EP3356579B1 - Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats - Google Patents

Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats Download PDF

Info

Publication number
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
Authority
EP
European Patent Office
Prior art keywords
palladium
alloy
copper
substrate
layer
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.)
Revoked
Application number
EP16778284.6A
Other languages
English (en)
French (fr)
Other versions
EP3356579A1 (de
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
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=54249387&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3356579(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Coventya SpA filed Critical Coventya SpA
Publication of EP3356579A1 publication Critical patent/EP3356579A1/de
Application granted granted Critical
Publication of EP3356579B1 publication Critical patent/EP3356579B1/de
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

  • 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

Landscapes

  • 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)

Claims (13)

  1. Galvanisierungsbad zur elektrochemischen Abscheidung einer Cu-Sn-Zn-Pd Legierung auf einem Substrat, enthaltend oder bestehend aus
    a) Wasser;
    b) einer Quelle für Kupferionen;
    c) einer Quelle für Zinnionen;
    d) einer Quelle für Zinkionen;
    e) einem Palladiumsalz und/oder einem Palladiumkomplex; und
    f) einen anorganischen Glanzbildner ausgewählt aus der Gruppe bestehend aus einem Salz von Bismut, Antimon und/oder Selen, vorzugsweise Bismutnitrat, Bismutacetat, Bismutcitrat, Bismutchlorid, Kaliumantimonhexahydroxid, Antimonchlorid, Antimonnitrat, Natriumselenit, Selendioxid, Seleniumtetrachlorid, Selensulfid und/oder Mischungen davon;
    wobei das Galvanisierungsbad einen alkalischen pH-Wert aufweist, und
    wobei die Konzentration von
    Kupfer im Galvanisierungsbad zwischen 2,5 g/L und 25 g/L liegt; und die Konzentration von
    Zinn im Galvanisierungsbad zwischen 5 g/L und 35 g/L liegt; und die Konzentration von
    Zinkionen im Galvanisierungsbad zwischen 0,25 g/L und 5 g/L liegt; und
    das Palladium als Palladiumsalz und/oder Palladiumkomplex im Galvanisierungsbad zwischen 5 und 200 mg/L liegt.
  2. Galvanisierungsbad nach dem vorstehenden Anspruch, dadurch gekennzeichnet, dass
    a) die Quelle für Kupferionen ausgewählt ist aus der Gruppe bestehend aus Kupfersulfat, Kupferoxid, Kupferhydroxid, Kupferchlorid, Kupfernitrat, Kupferacetat, Kupfercarbonat und Kupfercyanid oder einem Gemisch davon, vorzugsweise Kupfercyanid; und/oder
    b) die Quelle der Zinnionen eine Zinn(II)- und/oder Zinn(IV)-Verbindung ist, bevorzugt ein Zinn(IV)-Salz, besonders bevorzugt Kaliumstannat; und/oder
    c) die Quelle der Zinkionen Zinkacetat, Zinkchlorid, Zinkcyanid, Zinksulfat und/oder ein Alkalizinkat ist; und/oder
    d) das Palladiumsalz und/oder der Palladiumkomplex ausgewählt ist aus der Gruppe bestehend aus Palladiumchlorid, Palladiumbromid, Palladiumcyanid, Palladiumnitri, Palladiumnitrat, Palladiumsulfat, Palladiumthiosulfat, Palladiumacetat, Palladiumhydrogencarbonat, Palladiumhydroxid und Palladiumoxid, mit oder ohne Liganden ausgewählt aus der Gruppe Ammoniak und Amine, bevorzugt Komplexe ausgewählt aus der Gruppe bestehend aus Palladiumdiammindichlorid, Palladiumdiamminsulfat, Palladiumdiammindinitrat, Tetraamminpalladiumchlorid, Tetraamminpalladiumsulfat, Tetraamminpalladinnitrat, Tetraamminpalladiumhydrogencarbonat, Palladiumethylendiaminchlorid, Palladiumethylendiaminsulfat, Palladiumethylendiaminsulfat, Palladiumkaliumthiosulfat und Mischungen davon.
  3. Galvanisierungsbad nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Galvanisierungsbad weiterhin enthält
    a) einen Komplexbildner, vorzugsweise Kaliumcyanid und/oder Natriumcyanid, bevorzugt in einer Konzentration von 20 bis 80 g/L, besonders bevorzugt 25 bis 60 g/L; und/oder
    b) eine Base, vorzugsweise Kaliumhydroxid und/oder Natriumhydroxid, bevorzugt in einer Konzentration von 1 bis 60 g/L, besonders bevorzugt 2 bis 40 g/L; und/oder
    c) ein Leitsalz, vorzugsweise Rochellesalz, Kaliumcarbonat und/oder Natriumcarbonat, bevorzugt in einer Konzentration von 10 bis 100 g/L; und/oder
    d) ein Tensid, vorzugsweise ein amphoteres, anionisches und/oder nichtionisches Tensid, das bevorzugt ausgewählt ist aus der Gruppe bestehend aus Betainen, Sulfobetainen, Alkylsulfaten, Alkylethersulfaten, Alkyletherphosphaten, Alkylsulfonaten, Alkylsulfosuccinaten, Alkylbenzolsulfonaten, Alkoholpolyglykolethern, Polyethylenglykolen und Mischungen davon, wobei die Tensidkonzentration bevorzugt 0,05 g/L bis 1 g/L, besonders bevorzugt 0,15 g/L bis 0,5 g/L beträgt.
  4. Verfahren zur elektrochemischen Abscheidung einer Cu-Sn-Zn-Pd-Legierung auf einem Substrat, umfassend die Schritte
    a) Bilden eines elektrischen Kontaktes zwischen einem Substrat und der negativen Elektrode einer Stromquelle;
    b) Kontaktieren des Substrates mit einem Galvanisierungsbad nach einem der Ansprüche 1 bis 3;
    c) Kontaktieren der positiven Elektrode der Stromquelle mit dem Galvanisierungsbad nach einem der Ansprüche 1 bis 3; und
    d) Anlegen einer Spannung zwischen der positiven und negativen Elektrode der Stromquelle, bis sich auf dem Substrat eine Abscheidung einer Cu-Sn-Zn-Pd-Legierung gebildet hat.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass ein Substrat verwendet wird, das ein Metall oder eine Legierung ausgewählt aus der Gruppe bestehend aus Bronze, Messing, Zamak, Alpaka, Kupferlegierung, Zinn-AI-Legierung, Stahl und Mischungen daraus umfasst oder daraus besteht und/oder das verwendete Substrat ein metallplattierter Gegenstand aus Kunststoff und/oder Legierungs-beschichteter Gegenstand aus Kunststoff ist.
  6. Verfahren nach einem der Ansprüche 4 oder 5, dadurch gekennzeichnet, dass eine positive Elektrode verwendet wird, die ein unlösliches Anodenmaterial, vorzugsweise Graphit, Mischmetalloxide, platiniertes Titan und/oder Edelstahl, enthält oder daraus besteht.
  7. Verfahren nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass die angelegte Spannung so eingestellt wird, dass eine Stromdichte auf der Substratoberfläche von 0,05 bis 5 A/dm2, vorzugsweise 0,2 bis 3 A/dm2 bereitgestellt wird.
  8. Verfahren nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass die Temperatur des Galvanisierungsbades zwischen 20 und 80 °C, vorzugsweise zwischen 40 und 70 °C, gehalten wird.
  9. Substrat, enthaltend eine elektrochemisch abgeschiedene Cu-Sn-Zn-Pd Legierungschicht, wobei die Legierungsschicht
    a) 30 bis 90 Gew.-% Kupfer;
    b) 5 bis 60 Gew.-% Zinn;
    c) 1 bis 20 Gew.-% Zink; und
    d) ≥0,25 bis ≤ 5 Gew.-% Palladium,
    enthält oder daraus besteht,
    wobei das Substrat mit dem Verfahren nach einem der Ansprüche 4 bis 8 herstellbar ist, und
    wobei das Substrat zusätzlich eine elektrochemisch abgeschiedene Oberflächenschicht aufweist, die Kupfer enthält oder aus Kupfer besteht, wobei die Schicht eine Dicke von 1 nm bis 1 mm aufweist.
  10. Substrat nach Anspruch 9, dadurch gekennzeichnet, dass die Legierung
    a) 40 bis 85 Gew.-% Kupfer, optional 45 bis 80 Gew.-%; und/oder
    b) 10 bis 50 Gew.-% Zinn, gegebenenfalls 15 bis 45 Gew.-%; und/oder
    c) 2 bis 15 Gew.-% Zink, optional 3 bis 10 Gew.-%; und/oder
    d) kein Silber; und/oder
    e) kein Indium; und/oder
    f) kein Nickel; und/oder
    g) kein Quecksilber
    enthält.
  11. Substrat nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, dass die Dicke der elektrochemisch abgeschiedenen Cu-Sn-Zn-Pd Legierungsschicht 1 nm bis 25 µm, vorzugsweise 10 nm bis 20 µm, bevorzugt 0,1 µm bis 15 µm, besonders bevorzugt 1 µm bis 10 µm, am bevorzugtesten 2 µm bis 5 µm beträgt.
  12. Substrat nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, dass
    a) die elektrochemisch abgeschiedene Schicht, enthaltend oder bestehend aus Kupfer eine Dicke von 10 nm bis 500 µm, bevorzugt 0,1 µm bis 100 µm, besonders bevorzugt 1 µm bis 50 µm, am bevorzugtesten 5 µm bis 20 µm aufweist, und wobei sich die Schicht zwischen dem Substrat und der elektrochemisch abgeschiedenen Cu-Sn-Zn-Pd-Legierungsschicht befindet; und/oder
    b) das Substrat zusätzlich eine elektrochemisch abgeschiedene Oberflächenschicht aufweist, die ein Edelmetall enthält oder aus einem Edelmetall besteht, eine Dicke von 0,01 µm bis 100 µm, vorzugsweise 0,02 bis 50 µm, bevorzugt 0,05 bis 5 µm, besonders bevorzugt 0,1 µm bis 3 µm aufweist, und wobei sich die elektrochemisch abgeschiedene Cu-Sn-Zn-Pd-Legierungsschicht unterhalb der Endbeschichtung befindet.
  13. Verwendung des Substrates nach einem der Ansprüche 9 bis 12 als Modeartikel, vorzugsweise als Artikel ausgewählt aus der Gruppe bestehend aus Schmuck, Mode, Lederartikel, Uhr, Brille, Verschluss und/oder Parfümverpackung.
EP16778284.6A 2015-09-30 2016-09-30 Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats Revoked EP3356579B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15187511.9A EP3150744B1 (de) 2015-09-30 2015-09-30 Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd legierungsschicht, verfahren zur elektrochemischen abscheidung der legierungsschicht, substrat mit der legierungsschicht und verwendungen des beschichteten substrats
PCT/EP2016/073427 WO2017055553A1 (en) 2015-09-30 2016-09-30 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

Publications (2)

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

Family

ID=54249387

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15187511.9A Revoked EP3150744B1 (de) 2015-09-30 2015-09-30 Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd legierungsschicht, verfahren zur elektrochemischen abscheidung der legierungsschicht, substrat mit der legierungsschicht und verwendungen des beschichteten substrats
EP16778284.6A Revoked EP3356579B1 (de) 2015-09-30 2016-09-30 Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP15187511.9A Revoked EP3150744B1 (de) 2015-09-30 2015-09-30 Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd legierungsschicht, verfahren zur elektrochemischen abscheidung der legierungsschicht, substrat mit der legierungsschicht und verwendungen des beschichteten substrats

Country Status (5)

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

Families Citing this family (6)

* 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
EP3540097A1 (de) 2018-03-13 2019-09-18 COVENTYA S.p.A. Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte
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

Citations (12)

* 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
EP0193848A1 (de) 1985-03-01 1986-09-10 Heinz Emmenegger Galvanisches Bad für das Elektroplattieren von Goldlegierungen
JPH06293990A (ja) 1993-04-07 1994-10-21 Nippon Shinkinzoku Kako Kk 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
JPH10219467A (ja) 1997-02-13 1998-08-18 Bikutoria:Kk 銅−パラジウム系合金メッキ液及びメッキ基材
US5972526A (en) 1995-12-07 1999-10-26 Citizen Watch Co., Ltd. Decorative member
US6780527B2 (en) 2000-06-27 2004-08-24 Citizen Watch Co., Ltd. Decorative article having white film and production method therefor
US20140055026A1 (en) 2011-03-09 2014-02-27 Umicore Ag & Co. Kg Amalgam balls having an alloy coating
EP2799595A1 (de) 2013-05-03 2014-11-05 Delphi Technologies, Inc. Elektrisches Kontaktelement
WO2017021916A2 (en) * 2015-08-05 2017-02-09 Bluclad S.R.L. Tin/copper alloys containing palladium, method for their preparation and use thereof
WO2017055553A1 (en) 2015-09-30 2017-04-06 Coventya S.P.A. 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
EP2071057B1 (de) 2007-12-12 2019-01-23 Rohm and Haas Electronic Materials LLC Galvanische abscheidung von kupfer-zinn-legierung

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3440151A (en) 1965-06-02 1969-04-22 Robert Duva Electrodeposition of copper-tin alloys
BE805602A (en) 1973-10-03 1974-02-01 Johnson Matthey Co Ltd Cyanide-free gold electroplating bath - contg alkali metal gold complex and complexing agent and additives
CN1097644C (zh) 1995-12-07 2003-01-01 西铁城钟表有限公司 装饰件
CN101096769A (zh) 2006-06-26 2008-01-02 比亚迪股份有限公司 一种电镀方法
EP1930478B1 (de) 2006-12-06 2013-06-19 Enthone, Inc. Zusammensetzung eines Elektrolyten und Verfahren zur Beschichtung von quaternären Kupferlegierungen
EP2757180B1 (de) 2013-01-18 2015-08-12 Valmet Plating S.R.L. Verfahren zur elektrolytischen Abscheidung einer zinn- und rutheniumbasierten Legierung, Elektrolyt zur Ermöglichung der Abscheidung der besagten Legierung sowie die mittels des besagten Verfahrens erhaltene Legierung
AT514818B1 (de) 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten

Patent Citations (13)

* 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
EP0193848A1 (de) 1985-03-01 1986-09-10 Heinz Emmenegger Galvanisches Bad für das Elektroplattieren von Goldlegierungen
JPH06293990A (ja) 1993-04-07 1994-10-21 Nippon Shinkinzoku Kako Kk 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
US5972526A (en) 1995-12-07 1999-10-26 Citizen Watch Co., Ltd. Decorative member
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
JPH10219467A (ja) 1997-02-13 1998-08-18 Bikutoria:Kk 銅−パラジウム系合金メッキ液及びメッキ基材
US6780527B2 (en) 2000-06-27 2004-08-24 Citizen Watch Co., Ltd. Decorative article having white film and production method therefor
EP2071057B1 (de) 2007-12-12 2019-01-23 Rohm and Haas Electronic Materials LLC Galvanische abscheidung von kupfer-zinn-legierung
US20140055026A1 (en) 2011-03-09 2014-02-27 Umicore Ag & Co. Kg Amalgam balls having an alloy coating
EP2799595A1 (de) 2013-05-03 2014-11-05 Delphi Technologies, Inc. Elektrisches Kontaktelement
WO2017021916A2 (en) * 2015-08-05 2017-02-09 Bluclad S.R.L. Tin/copper alloys containing palladium, method for their preparation and use thereof
WO2017055553A1 (en) 2015-09-30 2017-04-06 Coventya S.P.A. 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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Prepration of inorganic brightener solutions", EXPERIMENTAL REPORT, 4 December 2020 (2020-12-04), pages 1 - 19, XP055762618
RICHARD E DEPOTO; AL GRUENWALD: "White Bronze, Copper-Tin-Zinc Tri-metal: Expanding Applications and New Developments in a Changing Landscape", PRODUCTS FINISHING, 20 May 2013 (2013-05-20), pages 1 - 21, XP055142805

Also Published As

Publication number Publication date
WO2017055553A1 (en) 2017-04-06
PT3150744T (pt) 2020-05-12
EP3356579A1 (de) 2018-08-08
ES2790583T3 (es) 2020-10-28
EP3150744A1 (de) 2017-04-05
CN108138346B (zh) 2021-03-05
CN108138346A (zh) 2018-06-08
EP3150744B1 (de) 2020-02-12
PT3356579T (pt) 2020-06-16
ES2791197T3 (es) 2020-11-03

Similar Documents

Publication Publication Date Title
EP3356579B1 (de) Galvanikbad zur elektrochemischen abscheidung einer cu-sn-zn-pd-legierung, verfahren zur elektrochemischen abscheidung von dieser legierung, substrat mit dieser legierung und verwendung des substrats
Jung et al. Electrochemical plating of Cu-Sn alloy in non-cyanide solution to substitute for Ni undercoating layer
CN101665963B (zh) 一种环保型无氰银电镀液
US8147671B2 (en) Electroplating method and electroplated product
EP2655702B1 (de) Substrat mit einer korrosionsbeständigen beschichtung und verfahren zu dessen herstellung
EP2980279B1 (de) Zink-nickel-legierungsplattierungslösung und plattierungsverfahren
CN101289756B (zh) 用于金铜合金电解沉积的电解组合物及方法
EP2171130B1 (de) Verfahren zur bereitstellung einer metallischen überzugsschciht
EP3159436B1 (de) Artikel mit mehrschichtiger plattierungsschicht
EP3030698B1 (de) Elektrolyt für die elektrolytische abscheidung von silber-palladium-legierungen und verfahren zur abscheidung davon
CN110359045A (zh) 具有镀层的铝合金构件和表面处理方法
EP3765658B1 (de) Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte
EP2017373B1 (de) Hochgeschwindigkeitsverfahren zur plattierung von palladiumlegierungen
CN102108533A (zh) 一种无氰电镀铜-锡合金层为表层的用于造币的多层电镀工艺
EP2730682B1 (de) Alkalische, cyanidfreie lösung zur elektroplattierung von goldlegierungen, verfahren zur elektroplattierung und substrat mit einer heller, korrosionsfreien ablagerung einer goldlegierung
JP5149503B2 (ja) 金属黒化処理液、当該金属黒化処理液を用いた金属黒化処理方法、当該金属黒化処理方法を用いた黒化処理品
CN102605394A (zh) 一种无氰酸性白铜锡电镀液
CN104233401A (zh) 一种Cu-Co合金的电镀制备方法
WO2021199087A1 (en) Galvanic process for the electrodeposition of a protective layer, and associated bath
Gamburg et al. Technologies for the electrodeposition of metals and alloys: electrolytes and processes
Wilkinson Palladium-nickel
EP3686319A1 (de) Indium-elektroplattierungszusammensetzungen und indium-elektroplattierungsverfahren auf nickel
WO2004001101A2 (en) Electrolytic bath for the electrodeposition of noble metals and their alloys
JPH0711477A (ja) 貴金属めっき品
CN116917549A (zh) 用于电镀电沉积的方法以及相关的电镀池

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180208

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190212

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191125

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1243243

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016031614

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: DENNEMEYER AG, CH

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 3356579

Country of ref document: PT

Date of ref document: 20200616

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20200602

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200611

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200612

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200611

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200711

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2791197

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20201103

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602016031614

Country of ref document: DE

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: BLUCLAD S.P.A.

Effective date: 20201211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200930

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200930

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200930

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200930

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200311

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1243243

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200311

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20220818

Year of fee payment: 7

Ref country code: RO

Payment date: 20220921

Year of fee payment: 7

Ref country code: PT

Payment date: 20220818

Year of fee payment: 7

Ref country code: IT

Payment date: 20220825

Year of fee payment: 7

Ref country code: DE

Payment date: 20220818

Year of fee payment: 7

Ref country code: AT

Payment date: 20220819

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20220819

Year of fee payment: 7

REG Reference to a national code

Ref country code: DE

Ref legal event code: R103

Ref document number: 602016031614

Country of ref document: DE

Ref country code: DE

Ref legal event code: R064

Ref document number: 602016031614

Country of ref document: DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20221003

Year of fee payment: 7

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20221001

Year of fee payment: 7

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

27W Patent revoked

Effective date: 20230119

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 1243243

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230119

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC