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EP3356579A1 - Bain de dépôt électrolytique pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique dudit alliage, substrat comprenant ledit alliage et utilisations du substrat - Google Patents

Bain de dépôt électrolytique pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique dudit alliage, substrat comprenant ledit alliage et utilisations du substrat

Info

Publication number
EP3356579A1
EP3356579A1 EP16778284.6A EP16778284A EP3356579A1 EP 3356579 A1 EP3356579 A1 EP 3356579A1 EP 16778284 A EP16778284 A EP 16778284A EP 3356579 A1 EP3356579 A1 EP 3356579A1
Authority
EP
European Patent Office
Prior art keywords
palladium
μιη
alloy
substrate
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16778284.6A
Other languages
German (de)
English (en)
Other versions
EP3356579B1 (fr
Inventor
Coline Nelias
Samuele CIAPPELLI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coventya SpA
Original Assignee
Coventya SpA
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Filing date
Publication date
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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
    • C25D3/56—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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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

Definitions

  • Electroplating bath for electrochemical deposition of a Cu-Sn-Zn-Pd alloy method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate
  • the invention provides an electroplating bath for electrochemical deposition of a novel Cu-Sn-Zn-Pd alloy on a substrate.
  • the novel alloy is characterized by exceptional corrosion resistance.
  • the commonly used precious metal intermediate layer e.g. a Pd-layer
  • the novel alloy can be provided free of toxic metals (e.g. free of nickel) which makes it hypoallergenic and not prone to cause skin irritation.
  • the plating of the inventive alloy between a substrate and its finishing layer prevents discolouration or colour fading of the finishing layer over time. All these advantages render the novel alloy particularly suitable for plating it on items of the fashion industry.
  • Nickel has been highlighted as an allergenic metal and its use in consumer products is strongly restricted. Prior to these restrictions, a decorative galvanic layer sequence comprised a nickel layer to reach the bright aspect of the final article, but also to optimize the corrosion resistance properties and to function as a copper diffusion barrier. A high robustness is required for the final object in order to resist the aggressive media created by environmental pollution. A specific nickel-phosphorus alloy was also proposed in order to protect articles produced for the Asian market, where the atmosphere tends to contain high nitrogen and sulphur oxide concentrations.
  • bronze as a protective under-layer does not provide the provision of a corrosion resistance like the one previously achieved with nickel. These copper alloys are also less efficient as copper diffusion barriers.
  • a nickel layer with a bronze layer most variants require the use of a precious metal under-layer like palladium which is commonly applied between the bronze layer and the final decorative finishing layer. This additional under-layer considerably increases the production costs and can lead to a lack of adhesion of the finishing layer due to palladium passivity.
  • Tin and other tin alloys as barrier layers with high tin content have also been developed, but are not really efficient regarding the high brightness required by the fashion market or the high resistance necessary to pass pertinent corrosion tests.
  • EP 1 930 478 Bl presents a quaternary bronze alloy where the fourth metal is gallium, indium or thallium.
  • Thallium was introduced into the decorative market as a grain refining agent to substitute lead previously present in typical cyanide bronze electrolytes.
  • the use of thallium does not raise the bronzes corrosion resistance i.e. the alloy is still highly sensitive to acidity generated by nitrogen and sulphur oxides present ubiquitously in polluted atmospheres.
  • thallium is highly toxic.
  • Gallium and indium alloys have the disadvantage that they are poorly resistant to aggressive media such as synthetic sweat or saline humidity.
  • EP 2 035 602 Bl proposes the introduction of a palladium, ruthenium, rhodium or cobalt layer between the copper-tin layer and the finishing layer. These metals raise considerably the production costs of the final article.
  • EP 2 757 180 Al recommends the use of tin alloys with a precious metal, ruthenium in this particular case.
  • the ruthenium content needs to be high and this does not allow reducing the production costs due to the high price of ruthenium.
  • the process does not yield products with the bright aspect required by the decorative and fashion industries.
  • CN 1 175 287 A discloses the deposition of white ornamental surfaces built on a base material covered with copper with a thickness of 1 micron as an under- layer. Said layer is followed by a layer of a Sn-Cu-Pd alloy in a thickness of 0.2 microns or higher, comprising 10-20 wt.-% Sn, 10-80 wt.-% Cu and 10-50 wt.- % Pd as the essential components. Owing to the lack of zinc in this alloy, it does not give the required performance regarding the efficiency as a copper migration barrier.
  • This ternary copper-tin-palladium alloy is not suitable as a nickel substitute since the deposit is not bright and shows only poor corrosion resistance.
  • an electroplating bath for electrochemical deposition of a Cu-Sn-Zn-Pd alloy (preferably a quaternary Cu-Sn-Zn-Pd alloy) on a substrate is provided, the bath comprising or consisting of
  • the electroplating bath has an alkaline pH.
  • the inventive electroplating bath allows the provision of a substrate having an alloy layer which comprises the precious metal palladium.
  • the novel alloy resists aggressive atmospheric and other environmental conditions and considerably increases the shelf and usage life of substrates (plated articles). Even without an intermediate precious metal under-layer (e.g. a palladium under- layer) between the substrate and the finishing layer, excellent corrosion protection is provided (pertinent standardized corrosion tests are successfully passed).
  • the use of the inventive alloy allows a substantial reduction of the production costs compared to the use of a pure precious metal underlayer.
  • the final article can be provided free of toxic metals (e.g. free of nickel) which renders it hypoallergenic and not prone to cause skin irritation.
  • the new alloy provides a smooth coating to the article and prevents diffusion of metallic components from the lower layers to the finishing layer and vice versa. Thus, a colour fading or discolouration of the final aspect is prevented.
  • the new bronze alloy layer has lower production costs, very high brightness, very high corrosion resistance and excellent ageing behaviour.
  • the final colour (yellow or white bronze) may be adjusted.
  • a concentration range of 1 to 20 % wt.-% zinc in the final alloy is sufficient.
  • the palladium content of > 0.25 wt.-% in the alloy was found sufficient for providing the required corrosion resistance.
  • Production costs can be minimized by keeping the palladium concentration ⁇ 5 wt.-% in the final alloy while corrosion protection performance is maintained. It was found that a palladium content higher than 5 wt.-% in the alloy considerably raises the production costs without significantly improving corrosion resistance.
  • a) copper in the electroplating bath may be between 2.5 g/L and 25 g/L, preferably 3.5 g/L to 20 g/L; and/or
  • tin in the electroplating bath may be between 5 g/L to 35 g/L, preferably 9.75 g/L to 26.25 g/L; and/or
  • c) zinc in the electroplating bath may be between 0.25 g/L to 5 g/L; and/or d) palladium as palladium salt and/or palladium complex in the electroplating bath may be between 5 to 200 mg/L.
  • the source of copper ions is selected from the group consisting of copper sulphate, copper oxide, copper hydroxide, copper chloride, copper nitrate, copper acetate, copper carbonate and copper cyanide, or a mixture thereof, preferably copper cyanide; and/or
  • the source of tin ions is a tin(ll) and/or tin(IV) compound, preferably a tin(IV) salt, more preferably potassium stannate; and/or
  • the source of zinc ions is zinc acetate, zinc chloride, zinc cyanide, zinc sulphate and/or an alkali zincate; and/or
  • the palladium salt and/or palladium complex is selected from the group consisting of palladium chloride, palladium bromide, palladium cyanide, palladium nitrite, palladium nitrate, palladium sulphate, palladium thiosul- phate, palladium acetate, palladium hydrogencarbonate, palladium hydroxide and palladium oxide, with or without ligands selected from the group of ammonia and amines, most preferably complexes selected from the group consisting of palladium diamino dichloride, palladium diamino sulphate, palladium diamino dinitrate, tetramine palladium chloride, tetramine palladium sulphate, tetramine palladium nitrate, tetramine palladium hydrogencarbonate, palladium ethylenediamine chloride, palladium ethylenediamine sulphate, palladium potassium thios
  • the electroplating bath does not comprise a source of nickel ions, preferably no source of nickel and silver ions, optionally no source of nickel, silver and indium ions.
  • the electroplating bath may further comprise
  • a complexing agent preferably potassium cyanide and/or sodium cyanide, preferably at a concentration of 20 to 80 g/L, more preferably, 25 to 60 g/L; and/or
  • a base preferably potassium hydroxide and/or sodium hydroxide, preferably at a concentration of 1 to 60 g/L, more preferably 2 to 40 g/L; and/or c) a conductive salt, preferably Rochelle salt, potassium carbonate and/or sodium carbonate, preferably at a concentration of 10-100 g/L; and/or d) a surfactant, preferably an amphoteric, anionic and/or non-ionic surfactant, more preferably selected from the group consisting of betaines, sul- fobetaines, alkyl sulphates, alkyl ether sulphates, alkyl ether phosphates, alkyl sulfonates, alkyl sulfosuccinates, alkyl benzene sulfonates, alcohol po- lyglycol ethers, polyethylene glycols, and mixtures thereof, wherein the surfactant concentration is preferably 0.05 g/L to 1 g/
  • an inorganic brightening agent preferably selected from the group consisting of a salt of bismuth, antimony and/or selenium, more preferably bismuth nitrate, bismuth acetate, bismuth citrate, bismuth chloride, potassium antimony hexahydroxide, antimony chloride, antimony nitrates, sodium selenite, selenium dioxide, selenium tetrachloride, selenium sulphide and/or mixtures thereof; and/or
  • an organic brightening agent preferably selected from the group consisting of reaction product of an amine and epihalohydrine derivatives.
  • the electroplating bath comprises a complexing agent and a surfactant, preferably a complexing agent, a surfactant and a brightening agent (inorganic and/or organic), more preferably a complexing agent, a surfactant, a brightening agent and a base.
  • a method for the electrochemical deposition of a Cu-Sn-Zn-Pd alloy on a substrate is provided, the method comprising the steps
  • the method may be characterized in that a substrate is used that comprises or consists of a metal or an alloy selected from the group consisting of bronze, brass, Zamack, alpaca, copper alloy, tin alloy, steel and mixtures thereof and/or the substrate used is a metal-plated object of plastic and/or an alloy- plated object of plastic.
  • a positive electrode may be used that comprises or consists of an insoluble anode material, preferably graphite, mixed metal oxides, platinated titanium and/or stainless steel.
  • the applied voltage is adjusted to provide a current density of 0.05 to 5 A/dm 2 , preferably 0.2 to 3 A/dm 2 .
  • the temperature of the electroplating bath may be kept at between 20 and 80 °C, preferably at between 40 to 70 °C. At temperatures below 20 °C, the coating is less bright, not homogeneous and not uniform in its colour. Above 80 °C, the electroplating results in too many break-down products which results in a quick build-up of potassium carbonate as well as a rapid ageing of the electrolyte. The optimum temperature range was discovered to be between 40 to 70°C.
  • a substrate comprising an electro- chemically deposited Cu-Sn-Zn-Pd alloy layer
  • the alloy layer comprising or consisting of
  • the Cu-Sn-Zn-Pd alloy layer electrochemically deposited on the inventive substrate is free of cracks, bright and provides the substrate with excellent corrosion resistance. Moreover, the inventive substrate is characterized by an excellent ageing behaviour i.e. it does not show discolouration or colour fading over time.
  • the alloy comprises
  • a concentration of zinc between 2 and 15% wt.-%.in the alloy was discovered to give the most effective copper diffusion barrier.
  • the alloy layer is free of nickel, preferably free of nickel and silver, optionally free of nickel, silver and indium or free of nickel, silver, indium and mercury.
  • the thickness of the electrochemically deposited Cu-Sn-Zn-Pd alloy layer may be 1 nm to 25 ⁇ , preferably 10 nm to 20 ⁇ , more preferably 0.1 ⁇ to 15 ⁇ , even more preferably 1 ⁇ to 10 ⁇ , most preferably 2 ⁇ to 5 ⁇ .
  • the inventive substrate may be characterized in that it comprises additionally a) an electrochemically deposited layer comprising or consisting of acidic copper, wherein said layer is preferably located between the substrate and the electrochemically deposited Cu-Sn-Zn-Pd alloy layer; and/or b) an electrochemically deposited finishing layer comprising or consisting of a noble metal, wherein the electrochemically deposited Cu-Sn-Zn-Pd alloy layer is preferably located between the substrate and the electrochemically deposited finishing layer.
  • the electrochemically deposited layer comprising or consisting of acidic copper has a thickness of 1 nm to 1 mm, preferably 10 nm to 500 ⁇ , more preferably 0.1 ⁇ to 100 ⁇ , even more preferably 1 ⁇ to 50 ⁇ , most preferably 5 ⁇ to 20 ⁇ or even 10 ⁇ to 15 ⁇ .
  • the electrochemically deposited finishing layer may optionally have a thickness of 0.01 ⁇ to 20 ⁇ , preferably 0.02 to 10 ⁇ , more preferably 0.05 to 5 ⁇ , most preferably 0.1 ⁇ to 3.0 ⁇ or even 0.2 ⁇ to 0.5 ⁇ .
  • the substrate is producible with the inventive method.
  • the inventive substrate as fashion item is suggested, preferably as an article selected from the group consisting of jewellery, fashion, leather article, watch, eyewear, trinket, lock and/or perfume packaging application.
  • the inventive substrate fulfils all requirements of the fashion industry (especially the one for jewellery and leather goods articles), namely:
  • the electroplating method for depositing an alloy on a substrate comprised the following plating sequence:
  • Example 1 Electrodeposition of a quaternary white bronze Cu-Sn-Zn-Pd deposit
  • the deposit was obtained using the following electrolyte solution
  • the electrodeposition was performed at 60 °C since this temperature turned out to be the best compromise for spreading the (white) brightness range to its maximum and obtaining a homogeneous alloy throughout the current density range.
  • the copper plated substrate is introduced into the electrolyte after proper cleaning and activation, with a current density of 1 A/dm 2 applied for 20 minutes in order to raise the Cu-Sn-Zn-Pd bronze layer thickness to 5 microns.
  • the final aspect of the ternary Cu-Sn-Zn-Pd bronze layer is bright and presents a white colour.
  • Example 2 Electrodeposition of a quaternary yellow bronze Cu-Sn-Zn-Pd deposit
  • the deposit was obtained using the following electrolyte solution:
  • the electrodeposition was performed at 50°C since this temperature turned out to be the best compromise for spreading the (yellow) brightness range at its maximum and obtain a homogeneous alloy through the current density range.
  • the copper plated substrate is introduced into the electrolyte after proper cleaning and activation with a current density at 1.5 A/dm 2 applied for 15 minutes in order to raise the Cu-Sn-Zn-Pd bronze layer thickness to 5 microns.
  • the final aspect of the quaternary Cu-Sn-Zn-Pd bronze layer is bright and presents a pale yellow colour.
  • Example 3 Electrodeposition of quaternary white bronze Cu-Sn-Zn-Pd deposit with claimed Zinc content (1 - 20 wt.-%)
  • the deposit was obtained using the following electrolyte solution:
  • the quaternary bronze alloy electrodeposition is performed at 60°C, since this temperature turned out to be the best compromise to obtain a bright and homogeneous alloy on the whole range of current density.
  • the copper plated substrate is introduced into the electrolyte after proper cleaning and activation, current density was fixed at 1 A/dm 2 and applied for 15 minutes in order to obtain a bronze layer thickness of 3 microns.
  • the final aspect of the quaternary Cu-Sn-Zn-Pd bronze layer is bright and presents a white colour.
  • Reference example 1 Electrodeposition of a ternary white bronze Cu-Sn-Zn deposit
  • a deposit was obtained using the following electrolyte solution:
  • the electrodeposition is performed using the same conditions as in Example 1.
  • the final aspect of the ternary Cu-Sn-Zn bronze layer is bright and presents a white colour.
  • Reference example 2 Electrodeposition of a ternary white bronze Cu-Sn-Pd deposit
  • the deposit was obtained using the following electrolyte solution:
  • the electrodeposition is performed using same conditions as in Example 1.
  • the final aspect of the ternary Cu-Sn-Pd bronze layer is hazy and presents a grey colour.
  • the aspect of the deposit is not homogeneous.
  • the deposit was obtained using the following electrolyte solution:
  • the electrodeposition is performed using the same conditions as in Example 2.
  • the final aspect of the ternary Cu-Sn-Zn bronze layer is bright and presents a pale yellow colour.
  • the deposit was obtained using the following electrolyte solution:
  • the electrodeposition is performed using the same conditions as in Examph 2.
  • the final aspect of the ternary Cu-Sn-Pd bronze layer is bright and presents yellow colour.
  • This nickel layer sequence is used as a reference to highlight the comparable behaviour of the new quaternary Cu-Sn-Zn-Pd alloy regarding corrosion resistance of final articles.
  • - substrate copper alloys (brass or Zamack)
  • Reference Example 6 Electrodeposition of a white ternary Cu-Sn-Zn alloy and a precious metal underlayer sequence
  • the deposit was obtained using the following electrolyte solution:
  • the quaternary bronze alloy electrodeposition is performed at 60°C, since this temperature turned out to be the best compromise to obtain a bright and homogeneous alloy on the whole range of current density.
  • the copper plated substrate is introduced into the electrolyte after proper cleaning and activation, current density was fixed at 1 A/dm 2 and applied for 15 minutes in order to obtain a bronze layer thickness of 3 microns.
  • the final aspect of the quaternary Cu-Sn-Zn-Pd bronze layer is slightly hazy and presents a white colour.
  • Reference Example 8 Electrodeposition of quaternary white bronze Cu-Sn- Pd deposit with high Zinc content (> 25 wt.-%)
  • the deposit was obtained using the following electrolyte solution:
  • the quaternary bronze alloy electrodeposition is performed at 60°C, since this temperature turned out to be the best compromise to obtain a bright and homogeneous alloy on the whole range of current density.
  • the copper plated substrate is introduced into the electrolyte after proper cleaning and activation, current density was fixed at 1 A/dm 2 and applied for 15 minutes in order to obtain a bronze layer thickness of 3 microns.
  • the final aspect of the quaternary Cu-Sn-Zn-Pd bronze layer is slightly hazy and presents white colour.
  • the electroplated products obtained in Examples 1 to 3 and Reference Examples 1 to 8 were subjected to corrosion resistance tests. Salt spray tests were performed according to the ISO 9227 standard. Synthetic sweat resistance tests were conducted following NFS 80722 requirements, and leather interaction resistance was evaluated in accordance with ISO 4611 testing conditions. The resistance to a S0 2 /NO x atmosphere was tested in a close container with high S0 2 and NO x gas concentrations. The results are shown in Table 2.
  • Example 3 an additional synthetic sweat resistance tests has been performed, namely an ageing with TURBULA for 3 minutes has been performed. After said ageing, Example 3 still shows no sign of oxidation or change of colour. On the contrary, in Reference Example 7, green salt and exfoliations from the copper layer were observed and in Reference Example 8, white rust and exfoliations from the copper layer were observed.
  • the comparison of the data obtained with Example 3 with the data obtained with Reference Examples 7 and 8 demonstrates that the zinc content in the alloy is important to ensure a sufficient corrosion protection. Indeed, it has become evident that if the final alloy comprises zinc below or above the range of 1 to 20 wt.-%, the corrosion resistance is lost. Table 3: Evaluation of the copper migration barrier properties
  • Table 3 A comparison of the results of the copper migration tests for the selected embodiments of the invention and for the Reference Examples demonstrates the improvements reached with the quaternary Cu-Sn-Zn-Pd alloy.
  • Example 3 and Reference Examples 7 and 8 highlight the importance of zinc content in the electroplated alloy to ensure a copper diffusion barrier. Indeed, it has become clear that if the final alloy comprises zinc below or above the range of 1 to 20 wt.-%, the copper migration barrier property is lost.
  • the nitric acid resistance tests are conducted by dipping the plated article into a 65 % aqueous solution of HN0 3 . The results are shown in Table 4.

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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)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un bain de dépôt électrolytique pour le dépôt électrochimique d'un nouvel alliage Cu-Sn-Zn-Pd sur un substrat. Ce nouvel alliage est caractérisé par une résistance exceptionnelle à la corrosion et par le fait que la couche intermédiaire de métal précieux communément utilisée (par exemple une couche de Pd) entre le substrat et la couche de finition n'est plus nécessaire, ce qui permet une réduction sensible des coûts de fabrication des substrats revêtus.
EP16778284.6A 2015-09-30 2016-09-30 Bain d'électrodéposition pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cet alliage, substrat comprenant ledit alliage et utilisations de ce substrat Revoked EP3356579B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15187511.9A EP3150744B1 (fr) 2015-09-30 2015-09-30 Bain galvanique pour le dépôt électrochimique d'une couche d'alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cette couche d'alliage, substrat comprenant cette couche d'alliage et utilisations du substrat revêtu
PCT/EP2016/073427 WO2017055553A1 (fr) 2015-09-30 2016-09-30 Bain de dépôt électrolytique pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique dudit alliage, substrat comprenant ledit alliage et utilisations du substrat

Publications (2)

Publication Number Publication Date
EP3356579A1 true EP3356579A1 (fr) 2018-08-08
EP3356579B1 EP3356579B1 (fr) 2020-03-11

Family

ID=54249387

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15187511.9A Revoked EP3150744B1 (fr) 2015-09-30 2015-09-30 Bain galvanique pour le dépôt électrochimique d'une couche d'alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cette couche d'alliage, substrat comprenant cette couche d'alliage et utilisations du substrat revêtu
EP16778284.6A Revoked EP3356579B1 (fr) 2015-09-30 2016-09-30 Bain d'électrodéposition pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cet alliage, substrat comprenant ledit alliage et utilisations de ce substrat

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP15187511.9A Revoked EP3150744B1 (fr) 2015-09-30 2015-09-30 Bain galvanique pour le dépôt électrochimique d'une couche d'alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cette couche d'alliage, substrat comprenant cette couche d'alliage et utilisations du substrat revêtu

Country Status (5)

Country Link
EP (2) EP3150744B1 (fr)
CN (1) CN108138346B (fr)
ES (2) ES2790583T3 (fr)
PT (2) PT3150744T (fr)
WO (1) WO2017055553A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022128608A1 (fr) * 2020-12-18 2022-06-23 Linxens Holding Procédé de dépôt d'un alliage de bronze sur un circuit imprimé et circuit imprimé obtenu par ce procédé

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2790583T3 (es) 2015-09-30 2020-10-28 Coventya S P A Baño de galvanoplastia para el depósito electroquímica de una aleación de Cu-Sn-Zn-Pd, procedimiento para el depósito electroquímica de dicha aleación, sustrato que comprende dicha aleación y usos del sustrato
IT201700014377A1 (it) * 2017-02-09 2018-08-09 Bluclad S R L Bronzo giallo/rosa inox e suo impiego in prodotti galvanizzati
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
IT201800004235A1 (it) * 2018-04-05 2019-10-05 Lega di bronzo bianco, bagno galvanico e procedimento al fine di produrre la lega di bronzo bianco tramite deposizione elettrogalvanica
CN108864200B (zh) * 2018-08-06 2020-12-11 金川集团股份有限公司 电镀用硫酸乙二胺钯的一步制备方法
IT202000011203A1 (it) * 2020-05-15 2021-11-15 Bluclad S P A Lega di bronzo inossidabile e suo impiego in prodotti galvanizzati
CN119776940B (zh) * 2024-12-31 2025-11-14 西安理工大学 一种交错氧化亚铜微米立方体的电化学制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2916423A (en) 1957-06-19 1959-12-08 Metal & Thermit Corp Electrodeposition of copper and copper alloys
US3440151A (en) 1965-06-02 1969-04-22 Robert Duva Electrodeposition of copper-tin alloys
BE805602A (fr) 1973-10-03 1974-02-01 Johnson Matthey Co Ltd Procede de depot electrolytique d'or
CH662583A5 (fr) 1985-03-01 1987-10-15 Heinz Emmenegger Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc.
JP3029948B2 (ja) * 1993-04-07 2000-04-10 シチズン時計株式会社 Ｓｎ−Ｃｕ−Ｐｄ合金めっき部材、その製造に用いるめっき浴
JPH0827590A (ja) 1994-07-13 1996-01-30 Okuno Chem Ind Co Ltd 光沢銅−錫合金めっき浴
CN1097644C (zh) 1995-12-07 2003-01-01 西铁城钟表有限公司 装饰件
EP0808921B1 (fr) 1995-12-07 2001-11-14 Citizen Watch Co., Ltd. Element ornemental
JP2977503B2 (ja) 1997-02-13 1999-11-15 株式会社ビクトリア 銅−パラジウム系合金メッキ液及びメッキ基材
KR100494820B1 (ko) * 2000-06-27 2005-06-14 시티즌 도케이 가부시키가이샤 백색 피막을 갖는 장식품 및 그 제조 방법
CN101096769A (zh) 2006-06-26 2008-01-02 比亚迪股份有限公司 一种电镀方法
EP1930478B1 (fr) 2006-12-06 2013-06-19 Enthone, Inc. Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre
JP5642928B2 (ja) 2007-12-12 2014-12-17 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． 青銅の電気めっき
EP2975143B1 (fr) * 2011-03-09 2018-12-19 SAXONIA Technical Materials GmbH Procédé de préparation de sphères d'amalgame
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
EP2799595A1 (fr) * 2013-05-03 2014-11-05 Delphi Technologies, Inc. Elément de contact électrique
AT514818B1 (de) 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
ITUB20152876A1 (it) * 2015-08-05 2017-02-05 Bluclad S R L Leghe stagno/rame contenenti palladio, metodo per la loro preparazione e loro uso.
ES2790583T3 (es) 2015-09-30 2020-10-28 Coventya S P A Baño de galvanoplastia para el depósito electroquímica de una aleación de Cu-Sn-Zn-Pd, procedimiento para el depósito electroquímica de dicha aleación, sustrato que comprende dicha aleación y usos del sustrato

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022128608A1 (fr) * 2020-12-18 2022-06-23 Linxens Holding Procédé de dépôt d'un alliage de bronze sur un circuit imprimé et circuit imprimé obtenu par ce procédé
FR3118067A1 (fr) * 2020-12-18 2022-06-24 Linxens Holding Procédé de dépôt d’un alliage de bronze sur un circuit imprimé et circuit imprimé obtenu par ce procédé

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ES2790583T3 (es) 2020-10-28
CN108138346A (zh) 2018-06-08
CN108138346B (zh) 2021-03-05
EP3150744B1 (fr) 2020-02-12
EP3150744A1 (fr) 2017-04-05
PT3150744T (pt) 2020-05-12
PT3356579T (pt) 2020-06-16
WO2017055553A1 (fr) 2017-04-06
EP3356579B1 (fr) 2020-03-11

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