 2 is particularly suitable.
  • the coating is also a coating, in particular produced in a method described above, wherein the coating consists of a binary alloy of 30% by weight to 70% by weight Pd and 70% by weight to 30% by weight Ru and has a whiteness of L* ⁇ 82 in the CIELAB color space.
  • the coating has high abrasion resistance and good corrosion resistance. Due to the light color, the coating is particularly suitable for fashion jewelry.
  • the coating can be provided as the outermost final layer, since it has a particularly elegant appearance.
  • a coating with a layer thickness between 0.1 and 3 ⁇ m is particularly advantageous.
  • the coating With a layer thickness of 0.05 to 2 ⁇ m, the coating is particularly well suited as a diffusion barrier layer in a multi-layer coating system.
  • a diffusion barrier layer can a diffusion of copper ions from the for Avoid fashion jewelry items commonly used copper sub-layer in the outermost final layer, so that there is no tarnishing of the final layer.
  • According to the invention is also an object, in particular a costume jewelery or decorative article, coated with a coating described above.
  • Such an object in particular a piece of costume jewelry, has good durability even with longer and more frequent use.
  • the coating makes it possible to dispense with coatings containing nickel, so that such an object is particularly physiologically compatible.
  • the coating can be provided as the outermost final layer since it has a noble appearance. It is also possible that the coating is provided as an intermediate layer in a multi-layer coating system.
  • the object can consist, for example, of copper, brass, tin, zinc, iron, steel or their alloys. It is also possible to coat plastics prepared for electroplating.
  • the article can advantageously be coated with a multi-layer coating system, the coating being provided as an intermediate layer.
  • the coating is provided as a diffusion barrier layer, it being preferably provided that the coating has a layer thickness of 0.05 to 2 ⁇ m.
  • the coating with 0.2 to 3 ⁇ m, in particular with 1 ⁇ m, is particularly suitable as an anti-corrosion layer.
  • the object is coated with a coating system, the coating system having an underlayer made of copper, the coating being arranged over the copper layer, and a final layer comprising at least one noble metal, in particular gold or rhodium, over the coating , is arranged.
  • a coating system having an underlayer made of copper, the coating being arranged over the copper layer, and a final layer comprising at least one noble metal, in particular gold or rhodium, over the coating , is arranged.
  • a bronze layer in particular made of a Cu/Sn/Zn alloy, is arranged between the copper layer and the coating.
  • an adhesive gold layer is arranged directly over the coating.
  • Such a bonding gold layer can have a thickness of 0.05 to 0.3 ⁇ m.
  • the outer final layer can be made of a noble metal, in particular gold, rhodium, platinum, ruthenium or an alloy thereof.
  • the coating is particularly suitable for objects that have an outer final layer made of a rhodium-ruthenium alloy, in particular a binary alloy with 70% by weight to 90% by weight rhodium, preferably with 80% by weight rhodium.
  • a costume jewelery article has therefore proven to be particularly advantageous with a coating system comprising an underlayer of copper, in particular a bronze layer arranged directly above it, a previously described coating arranged above it, and an outermost final layer of a binary rhodium-ruthenium alloy arranged directly above the coating 70% to 90% by weight rhodium.
  • a coating system comprising an underlayer of copper, in particular a bronze layer arranged directly above it, a previously described coating arranged above it, and an outermost final layer of a binary rhodium-ruthenium alloy arranged directly above the coating 70% to 90% by weight rhodium.
  • Example 1 Various alloy compositions
  • the pH was adjusted to 8.0 using ammonia water.
  • the indication of g/l Pd relates to palladium ions, and the indication of g/l Ru also relates to ruthenium ions.
  • Test plates made of brass were electrolytically degreased in a weakly alkaline, cyanide-free cleaner, "Degreasing 1018", product from Ing. W. Garhöfer GesmbH) at 25° C. for 30 s at 10 A/dm 2 .
  • test slides were then rinsed in deionized water and pickled in 5% sulfuric acid solution for 30 seconds.
  • an acidic copper bath with 50 g/l Cu and 60 g/l sulfuric acid ("IWG Cu 550", product of Ing. W. Garhöfer GesmbH)
  • 20 ⁇ m copper were leveled and given a high gloss finish at 4 A/dm 2 and 25° C deposited.
  • the test slides were rinsed again.
  • the whiteness L* is >82 from palladium alloy concentrations of 30% by weight. This is shown in Table 1. 1 shows that at a concentration of 30 wt.% palladium, there is an unexpected, sudden increase in L* values, almost reaching the whiteness of pure palladium.
  • the exemplary coating is particularly suitable for any metallic white, decorative coating, e.g. of costume jewellery, due to its good durability and light colour. Due to the good corrosion resistance and the improved abrasion resistance, the alloys are also particularly suitable for industrial applications, such as in the electronics industry in particular.
  • Example 2 Coating of a brass jewelry blank
  • a brass jewelry blank was coated with an exemplary electrolytic bath.
  • the pH was adjusted to 8.0 using ammonia water.
  • the indication of g/l Pd relates to palladium ions, and the indication of g/l Ru also relates to ruthenium ions.
  • the brass jewelery blank to be coated was electrolytically degreased in a weakly alkaline, cyanide-free cleaner, "Degreasing 1018", product from Ing. W. Garhöfer GesmbH) at 25° C. for 30 s at 10 A/dm 2 .
  • the jewelry blank was then rinsed in deionized water and pickled in 5% sulfuric acid solution for 30 seconds.
  • an acidic copper bath with 50 g/l Cu and 60 g/l sulfuric acid ("IWG Cu 550", product of Ing. W. Garhöfer GesmbH)
  • 20 ⁇ m copper were leveled and given a high gloss finish at 4 A/dm 2 and 25° C deposited.
  • the blank was rinsed again.
  • Corrosion resistance according to DIN 50018 The corrosion resistance of the galvanized jewelery part was tested in accordance with DIN 50018, test in an alternating condensation climate with an atmosphere containing sulfur dioxide, June 1997.
  • the corrosion resistance of the palladium-ruthenium alloy was just as good in comparison with a coating made of a pure palladium electrolyte (Gapal TS, product from Garhöfer GesmbH), produced on the same base material in the SO 2 test.
  • Gapal TS pure palladium electrolyte
  • Abrasion resistance using Taser Abraser A brass disc was coated in the above electrolytic bath according to the process described above. As a comparison, a brass disk was coated with 2 ⁇ m palladium in a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH). Both panes were then rubbed down. The pure palladium was worn through much earlier than the palladium-ruthenium alloy.
  • Example 3 Coating of an object made of die-cast zinc
  • the jewelery blank was electrolytically degreased in a weakly alkaline, cyanide-free cleaner (Degreasing 1018, product from Ing. W. Garhöfer GesmbH) at 25° C. for 30 seconds at 10 A/dm 2 .
  • the jewelery blank was then rinsed in deionized water and 5 ⁇ m copper were treated at 1 A/min in an alkaline cyanide pre-copper bath with 22 g/l Cu and 34 g/l KCN ("Cuproga", product from Ing. W. Garhöfer GesmbH). dm 2 and 50 °C deposited.
  • the pre-coppered jewelry blank was then pickled in 5% sulfuric acid solution for 30 seconds.
  • 5% sulfuric acid solution for 30 seconds.
  • an acidic copper bath with 50 g/l Cu and 60 g/l sulfuric acid ("IWG Cu 550", product of Ing. W. Garhöfer GesmbH)
  • 15 ⁇ m copper were leveled and given a high gloss finish at 4 A/dm 2 and 25° C deposited.
  • the article thus copper-plated was rinsed and pre-dipped in a 10% KCN solution.
  • the piece of jewelery obtained in this way was, after renewed rinsing and acid immersion, treated with 0.1 ⁇ m adhesive gold from a weakly acidic electrolyte with 2.5 g/l Au ("MC 218", product from Ing. W. Garhöfer GesmbH) at 1.5 A/dm 2 and 35 °C provided. Then it was carefully rinsed in demineralized water, pickled in 5% sulfuric acid solution and treated with 0.2 ⁇ m rhodium from an electrolyte with 2 g/l Rh and 50 g/l sulfuric acid ("Rhodium C2", product from Ing. W. Garhöfer GesmbH) rhodium-plated at 3V and 35 °C.
  • Corrosion resistance according to DIN 50018 The electroplated piece of jewelery performed as well in the corrosion tests as a piece of jewelery coated using the same method but with pure palladium.
  • the jewelery blank was electrolytically degreased in a weakly alkaline, cyanide-free cleaner (Degreasing 1018, product from Ing. W. Garhöfer GesmbH) at 25° C. for 30 seconds at 10 A/dm 2 .
  • the jewelry blank was then rinsed in deionized water and in an alkaline cyanide pre-copper bath 22 g/l Cu and 34 g/l KCN ("Cuproga", product of Ing. W. Garhöfer GesmbH) were deposited on 5 ⁇ m copper at 1 A/dm 2 and 50°C.
  • the pre-coppered jewelry blank was then pickled in 5% sulfuric acid solution for 30 seconds.
  • the piece of jewelery obtained in this way was, after renewed rinsing and acid immersion, treated with 0.1 ⁇ m adhesive gold from a weakly acidic electrolyte with 2.5 g/l Au ("MC 218", product from Ing. W. Garhöfer GesmbH) at 1.5 A/dm 2 and 35 °C provided. Then it was carefully rinsed in demineralized water, pickled in 5% sulfuric acid solution and treated with 0.2 ⁇ m rhodium from an electrolyte with 2 g/l Rh and 50 g/l sulfuric acid ("Rhodium C2", product from Ing. W. Garhöfer GesmbH) rhodium-plated at 3V and 35 °C.
  • Corrosion resistance according to DIN 50018 The electroplated piece of jewelery performed as well in the corrosion tests as a piece of jewelery coated using the same method but with pure palladium.
  • Example 5 Coating of an object made of cast brass
  • the jewelery blank was electrolytically degreased in a weakly alkaline, cyanide-free cleaner (Degreasing 1018, product from Ing. W. Garhöfer GesmbH) at 25° C. for 30 seconds at 10 A/dm 2 .
  • the jewelery blank was then rinsed in deionized water and 5 ⁇ m copper were treated at 1 A/min in an alkaline cyanide pre-copper bath with 22 g/l Cu and 34 g/l KCN ("Cuproga", product from Ing. W. Garhöfer GesmbH). dm 2 and 50 °C deposited.
  • the pre-coppered jewelry blank was then pickled in 5% sulfuric acid solution for 30 seconds.
  • an acidic copper bath with 50 g/l Cu and 60 g/l sulfuric acid ("IWG Cu 550", product of Ing. W. Garhöfer GesmbH)
  • 15 ⁇ m copper were leveled and given a high gloss finish at 4 A/dm 2 and 25° C deposited.
  • the article thus copper-plated was rinsed and pre-dipped in a 10% KCN solution.
  • 2 ⁇ m bronze alloy was then deposited from the electrolyte at 60° C. and 1 A/dm 2 within 10 minutes from a bronze electrolyte bath (“white bronze CT 15 LF, product from Ing. W. Garhöfer GesmbH). This was followed by deionized water rinsed and pickled in 5% sulfuric acid solution.
  • the piece of jewelery obtained in this way was, after renewed rinsing and acid immersion, treated with 0.1 ⁇ m adhesive gold from a weakly acidic electrolyte with 2.5 g/l Au ("MC 218", product from Ing. W. Garhöfer GesmbH) at 1.5 A/dm 2 and 35 °C provided. Then it was carefully rinsed in demineralized water, pickled in 5% sulfuric acid solution and treated with 0.2 ⁇ m rhodium from an electrolyte with 2 g/l Rh and 50 g/l sulfuric acid ("Rhodium C2", product from Ing. W. Garhöfer GesmbH) rhodium-plated at 3V and 35 °C.
  • Corrosion resistance according to DIN 50018 The electroplated piece of jewelery performed as well in the corrosion tests as a piece of jewelery coated using the same method but with pure palladium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP21193782.6A 2020-09-08 2021-08-30 Bain d'électrodéposition pour revêtements palladium-ruthénium Pending EP3964610A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ATA50754/2020A AT523922B1 (de) 2020-09-08 2020-09-08 Elektrolytbad für Palladium-Ruthenium-Beschichtungen

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EP3964610A1 true EP3964610A1 (fr) 2022-03-09

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Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020131371A1 (de) * 2020-11-26 2022-06-02 Umicore Galvanotechnik Gmbh Rutheniumlegierungsschicht und deren Schichtkombinationen

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3458409A (en) 1964-10-12 1969-07-29 Shinichi Hayashi Method and electrolyte for thick,brilliant plating of palladium
US3576724A (en) 1967-10-18 1971-04-27 Int Nickel Co Electrodeposition of rutenium
US3972787A (en) 1974-06-14 1976-08-03 Lea-Ronal, Inc. Palladium electrolyte baths utilizing quaternized pyridine compounds as brighteners
US4082625A (en) 1976-06-08 1978-04-04 The International Nickel Company, Inc. Electrodeposition of ruthenium
DE4412253A1 (de) 1993-04-07 1994-10-13 Atotech Deutschland Gmbh Elektrolytische Abscheidung von Palladium oder Palladiumlegierungen
EP0916747A1 (fr) * 1997-11-15 1999-05-19 AMI Doduco GmbH Bain électrolytique pour le dépÔt de palladium et d'alliages de palladium
WO2009110598A1 (fr) * 2008-03-06 2009-09-11 日鉱商事株式会社 Produit à placage d'alliage ruthénium-palladium et son procédé de fabrication
EP3067444A2 (fr) * 2015-03-09 2016-09-14 Ing. W. Garhöfer Gesellschaft mbH Separation de revetements decoratifs en alliage palladium-fer sur des substances metalliques

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NL135500C (fr) * 1964-03-04
CH512590A (fr) * 1970-03-20 1971-09-15 Sel Rex Corp Procédé pour le dépôt électrolytique d'alliages de ruthénium, bain aqueux pour la mise en oeuvre de ce procédé, et article revêtu d'un alliage de ruthénium obtenu par ce procédé
SU645993A1 (ru) * 1976-07-08 1979-02-05 Университет Дружбы Народов Имени Патриса Лумумбы Электролит дл нанесени покрытий сплавом палладий-рутений
JPH1150295A (ja) * 1997-07-28 1999-02-23 Daiwa Kasei Kenkyusho:Kk めっき浴
KR101234429B1 (ko) * 2006-01-06 2013-02-18 엔쏜 인코포레이티드 무광택 금속층을 침착하기 위한 전해질 및 방법
EP2757180B1 (fr) * 2013-01-18 2015-08-12 Valmet Plating S.R.L. Procédé de dépôt électrolytique d'un alliage à base de ruthénium et d'étain, bain électrolytique qui permet le dépôt de l'alliage et alliage obtenu au moyen dudit procédé

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3458409A (en) 1964-10-12 1969-07-29 Shinichi Hayashi Method and electrolyte for thick,brilliant plating of palladium
US3576724A (en) 1967-10-18 1971-04-27 Int Nickel Co Electrodeposition of rutenium
US3972787A (en) 1974-06-14 1976-08-03 Lea-Ronal, Inc. Palladium electrolyte baths utilizing quaternized pyridine compounds as brighteners
US4082625A (en) 1976-06-08 1978-04-04 The International Nickel Company, Inc. Electrodeposition of ruthenium
DE4412253A1 (de) 1993-04-07 1994-10-13 Atotech Deutschland Gmbh Elektrolytische Abscheidung von Palladium oder Palladiumlegierungen
EP0916747A1 (fr) * 1997-11-15 1999-05-19 AMI Doduco GmbH Bain électrolytique pour le dépÔt de palladium et d'alliages de palladium
WO2009110598A1 (fr) * 2008-03-06 2009-09-11 日鉱商事株式会社 Produit à placage d'alliage ruthénium-palladium et son procédé de fabrication
EP3067444A2 (fr) * 2015-03-09 2016-09-14 Ing. W. Garhöfer Gesellschaft mbH Separation de revetements decoratifs en alliage palladium-fer sur des substances metalliques

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AT523922B1 (de) 2022-01-15

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