EP3356579B1 - 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 - Google Patents

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 Download PDF

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EP3356579B1
EP3356579B1 EP16778284.6A EP16778284A EP3356579B1 EP 3356579 B1 EP3356579 B1 EP 3356579B1 EP 16778284 A EP16778284 A EP 16778284A EP 3356579 B1 EP3356579 B1 EP 3356579B1
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Prior art keywords
palladium
alloy
copper
substrate
layer
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EP3356579A1 (fr
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Coline Nelias
Samuele CIAPPELLI
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Coventya SpA
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Coventya SpA
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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
    • C25D3/56—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

  • 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 1930 478 B1 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 B1 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. Moreover, the passivity of these electroplated layers results in poor adhesion of the final layer and in poor performance regarding corrosion resistance.
  • EP 2 757 180 A1 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 1175 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.
  • JP 2 977503 B2 discloses an alkaline copper-palladium alloy plating liquid comprising a soluble zinc compound, an alkaline salt, a soluble copper compound, a soluble palladium component and a soluble stannic alkaline compound, wherein the concentration of the palladium component is 5 to 20 g/L.
  • WO 2017/021916 A2 with publication date 09-02-2017 discloses an electroplating bath for electrochemical deposition of a Cu-Sn-Zn-Pd alloy on a substrate, comprising water, a source of copper ions, a source of tin ions, a source of zinc ions and a palladium complex.
  • 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 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.
  • 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
  • the electroplating bath comprises an inorganic brightening agent selected from the group consisting of bismuth nitrate, bismuth acetate, bismuth citrate, bismuth chloride, potassium antimony hexahydroxide, antimony chloride, antimony nitrates, sodium selenite, selenium dioxide, selenium tetrachloride, selenium sulphide and mixtures thereof.
  • an inorganic brightening agent selected from the group consisting of bismuth nitrate, bismuth acetate, bismuth citrate, bismuth chloride, potassium antimony hexahydroxide, antimony chloride, antimony nitrates, sodium selenite, selenium dioxide, selenium tetrachloride, selenium sulphide and mixtures thereof.
  • a method for the electrochemical deposition of a Cu-Sn-Zn-Pd alloy on a substrate 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 electrochemically 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 ⁇ m, preferably 10 nm to 20 ⁇ m, more preferably 0.1 ⁇ m to 15 ⁇ m, even more preferably 1 ⁇ m to 10 ⁇ m, most preferably 2 ⁇ m to 5 ⁇ m.
  • the inventive substrate is characterized in that it comprises additionally an electrochemically deposited layer comprising or consisting of copper.
  • the electrochemically deposited layer comprising or consisting of copper is preferably located between the substrate and the electrochemically deposited Cu-Sn-Zn-Pd alloy layer.
  • the electrochemically deposited layer comprising or consisting of copper has a thickness of 1 nm to 1 mm, preferably 10 nm to 500 ⁇ m, more preferably 0.1 ⁇ m to 100 ⁇ m, even more preferably 1 ⁇ m to 50 ⁇ m, most preferably 5 ⁇ m to 20 ⁇ m or even 10 ⁇ m to 15 ⁇ m.
  • the electrochemically deposited finishing layer may optionally have a thickness of 0.01 ⁇ m to 20 ⁇ m, preferably 0.02 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, most preferably 0.1 ⁇ m to 3.0 ⁇ m or even 0.2 ⁇ m to 0.5 ⁇ m.
  • 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: - copper layer on substrate: 10 - 15 microns layer thickness - bronze layer on copper layer: ⁇ 2 microns layer thickness - gold finishing layer on bronze layer: 0.2 - 0.5 microns layer thickness
  • Example 1 Electrodeposition of a quaternary white bronze Cu-Sn-Zn-Pd deposit
  • the deposit was obtained using the following electrolyte solution: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - zinc as Zn(CN) 2 : 1 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 50 mg/L - free potassium cyanide: 50 g/L -free potassium hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
  • 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: - copper as CuCN: 15 g/L - tin as K 2 SnO 3 : 12 g/L - palladium as Pd(NH 3 ) 4 Cl 2 : 30 mg/L - zinc as Zn(CN) 2 : 1 g/L - free potassium cyanide: 35 g/L -free potassium hydroxide: 15 g/L - surfactant solution: 3 mL/L - brightening agent solution: 5 mL/L
  • 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: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - zinc as ZnCN 2 : 2 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 50 mg/L - free Potassium Cyanide: 50 g/L - free Potassium Hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
  • 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: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - zinc as Zn(CN) 2 : 1 g/L - free potassium cyanide: 50 g/L -free potassium hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
  • 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: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 50 mg/L - free potassium cyanide: 50 g/L - free potassium hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
  • 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: - copper as CuCN: 15 g/L - tin as K 2 SnO 3 : 12 g/L - zinc as Zn(CN) 2 : 1 g/L - free potassium cyanide: 35 g/L - free potassium hydroxide: 15 g/L - surfactant solution: 3 mL/L - brightening agent solution 2: 5 mL/L
  • 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: - copper as CuCN: 15 g/L - tin as K 2 SnO 3 : 12 g/L - palladium as Pd(NH 3 ) 4 Cl 2 : 30 mg/L - free potassium cyanide: 35 g/L - free potassium hydroxide: 15 g/L - surfactant solution: 3 mL/L - brightening agent solution: 5 mL/L
  • the electrodeposition is performed using the same conditions as in Example 2.
  • the final aspect of the ternary Cu-Sn-Pd bronze layer is bright and presents a 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)
  • - copper 15 microns
  • - bright nickel 10 microns
  • nickel phosphorus 3 microns
  • finishing gold
  • Reference Example 6 Electrodeposition of a white ternary Cu-Sn-Zn alloy and a precious metal underlayer sequence
  • the layer of ternary bronze and palladium as underlayer sequence is used as a reference to highlight the advantages of the nickel-free quaternary Cu-Sn-Zn-Pd alloy regarding corrosion resistance and the savings in production costs in comparison of the actual hypoallergenic solution.
  • - substrate copper alloys (brass or Zamack)
  • - copper 15 microns
  • ternary Cu-Sn-Zn alloy 5 microns
  • palladium alloy 0.3 microns
  • gold finishing 0.5 microns
  • Reference Example 7 Electrodeposition of quaternary white bronze Cu-Sn-Zn-Pd deposit with low Zinc content (0.5 wt.-%)
  • the deposit was obtained using the following electrolyte solution: - copper as CuCN: 8 g/L - tin as K 2 SnO 3 : 25 g/L - zinc as ZnCN 2 : 0.5 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 50 mg/L - free Potassium Cyanide: 45 g/L - free Potassium Hydroxide: 8 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
  • 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: - copper as CuCN: 9 g/L - tin as K 2 SnO 3 : 16 g/L - zinc as ZnCN 2 : 6 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 100 mg/L - free Potassium Cyanide: 45 g/L - free Potassium Hydroxide: 6 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
  • 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.
  • Example 1 Copper content Tin content Zinc content Palladium content
  • Example 1 White Cu-Sn-Zn-Pd alloy 49% 42% 7% 2%
  • Example 2 Yellow Cu-Sn-Zn-Pd alloy 79% 16% 4.5% 0.5%
  • Example 3 White Cu-Sn-Zn-Pd alloy 49% 42% 7% 2% Ref.
  • Example 1 White Cu-Sn-Zn alloy 44% 46% 9% - Ref.
  • Example 2 White Cu-Sn-Pd alloy 48% 49% - 3% Ref.
  • Example 3 Yellow Cu-Sn-Zn alloy 78% 18% 4% - Ref.
  • Example 4 Yellow Cu-Sn-Pd alloy 80% 19% - 1% Ref.
  • Example 7 White Cu-Sn-Zn-Pd alloy (low Zn content) 48% 49% 0.4% 2.6% Ref.
  • Example 8 White Cu-Sn-Zn-Pd alloy (high Zn content) 32% 40% 26% 2%
  • 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 SO 2 /NO x atmosphere was tested in a close container with high SO 2 and NO x gas concentrations. The results are shown in Table 2.
  • Example 1 WHITE Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m No oxidation at 96h No alteration after 48h (upper than required) Similar aspect after 96h (upper than required) No pitting
  • Example 2 YELLOW Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Oxidation visible at 72h Slight oxidation at 24h No oxidation at 48h Slight oxidation at 96h No pitting
  • Example 3 WHITE Cu-Sn-Zn-Pd alloy 3 ⁇ m Gold finishing 0.2 ⁇ m n/a No sign of oxidation or change of colour n/a n/a Ref.
  • Example 1 WHITE Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Oxidation visible after 48h Corrosion product after 12h Slight alteration after 48h Pitting Ref.
  • Example 2 WHITE Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Corrosion products visible after 24h Oxidation visible after 6h Alteration starts at 24h Strong pitting Ref.
  • Example 3 YELLOW Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Oxidation visible after 24h Corrosion product after 6h Alteration after 48h Pitting Ref.
  • Example 4 YELLOW Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Oxidation visible after 48h Corrosion product after 12h Alteration after 48h Slight pitting Ref.
  • Example 5 Nickel + Nickel Phosphorus (15 microns in total) Gold finishing 0.5 ⁇ m No oxidation at 96h No alteration after 48h (upper than required) Similar aspect after 96h (upper than required) No pitting Ref.
  • Example 6 WHITE Cu-Sn-Zn alloy 5 ⁇ m Palladium alloy 0.3 Gold finishing 0.5 ⁇ m Oxidation visible at 72h Slight oxidation at 24h No oxidation at 48h Slight oxidation at 96h Slight pitting Ref.
  • Example 7 WHITE Cu-Sn-Zn-Pd alloy 3 ⁇ m Gold finishing 0.2 ⁇ m (low Zn content) n/a Evolution of the general aspect: red deviation of the colour n/a n/a Ref.
  • 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.
  • Example 1 WHITE Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Bright Without alteration Bright Without alteration
  • Example 2 YELLOW Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Bright Without alteration Bright Without alteration
  • Example 3 WHITE Cu-Sn-Zn-Pd alloy 3 ⁇ m Gold finishing 0.2 ⁇ m Bright Without alteration Bright Without alteration Ref.
  • Example 1 WHITE Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Bright Without alteration Gold and white bronze layer mixed (white aspect) Ref.
  • Example 2 WHITE Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Hazy Without alteration Under-plated copper is migrating to the top of the final articles Ref.
  • Example 3 YELLOW Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Bright Without alteration Spots due to copper migration Ref.
  • Example 4 YELLOW Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Bright Without alteration Under-plated copper is migrating to the top of the final articles Ref.
  • Example 5 Nickel + Nickel Phosphorus (15 microns in total) Gold finishing 0.5 ⁇ m Bright Without alteration Bright Without alteration Ref.
  • Example 6 WHITE Cu-Sn-Zn alloy 5 ⁇ m Palladium alloy 0.3 ⁇ m Gold finishing 0.5 ⁇ m Bright Without alteration Bright Without alteration Ref.
  • Example 7 WHITE Cu-Sn-Zn-Pd alloy 3 ⁇ m Gold finishing 0.2 ⁇ m Slightly hazy aspect without alteration Copper underlayer migrates to the surface and the item presents pink colour Ref.
  • Example 8 WHITE Cu-Sn-Zn-Pd alloy 3 ⁇ m Gold finishing 0.2 ⁇ m Slightly Hazy aspect without alteration Copper underlayer migrates to the surface and visual alteration is observed
  • 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.
  • nitric acid resistance tests are conducted by dipping the plated article into a 65 % aqueous solution of HNO 3 . The results are shown in Table 4.
  • Table 4 Nitric acid resistance
  • Example 1 WHITE Cu-Sn-Zn-Pd alloy 5 ⁇ m Cu-Sn-Zn-Pd is not altered by nitric acid
  • Example 2 YELLOW Cu-Sn-Zn-Pd alloy 5 ⁇ m Nitric acid dissolves 25% of the alloy Ref.
  • Example 1: WHITE Cu-Sn-Zn alloy 5 ⁇ m Cu-Sn-Zn alloy is dissolved Ref.
  • Example 2 WHITE Cu-Sn-Pd alloy 5 ⁇ m Cu-Sn-Pd alloy is dissolved Ref.
  • Example 3 YELLOW Cu-Sn-Zn alloy 5 ⁇ m Cu-Sn-Zn alloy is dissolved Ref.
  • Example 4 YELLOW Cu-Sn-Pd alloy 5 ⁇ m Cu-Sn-Pd alloy is dissolved Ref.
  • Example 5 Nickel + Nickel Phosphorus (15 microns in total) Nickel phosphorus is not altered by nitric acid

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Claims (13)

  1. Bain de galvanoplastie pour le dépôt électrochimique d'un alliage Cu-Sn-Zn-Pd sur un substrat, comprenant ou consistant de
    a) l'eau;
    b) une source d'ions cuivre;
    c) une source d'ions étain;
    d) une source d'ions zinc;
    e) un sel de palladium et/ou un complexe de palladium; et
    f) un brillanteur inorganique choisi dans le groupe constitué par le nitrate de bismuth, l'acétate de bismuth, le citrate de bismuth, le chloride de bismuth, l'hexahydroxyde de potassium et d'antimoine, le chlorure d'antimoine, les nitrates antimonieux, le sélénite de sodium, le dioxyde de sélénium, le tetrachlorure de sélénium et le sulfure de sélénium ainsi que leurs mélanges;
    dans laquelle le bain de galvanoplastie a un pH alcalin, et
    dans laquelle la concentration
    du cuivre dans le bain de galvanoplastie se situe entre 2,5 g/L et 25 g/L ; et
    de l'étain dans le bain de galvanoplastie se situe entre 5 g/L et 35 g/L ; et
    des ions zinc dans le bain de galvanoplastie se situe entre 0,25 g/L et 5 g/L ; et
    du palladium sous forme de sel de palladium et/ou de complexe de palladium dans le bain d'électrodéposition se situe entre 5 et 200 mg/L.
  2. Bain de galvanoplastie selon la revendication précédente, caractérisé en ce que
    a) la source d'ions cuivre est choisie dans le groupe constitué par le sulfate de cuivre, l'oxyde de cuivre, l'hydroxyde de cuivre, le chlorure de cuivre, le nitrate de cuivre, l'acétate de cuivre, le carbonate de cuivre et le cyanide de cuivre, ou un mélange de ceux-ci, de préférence du cyanure de cuivre ; et/ou
    b) la source d'ions étain est un composé d'étain(II) et/ou d'étain(IV), de préférence un sel d'étain(IV), plus préférentiellement du stannate de potassium ; et/ou
    c) la source d'ions zinc est l'acétate de zinc, le chlorure de zinc, le cyanure de zinc, le sulfate de zinc et/ou un zincate alcalin ; et/ou
    d) le sel de palladium et/ou le complexe de palladium est choisi dans le groupe constitué par le chlorure de palladium, le bromure de palladium, le cyanure de palladium, le nitrite de palladium, le nitrate de palladium, le sulphate de palladium, le thiosulfate de palladium, l'acétate de palladium, le carbonate de palladium hydrogencarbonate, l'hydroxyde de palladium et l'oxyde de palladium avec ou sans ligands sélectionnés dans le groupe par ammoniaques et amines, le plus préférentiellement des complexes choisis dans le groupe comprenant le di-chlorure de palladium diamino, le sulfate de palladium diamino, le dinitrate de palladium diamino, le chlorure de tétramine palladium, le sulfate de tétramine palladium, le nitrate de palladium tétra-mine, le carbonate de palladium hydrogèné, le chlorure de palladium ethylène-diamine, le sulfate de palladium éthylène diamino, le potassi-ium thiosulfate, et leurs mélanges.
  3. Bain de galvanoplastie selon l'une des revendications précédentes, caractérisé en ce que le bain de galvanoplastie comprend en outre
    a) un complexant, de préférence du cyanure de potassium et/ou du cyanure de sodium, de préférence à une concentration de 20 à 80 g/L, de préférence de 25 à 60 g/L; et/ou
    b) une base, de préférence de l'hydroxyde de potassium et/ou de l'hydroxyde de sodium, de préférence à une concentration de 1 à 60 g/L, de préférence de 2 à 40 g/L; et/ou
    c) un sel conducteur, de préférence du sel de Rochelle, du carbonate de potassium et/ou du carbonate de sodium, de préférence à une concentration de 10-100 g/L; et/ou
    d) un tensioactif, de préférence un tensioactif amphotère, anionique et/ou non ionique, plus préférentiellement choisi dans le groupe constitué des bétaïnes, sulfobétaïnes, alkylsulfates, alkyléthersulfates, alkyléthersulfates, alkyléthersulfonates, alkylsulfonates, alkylsulfosuccinates, alkylbenzènesulfonates, alcool polyglycol éthers, polyéthylène glycols et leurs mélanges, où la concentration en tensioactif est, avant la prise, 0,05 g/l à 1 g/l et plus préférentiellement 0,15 g/l à 0,5 g/L.
  4. Procédé de dépôt électrochimique d'un alliage Cu-Sn-Zn-Pd sur un substrat, comprenant les étapes suivantes
    a) la formation d'un contact électrique entre un substrat et une électrode négative d'une source d'énergie ;
    b) la mise en contact du substrat avec un bain de galvanoplastie selon l'une des revendications 1 à 3 ;
    c) la mise en contact d'au moins une partie d'une électrode positive de la source d'alimentation avec le bain galvanique selon l'une des revendications 1 à 3 ; et
    d) l'application d'une tension entre les électrodes positive et négative de la source d'alimentation jusqu'à ce qu'un dépôt d'un alliage Cu-Sn-Zn-Pd se soit formé sur le substrat.
  5. Procédé selon la revendication 4, caractérisé en ce qu'on utilise un substrat qui comprend un métal ou un alliage choisi dans le groupe constitué par le bronze, le laiton, le Zamack, l'alpaga, l'alliage de cuivre, l'alliage d'étain, l'acier et leurs mélanges et/ou le substrat utilisé est un objet métallique en plastique et/ou un objet en plastique plaqué alliage.
  6. Procédé selon l'une des revendications 4 ou 5, caractérisé en ce qu'on utilise une électrode positive qui comprend ou consiste en un matériau anodique insoluble, de préférence du graphite, des oxydes métalliques mixtes, du titane platiné et/ou de l'acier inoxydable.
  7. Procédé selon l'une des revendications 4 à 6, caractérisé en ce que la tension appliquée est ajustée pour fournir une densité de courant de 0,05 à 5 A/dm2, de préférence 0,2 à 3 A/dm2.
  8. Procédé selon l'une des revendications 4 à 7, caractérisé en ce que la température du bain galvanique est maintenue entre 20 et 80 °C, de préférence entre 40 et 70 °C.
  9. Substrat comprenant une couche d'alliage Cu-Sn-Zn-Pd déposée par voie électrochimique, la couche d'alliage comprenant ou consistant en
    a) 30 à 90 % en poids de cuivre ;
    b) 5 à 60 % en poids d'étain ;
    c) 1 à 20 % en poids de zinc ; et
    d) ≥0,25 à ≤5 % en poids de palladium,
    dans laquelle le substrat peut être produit avec le procédé selon l'une des revendications 4 à 8, et
    dans laquelle le substrat a en outre une couche de finition déposée par voie électrochimique comprenant du cuivre ou consistant en cuivre, ladite couche ayant une épaisseur de 1 nm à 1 mm.
  10. Substrat selon la revendication 9, caractérisé en ce que l'alliage se compose de
    a) 40 à 85 % en poids de cuivre, éventuellement 45 à 80 % en poids ; et/ou
    b) 10 à 50 % en poids d'étain, éventuellement 15 à 45 % en poids ; et/ou
    c) 2 à 15 % en poids de zinc, éventuellement 3 à 10 % en poids ; et/ou
    d) pas d'argent ; et/ou
    e) pas d'indium ; et/ou
    f) pas de nickel ; et/ou
    g) pas de mercure.
  11. Substrat selon l'une des revendications 9 ou 10, caractérisé en ce que l'épaisseur de la couche d'alliage Cu-Sn-Zn-Pd déposée par voie électrochimique est de 1 nm à 25 µm, de préférence de 10 nm à 20 µm, de préférence de 0,1 µm à 15 µm, encore plus de 1 µm à 10 µm, de préférence de 2 µm à 5 µm.
  12. Substrat selon l'une des revendications 9 à 11, caractérisé en ce que
    a) la couche déposée par voie électrochimique comprenant du cuivre ou consistant en cuivre, dans laquelle ladite couche a éventuellement une épaisseur de 10 nm à 500 µm, plus préférablement de 0,1 µm à 100 µm, encore plus préférablement de 1 µm à 50 µm, plus préférablement de 5 µm à 20 µm, et dans laquelle ladite couche est située entre le substrat et la couche déposée par voie électrochimique en alliage Cu-Sn-Zn-Pd ; et/ou
    b) le substrat comporte en outre une couche de finition déposée par voie électrochimique comprenant un métal noble ou consistant en un métal noble a une épaisseur de 0,01 µm à 100 µm, de préférence de 0,02 à 50 µm, plus préférablement de 0,05 à 5 µm, plus préférablement de 0,1 µm à 3 µm, et où la couche d'alliage Cu-Sn-Zn-Pd déposée par voie électrochimique est située entre le substrat et la couche de finition.
  13. Utilisation du substrat selon l'une des revendications 9 à 12 en tant qu'article de mode, de préférence en tant qu'article choisi dans le groupe constitué par les bijoux, la mode, les articles en cuir, les montres, les lunettes, les bibelots, les serrures et/ou les emballages pour parfums.
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)

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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

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EP3356579B1 true EP3356579B1 (fr) 2020-03-11

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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

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CN (1) CN108138346B (fr)
ES (2) ES2790583T3 (fr)
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WO (1) WO2017055553A1 (fr)

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EP3150744B1 (fr) 2015-09-30 2020-02-12 COVENTYA S.p.A. 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
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
FR3118067B1 (fr) * 2020-12-18 2023-05-26 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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PT3150744T (pt) 2020-05-12
EP3150744A1 (fr) 2017-04-05
PT3356579T (pt) 2020-06-16
CN108138346B (zh) 2021-03-05
CN108138346A (zh) 2018-06-08
WO2017055553A1 (fr) 2017-04-06
ES2790583T3 (es) 2020-10-28
ES2791197T3 (es) 2020-11-03
EP3356579A1 (fr) 2018-08-08

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