WO2015000010A1 - Bain d'électrolyte ainsi que objets ou articles qui sont revêtus à l'aide du bain - Google Patents

Bain d'électrolyte ainsi que objets ou articles qui sont revêtus à l'aide du bain Download PDF

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Publication number
WO2015000010A1
WO2015000010A1 PCT/AT2014/050151 AT2014050151W WO2015000010A1 WO 2015000010 A1 WO2015000010 A1 WO 2015000010A1 AT 2014050151 W AT2014050151 W AT 2014050151W WO 2015000010 A1 WO2015000010 A1 WO 2015000010A1
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WO
WIPO (PCT)
Prior art keywords
copper
tin
objects
coating
alloy
Prior art date
Application number
PCT/AT2014/050151
Other languages
German (de)
English (en)
Inventor
Claudia GARHÖFER-ONDREICSKA
Christian GARHÖFER
Original Assignee
Ing. W. Garhöfer Gesellschaft M.B.H.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ing. W. Garhöfer Gesellschaft M.B.H. filed Critical Ing. W. Garhöfer Gesellschaft M.B.H.
Publication of WO2015000010A1 publication Critical patent/WO2015000010A1/fr

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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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/02—Slide fasteners

Definitions

  • the present invention is directed to an electrolytic bath composition for depositing new ternary copper or bronze alloys free of toxic heavy metals, and further to objects and articles coated with these novel alloys as well as to a corresponding deposition method and use of the bath ,
  • Field of application is in particular the production of fashion jewelery, furthermore the clothing industry, in particular for buttons, zipper closures, bra closures, belt buckles, leather applications and the production of furniture fittings.
  • the invention relates to a novel electrolyte bath for the electrodeposition of coatings based on copper-tin-indium alloys, consisting essentially of water, copper cyanide, at least one tin (IV) compound, at least one indium compound, an alkali metal cyanide, an alkali metal hydroxide , and at least one complexing agent, of wetting agents and brighteners.
  • copper-tin-indium alloys consisting essentially of water, copper cyanide, at least one tin (IV) compound, at least one indium compound, an alkali metal cyanide, an alkali metal hydroxide , and at least one complexing agent, of wetting agents and brighteners.
  • EP 0 636 713 A1 describes alkaline cyanide baths for the electrodeposition of bright copper-tin alloys, which in addition to the corresponding metal salts Complexing agent, alkene sulfonate, alkyne sulfonate, pyridine compounds or sulfur-containing propane sulfonates contains as brighteners.
  • US Pat. No. 5,534,129 A discloses baths for producing lustrous, leveling copper-tin alloys which, in addition to metal salts, contain one or more complexing agents, alkali metal cyanide, alkali metal hydroxide, alkali metal carbonates, various brighteners and lead.
  • lead may only be used to a limited extent under European legislation. With increasing duration and age of the baths, the concentration of lead usually increases and then exceeds the permitted limit values.
  • US 4814049 A describes alkaline cyanide baths for the production of copper-tin-zinc alloys containing small amounts of nickel.
  • copper-tin alloys are often used as a substitute for nickel coatings, especially for costume jewelery, but also for products that come into constant or prolonged contact with the skin to avoid contact allergies. Co-alloying nickel, even in small amounts, would make replacement impossible.
  • JP 08-013185 A which describes a bath liquid for electrochemical coating with a tin alloy, which also contains copper and indium as alloy constituents, is described in the state of the art, and according to its abstract, the metal compounds are in the bath liquid as complex compounds before and the bath also contains the usual additives.
  • the bath described therein contains tin (II) ions and copper (II) ions.
  • JP-A clearly refers to an acid bath and the additives are accordingly matched.
  • Such alloys are thereby very well suited for the decorative coating, e.g. from fashion jewelery, but also for industrial applications as well as in the electronics industry.
  • the invention relates to a new electrolyte bath for the cathodic deposition of ternary alloys and / or layer sequences to form white to red, corrosion-resistant glossy coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as the electrolyte at least one complex dissolved Contains copper and at least one such tin compound, which is characterized in that the bath is formed as an aqueous, alkaline solution of in the form of anion complexes, copper and tin compounds present and contains as a third component at least one indium compound, and additionally containing at least one of the grouping agents, surfactants, wetting agents, chelating agents and brightener agents commonly present in alkaline electrodeposition baths.
  • copper and tin in the electrolyte bath in the form of alkaline and / or cyanidisch-soluble compounds preferably copper as copper (l) cyanide and tin as stannate or hydroxystannate present.
  • an electrolyte bath which is characterized in that it has a content of free alkali metal cyanide of 15 to 70 g / l, preferably from 20 to 60 g / l, and particularly preferably from 25 to 45 g / l, and alkali hydroxide of from 5 to 40 g / l, preferably from 10 to 30 g / l, and the content of copper in the range of from 5 to 25 g / l, preferably from 8 to 15 g / l, the content at tin at 15 to 50 g / l, preferably at 20 to 30 g / l, and the content of indium in the range of 0.5 to 5 g / l, preferably from 1 to 3
  • the electrolyte bath has a content of free alkali metal cyanide of 10 to 60 g / l, preferably from 10 to 40 g / l, and particularly preferably from 15 to 30 g / l, and of alkali hydroxide from 10 to 40 g / l, preferably from 15 to 30 g / l, the content of copper in the range of 5 to 25 g / l, preferably from 10 to 20 g / l, the content of tin at 3 to 15 g / l, preferably at 5 to 12 g / l, and the content of indium from 0.5 to 5 g / l, preferably from 1 to 3 g / l, varies.
  • the electrolyte bath is characterized by having a content of free alkali metal cyanide of 15 to 70 g / l, preferably 20 to 60 g / l, and more preferably 25 to 45 g / l, and Alkali hydroxide of 10 to 40 g / l, preferably from 15 to 30 g / l, the content of copper in the range of 15 to 40 g / l, preferably from 20 to 30 g / l, the content of tin at 3 to 15 g / l, preferably at 5 to 12 g / l, and the content of indium in the range of 0.5 to 5 g / l, preferably from 1 to 3 g / l, varies.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • NTA nitrilotriacetic acid
  • phosphonates pyrophosphates, gluconates, citrates, salts tartaric acid
  • ATMP aminotrismethylenephosphonic acid
  • EDTMP ethylenediamine-tetramethylenephosphonic acid
  • DTPMP Diethylenetriaminepentamethylenephosphonic acid
  • HEDP 1-hydroxyethane-1, 1-diphosphonic acid
  • surfactants for example alkyl ether sulfonates, alkyl ether phosphates, betaines or sulfobetaines, and / or pyridine derivatives, epichlorohydrin polymers and aminic polymers as brightener additives
  • Another essential subject of the invention are objects or articles, in particular jewelery or decorative articles, and further electro-technical or electronic components and components of a physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or alloys thereof or provided with a coating of a ternary alloy of copper, tin and indium deposited from an electrolyte bath deposited as mentioned above.
  • these objects with a white coating are characterized in that, preferably on an on the surface of the object or article metal substrate layer, in particular of copper, an alloy having 45 to 62 wt%, preferably 48 to 60 wt. -%, copper, 32 to 48 wt .-%, preferably 35 to 45% by weight, tin and 3 to 15 wt .-%, preferably 6 to 10 wt .-%, indium.
  • the abovementioned objects with a yellow coating are characterized in that, preferably on an underlying metallic surface layer on the surface of the object or article, in particular of copper, an alloy with 76 to 82 wt.%, Preferably 77 to 80 wt. % Copper, 12 to 20 wt .-%, preferably 14 to 18 wt%, tin and 2 to 10 wt .-%, preferably 3 to 7 wt .-%, indium.
  • the total thickness of the new ternary Cu, Sn, In bronze coating normally to be achieved in the context of the invention is 0.5 to 15 ⁇ m, in particular approximately 1 to 3 ⁇ m, depending on the field of use.
  • the intermediate layer of palladium or a palladium alloy has a thickness of 0.1 to 1 ⁇ m, and that of adhesive gold has a thickness of 0.05 to 0.3 ⁇ m.
  • the new objects or articles should have a final layer of one with rhodium and ruthenium, preferably in the weight% ratio of (70 to 90) :( 30 to 10), in particular of about 80:20 , formed alloy.
  • the objects, objects or particles to be coated are immersed in the respective electrolyte bath according to the invention and switched there as a cathode.
  • the working temperature of the electrolyte baths according to the invention is between 40 and 70 ° C.
  • the current density can be set to between 0.01 and 10 amps / dm 2 , depending on the type of coating system.
  • insoluble anodes those made of a material selected from the group consisting of platinized titanium, graphite, iridium-transition metal mixed oxide and special carbon material ("Diamond Like Carbon" DLC) or combinations of these materials are preferably used.
  • Mixed oxide anodes of iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide are particularly preferably used.
  • a respective base material for example made of brass, zinc, iron, steel or their alloys or other materials made conductive at least on its surface is either directly or on a previously applied there copper undercoat, deposited from cyanide or non-cyanide alkaline and / or from acidic copper baths, the new ternary copper-tin-indium alloy deposited.
  • This copper-tin-indium alloy can be either final or final layer, or further coated according to methods known per se.
  • Other coatings may, as already mentioned above, be palladium-containing, gold-containing or other noble metal-containing layers such as those of rhodium, platinum, ruthenium or their alloys.
  • palladium is used as a nickel substitute, as a diffusion barrier and as corrosion protection.
  • the base material is first copper-plated, then coated with palladium and finally receives the desired finish by coating with gold, rhodium or other precious metals or their alloys.
  • a thickness of the palladium layer of about 0.5-5 ⁇ is recommended. Usually a layer thickness of about 1 ⁇ is considered sufficient.
  • rhodium-ruthenium alloy instead of a rhodium final layer. If, for example, an alloy in the ratio by weight of rhodium to ruthenium of 80:20 is deposited as the final layer, in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would be saved.
  • the invention further relates to a, in particular conventional, method for the cathodic deposition of the ternary alloys according to the invention on at least their surface metallic or electrically conductive or conductive coated objects or articles using the electrolyte according to the invention and further objects or articles, available, or obtained manufactured by such a method for the cathodic deposition of ternary alloys, using the electrolyte bath according to the invention.
  • the invention also relates to the use of the electrolyte bath according to the invention for the cathodic deposition of ternary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles.
  • Example 1 - white coating layer
  • a brass jewelry blank is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 s at 10 A / dm 2 .
  • a weakly alkaline cyanide-free cleaner degreasing 1018, product of the company Ing. W. Garhöfer GesmbH
  • the jewelry blank is rinsed in deionized water, dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company. Ing. Garhöfer GesmbH) 20 ⁇ copper einbnend and high gloss at 4 A / dm 2 and 25 ° C deposited.
  • the blank is rinsed again and pre-immersed in a 10% KCN solution.
  • the corrosion resistance of the galvanized decorative part was tested in accordance with DIN 50018, Testing in a condensed water climate with sulfur dioxide-containing atmosphere, June 1997.
  • the corrosion resistance of the white coating in comparison with a coating of a similar working electrolyte, the copper-tin-zinc layers produced on the same base material in the S0 2 -Test is about twice as good.
  • parts coated from the electrolytic bath containing only the three metals according to the invention could remain for at least six days without any detectable attack, while parts from a comparable electrolytic bath, but without indium, showed signs of attack after only one day.
  • Example 2 white coating layer:
  • a jewelry blank made of die-cast zinc is degreased electrolytically in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 . Subsequently, the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) 5 ⁇ copper at 1 A / dm 2 and 50 ° C deposited.
  • a weakly alkaline cyanide-free cleaner degreasing 1018, product of the company Ing. W. Garhöfer GesmbH
  • the pre-coppered jewelry blank is then dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15 ⁇ copper deposited niebnend and high gloss at 4 A / dm 2 and 25 ° C.
  • the part thus coppered is again rinsed and pre-immersed in a 10% KCN solution.
  • the jewelery piece thus obtained is treated with 0.1 ⁇ m adhesion gold from a weakly acidic electrolyte with 2.5 g / l Au ("MC 21 8", product of the company Ing. W. Garhöfer GesmbH) at 1, 5 A / dm 2 and 35 ° C. It is then carefully rinsed in demineralized water, stripped in 5% sulfuric acid solution and 0.2 ⁇ rhodium from an electrolyte with 2 g / l Rh and 50 g / l sulfuric acid ( "Rhodium C2", product of the company Ing. W. Garhöfer GesmbH) rhodinated at 3V and 35 ° C.
  • MC 21 8 product of the company Ing. W. Garhöfer GesmbH
  • a jewelery blank made of brass is degreased electrolytically in a weakly alkaline, cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 .
  • the jewelry blank is rinsed in deionized water, deboniert in 5% sulfuric acid solution 30s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH ) 20 ⁇ copper einbnend and high gloss at 4 A / dm 2 and 25 ° C deposited.
  • the part is again rinsed and pre-immersed in a 10% KCN solution.
  • the jewelry part is after renewed rinsing and acid immersion with 1 ⁇ gold from a weakly acidic electrolyte with 2.5 g / l Au ("MC 218", product of the company Ing. W. Garhöfer GesmbH) at 1, 5 A / dm second and 35 ° C as the final layer.
  • MC 218 product of the company Ing. W. Garhöfer GesmbH
  • the galvanized part of the jewelry performed significantly better in the corrosion tests than jewelry parts which had been coated by the same process but with a comparable copper-tin-zinc alloy.
  • Example 4 red coating layer:
  • a jewelery blank made of zinc die casting is electrolytically degreased in a weakly alkaline, cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 s at 10 A / dm 2 .
  • the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) 5 ⁇ copper at 1 A / dm 2 and 50 ° C deposited.
  • the pre-coppered jewelry blank is then dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of Fa. Ing. W. Garhöfer GesmbH) 15 ⁇ copper einbnend and high gloss deposited at 4 A / dm 2 and 25 ° C.
  • the part is again rinsed and pre-immersed in a 10% KCN solution.
  • the jewelry is after rinsing in demineralized water and pickling in 1 0% KCN solution with 1 ⁇ gold color 4N from a cyanide electrolyte with 5 g / l Au ("MC 1 18 PI", product of the company Ing. W Garhöfer GesmbH) at 0.7 A / dm 2 and 65 ° C as a final layer.
  • MC 1 18 PI product of the company Ing. W Garhöfer GesmbH
  • the galvanized jewelry obtained in this way or its surface was pink 4N and high gloss.
  • the galvanized jewelery piece performed much better in the corrosion tests than jewelery pieces which were coated by the same process but with a comparable copper-tin-zinc alloy.

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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)

Abstract

L'invention concerne un nouveau bain pour la séparation cathodique de nouveaux alliages ternaires de bronze ainsi que des objets ou des articles revêtus par les alliages. La composition d'électrolyte comprend, outre du cuivre et de l'étain, comme seul troisième constituant d'alliage métallique, de l'indium. Le nouvel alliage permet de déposer des dépôts ou des revêtements hautement brillants, blancs, jaunes ou rouges, présentant une résistance élevée à la corrosion sur les objets, en particulier des articles de bijouterie et des pièces électroniques, qui sont exempts de métaux lourds toxiques. Un alliage ternaire de cuivre-étain-indium est déposé directement sur une couche facultative de cuivre. Cette couche d'alliage peut être la couche finale ou être revêtue davantage, comme par exemple par du palladium, de l'or ou d'autres métaux nobles, tels que le rhodium, le ruthénium ou par des alliages correspondants.
PCT/AT2014/050151 2013-07-05 2014-07-03 Bain d'électrolyte ainsi que objets ou articles qui sont revêtus à l'aide du bain WO2015000010A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50444/2013 2013-07-05
ATA50444/2013A AT514427B1 (de) 2013-07-05 2013-07-05 Elektrolytbad sowie damit erhältliche Objekte bzw. Artikel

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Publication Number Publication Date
WO2015000010A1 true WO2015000010A1 (fr) 2015-01-08

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
IT201700014377A1 (it) * 2017-02-09 2018-08-09 Bluclad S R L Bronzo giallo/rosa inox e suo impiego in prodotti galvanizzati
RU2665855C1 (ru) * 2017-06-21 2018-09-04 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тверской государственный университет" Электролит для осаждения покрытия из сплава медь-индий
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
WO2022101474A1 (fr) * 2020-11-16 2022-05-19 Coventya S.P.A. Procédé de préparation d'un produit électrodéposé par dépôt d'une sous-couche, d'une couche barrière de diffusion et d'une couche supérieure sur la surface d'un substrat et produit électrodéposé ainsi préparé

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Publication number Priority date Publication date Assignee Title
IT201700014377A1 (it) * 2017-02-09 2018-08-09 Bluclad S R L Bronzo giallo/rosa inox e suo impiego in prodotti galvanizzati
WO2018146623A1 (fr) * 2017-02-09 2018-08-16 Bluclad S.R.L. Bronze inoxydable jaune/rose et son utilisation dans des produits galvanisés
RU2665855C1 (ru) * 2017-06-21 2018-09-04 Федеральное государственное бюджетное образовательное учреждение высшего образования "Тверской государственный университет" Электролит для осаждения покрытия из сплава медь-индий
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
WO2019175270A1 (fr) 2018-03-13 2019-09-19 Coventya S.P.A. Produits électroplaqués et bain d'électroplacage pour obtenir lesdits produits
WO2022101474A1 (fr) * 2020-11-16 2022-05-19 Coventya S.P.A. Procédé de préparation d'un produit électrodéposé par dépôt d'une sous-couche, d'une couche barrière de diffusion et d'une couche supérieure sur la surface d'un substrat et produit électrodéposé ainsi préparé
EP4001472A1 (fr) * 2020-11-16 2022-05-25 COVENTYA S.p.A. Procédé de préparation d'un produit électroplaqué par dépôt d'une sous-couche, d'une couche barrière de diffusion et d'une couche supérieure sur la surface d'un substrat et produit électroplaqué ainsi préparé

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