EP3312309B1 - Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations - Google Patents

Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations Download PDF

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EP3312309B1
EP3312309B1 EP16194360.0A EP16194360A EP3312309B1 EP 3312309 B1 EP3312309 B1 EP 3312309B1 EP 16194360 A EP16194360 A EP 16194360A EP 3312309 B1 EP3312309 B1 EP 3312309B1
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Prior art keywords
layer
copper
copper alloy
electroplated product
alloy
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EP3312309A1 (fr
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Coline Nelias
Daniele Petracchi
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Coventya SpA
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Coventya SpA
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Priority to PT161943600T priority Critical patent/PT3312309T/pt
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Priority to ES16194360T priority patent/ES2805102T3/es
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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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • This invention provides an electroplated product with a precious metal finishing layer that has an improved corrosion and abrasion resistance.
  • the electroplated product comprises two electroplated copper alloy layers having a different copper concentration (e.g. white bronze and yellow bronze).
  • the electroplated product is especially suitable for use in jewelry, fashion, leather, watch, eyewear, trinkets and/or lock industry.
  • Another advantage of the electroplated product is that the use of allergenic nickel or expensive palladium intermediate layers against copper migration can be dispensed with. This means that the electroplated product can be non-allergenic (nickel-free) and be provided in a more economical and environment-friendly manner.
  • a method for the production of the inventive electroplated product is presented. Furthermore, the use of the inventive electroplated product in the jewelry, fashion, leather, watch, eyewear, trinkets and/or lock industry is suggested.
  • the underlayers presently used in the fashion market to provide a high corrosion and wear resistant support for a top gold finishing layer comprises nickel and/or nickel based alloys.
  • the allergy associated with nickel and the classification of nickel salts as carcinogenic, mutagenic and reprotoxic substances makes the use of nickel and nickel based alloys more and more restricted in this market. Thus, its use has been strongly restricted, especially for fashion and jewelry applications.
  • WO 2013/164165 A1 discloses a multi-layered nickel-free surface coating for sanitary application having a copper layer, a coating of at least one metal layer consisting of an alloy of copper, tin and zinc or copper and tin, a coating of at least one metal layer consisting of chromium, copper, gold, palladium or iron and a final chromium layer.
  • the intermediate layer contains a precious metal (palladium or gold) that drastically increases the cost of the electroplated product or a metal such as chromium, copper and iron that drastically reduce adherence of the final decorative layer or lower the corrosion resistance of the electroplated product.
  • the electroplated product is less suitable for the high requirements in the jewelry and/or fashion industry.
  • WO 2008/003216 A1 discloses an electroplated product including a copper layer on the surface of the base material, characterized in that the electroplated copper metal layer further includes a metal layer as a nickel substitute, and this nickel substitute metal is a Cu-Sn alloy, Ru, Rh, Pd, or an alloy composed of 2, 3, or 4 elements selected from Ru, Rh, Pd, and Co.
  • this nickel substitute metal is a Cu-Sn alloy, Ru, Rh, Pd, or an alloy composed of 2, 3, or 4 elements selected from Ru, Rh, Pd, and Co.
  • the use of one single layer of Cu-Sn alloy is not sufficient to target the high corrosion resistance requirement for the jewelry or fashion market and the use of precious metal intermediate layers is very expensive.
  • US 2003/0059634 A1 discloses a low-priced personal ornament which has a white-colored inexpensive stainless steel outermost coating layer having long-term corrosion resistance and discloses a process for producing said ornament.
  • JP 2003 096592 A discloses external parts for timepieces which greatly expand color variations by applying a coating thereto.
  • the prior art does not fulfill the requirements of the decorative, fashion and jewelry industry of providing in an economic and easy manner an electroplated product which is non-allergenic and has a high level of brightness and improved corrosion and abrasion resistance.
  • an electroplated product comprising
  • the electroplated product diffusion of copper from a copper containing layer into a layer containing less copper and/or a precious metal layer (like e.g. gold layer) is generally thermodynamically favoured.
  • a precious metal layer like e.g. gold layer
  • the presence of zinc in the copper containing layer was found to strongly decrease copper diffusion.
  • the first layer acts as a copper sink and prevents copper migration from copper containing layers of the electroplated product into the finishing precious metal layer of the electroplated product.
  • the electroplated product fulfills the main requirements of the fashion industry in terms of corrosion resistance, wear resistance and copper diffusion barrier properties. Compared to known alternatives in the prior art of palladium-less and nickel-less electroplated products, the inventive electroplated product shows a better corrosion performance, a better abrasion performance, an increased shelflife and a decreased production cost.
  • the copper concentration of the first copper alloy may differ from the copper concentration of the second copper alloy (in wt.-%) by an absolute value of 1 to 99 wt.-%, preferably 5 to 80 wt.-%, more preferably 10 to 60 wt.-%, even more preferably 15 to 40 wt.-%, most prefer ably 20 to 30 wt.-%,
  • the copper concentration in the second alloy can be higher than the copper concentration in the first alloy.
  • the second alloy e.g. yellow bronze
  • the first alloy having a lower copper concentration e.g. white bronze
  • the white bronze layer is deposited on the first layer (e.g. copper layer), the third layer (e.g. yellow bronze layer) is deposited on the second layer (e.g. white bronze layer) and the fourth layer (e.g. gold layer) is deposited on the third layer (e.g. yellow bronze layer).
  • the first layer e.g. copper layer
  • the third layer e.g. yellow bronze layer
  • the second layer e.g. white bronze layer
  • the fourth layer e.g. gold layer
  • the first copper alloy and/or the second copper alloy comprises Bi, Pb and/or Sb, preferably Bi. Having Bi in the alloy has the advantage that the alloy becomes both brighter and has an improved blocking ability of copper migration.
  • the first copper alloy and/or the second copper alloy may also comprise phosphorus and/or silicon.
  • the first copper alloy is white bronze and/or the second copper alloy is yellow bronze.
  • the fourth layer may be disposed on the second or third layer.
  • the electroplated product does not comprise palladium.
  • the layer may comprise or consist of a hydrophobic substance and is preferably a monolayer of a hydrophobic substance, more preferably a monolayer of a hydrophobic substance being a corrosion inhibitor, most preferably a monolayer of a corrosion inhibitor comprising thiol groups, especially a monolayer of alkanethiol monomers or alkanethiol polymers like e.g. octadecanethiol monomers.
  • This has the advantage that the surface of the finishing precious metal layer is made more hydrophobic and thus less prone to corrosion. Especially acid corrosion and corrosion due to sweat or interaction with leather is decreased. If the layer is only monomolecular in thickness, it is not visible and does not affect the appearance of the electroplated products.
  • the precious metal is selected from the group consisting of gold, silver, platinum, ruthenium, rhodium, palladium, osmium, iridium and alloys thereof, preferably gold, silver, palladium and alloys thereof, more preferably gold, palladium and alloys thereof, most preferably gold.
  • the base material may comprise or consist of bronze, brass, zamak, alpaca, copper alloy, tin alloy and/or steel. It is especially preferred that the base material comprises or consists of zamak.
  • the base material may be an article selected from the group consisting of jewelry, fashion, leather industry, watches, eyewear, trinkets and locks.
  • Example 1 Composition and properties of employed white and yellow bronze
  • the sample forms the cathode and a thin (4 mm diameter) copper tube forms the anode.
  • a small O-ring separates the anode from the cathode.
  • High-purity argon is pumped into the anode chamber.
  • a high voltage (DC or RF) between sample and anode ionizes the argon to produce a glow discharge.
  • the excited argon ions bombard the electroplated product sample and cause uniform sputtering of the sample surface. Atoms ejected are then excited by an Argon plasma, and finally come back to their fundamental energy level, emitting a characteristic X-ray photon.
  • Emitted photons whose energy is characteristic of the energy level of a chemical element, are then collected by photomultipliers.
  • the intensity of each emission depends on the concentration of the element in the sample.
  • the recorded signals are processed to obtain the distribution of the elements according to the erosion time.
  • GDOES provides depth profiling analysis of solids like metals, powders, polymers, glasses and ceramics (in the present case: depth profiling of electroplated substrates).
  • GDOES GDOES-like e.g. C, N and 0.
  • the Figures 1 to 6 give the GDOES depth profile for the different electroplated products of Examples 4 and 8 before and after the heat treatment at 180°C for 24 hours.
  • concentration of each chemical element Au, Cu, Zn, Sn and eventually Ni is shown (y-axis in wt.-%) as a function of the distance from the surface of the finishing layer towards the base material of the electroplated product (x-axis in ⁇ m).
  • the thicknesses of the layers given for the process of the argon ablation (abscissa) and the metal concentrations (ordinate) are not normalized, but reflect the progress of the metal migration from the as-plated to the annealed state (annealing at 180 °C for 24 h).
  • An electroplated nickel-containing product of the prior art comprises the following layers electrolytically deposited on a brass substrate: bright nickel layer: 10 ⁇ m nickel phosphorus layer: 2 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • Said electroplated nickel-containing product has the following properties: NFS 80772: 24 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 96 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • Turbula test is to simulate general wear that results from wearing the parts.
  • the test was performed using an industrial rotating machine (Turbula, model T2F, Willy A. Bachofen AG Maschinenfabrik, Switzerland).
  • Abrasive load was composed of abrasion ceramic elements mixed with fresh water containing a surface tension agent. Detailed information on the size of the ceramic elements is described in the ISO 23160 reference (see Table 1 - page 3). Test duration was 30 minutes. Evaluation of wear was done by visual inspection and comparison with reference samples. In particular, a color change after abrasion was used to evaluate wear resistance of the tested parts. The Turbula test is considered positive if no colour change is visible in the tested parts, especially on the edges or regions that are more exposed.
  • An electroplated nickel-less product of the prior art comprises the following layers electrolytically deposited on a brass substrate: bright copper layer: 10 ⁇ m white bronze layer: 2 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • Said electroplated nickel-free product has the following properties: NFS 80772: 12 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 48-72 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • the reason for which the bronze layer is very thin is related with the level of quality of bronze plating processes known in the prior art that do not allow exceeding 2 ⁇ m of the deposit while maintaining the desired bright aspect. In other words, this is the reason why thicker deposits of white bronze are undesirable for the jewelry and/or fashion industry because of a lack of brightness.
  • the precious metal layers are regularly a very thin deposit (approx. 0.5 ⁇ m), it is easy for corrosive media or mechanical action to reach the underlying bronze layer.
  • Said bronze layer is softer than nickel and has a slightly lower thickness. Thus, it is less resistant to mechanical stress and can be damaged easily.
  • the underlying copper layer Upon damage of the white bronze layer, the underlying copper layer will appear and be exposed to the atmosphere and oxidation. For these reasons, the nickel-free plated parts are more easily damaged by aggressive media, like leather and the acid sweat of human skin.
  • An electroplated nickel-containing product of the prior art comprises the following layers electrolytically deposited on a brass substrate: bright copper layer: 10 ⁇ m white bronze layer: 2 ⁇ m palladium-nickel layer: 0.3 ⁇ m gold layer as finishing layer: 0.5 ⁇ m
  • Said electroplated nickel-free product has the following properties: NFS 80772: 24 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 48-72 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: change of color in article edges more exposed to abrasion (copper color)
  • the electroplated nickel-free products of the first and second example have the following properties: NFS 80772: 24 HOURS; ABRASION WITH TURBULA: 5 MINUTES LEATHER INTERACTION UNDER ISO 4611: 96 HOURS; ISO 4538: 48 HOURS; ISO 4524/2: 8 HOURS; ISO 4611: 96 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 30 min.
  • the improvement of performance is essentially related to the protection of the copper underlayer on the one hand and to the conservation of the quality of the top gold layer on the other hand by the presence of both the white and yellow bronze layer.
  • Example 7 Performance in corrosion and abrasion tests of a nickel-less electroplated product - assessing the influence of the sequence of the bronze layers
  • the electroplated nickel-free product has the following properties: NFS 80772: 12 HOURS; ABRASION WITH TURBULA: 3 MINUTES LEATHER INTERACTION UNDER ISO 4611: 56 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 60 min.
  • the properties of the electroplated nickel-free product obtained for the plating sequence of example 4 are better than the properties obtained for the plating sequence of this example, showing that the sequence bright copper/yellow bronze/white bronze is less adapted as underlayer of gold than the sequence copper/white bronze/yellow bronze.
  • the present sequence is more adapted as an underlayer of Palladium as final finish.
  • Example 8 Performance in corrosion and abrasion tests of two non-inventive nickel-less electroplated product - assessing the significance of the difference in copper concentration of the bronze layers
  • the electroplated nickel-free product has the following properties: NFS 80772: 12 HOURS; ABRASION WITH TURBULA: 3 MINUTES LEATHER INTERACTION UNDER ISO 4611: 48 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 60 min.
  • the electroplated nickel-free product has the following properties: NFS 80772: 6 HOURS; ABRASION WITH TURBULA: 3 MINUTES LEATHER INTERACTION UNDER ISO 4611: 48 HOURS; ABRASION TEST BY TURBULA UNDER ISO 23160: no color change after 120 min.
  • Example 9 Corrosion and abrasion resistance of an electroplated article which comprises a palladium alloy as intermediate layer
  • Zamac is massively used in the luxury industry due to its low cost: compared to brass, the proportion between copper and zinc are opposed and the massive object contains mainly zinc.
  • the zinc potential of corrosion is lower than copper and reduces the "nobility" of the final article.
  • the final object to be electroplated is stamped starting from ingots with low compactness.
  • the stamping step will compress the material, but porosity remains and is uncontrollable during the stamping process.
  • the galvanic sequence will have to protect the material either from the attacks coming from outside (such as oxidizing medias), but also from the inside considering holes residues for the original ingot and the stamping process.
  • the stamping process will concentrate the pores in the thickness of the final article but as it happens frequently, the base material external composition presents low porosity density close to the galvanic treatment.
  • the electroplated article contains a palladium layer as intermediate layer.
  • the ageing useful to evaluate abrasion and corrosion resistance is in line with the following parameters:
  • This example describes the known use of a precious metal such as palladium as intermediate layer to save production costs compared to the expensive gold finishing.
  • This example of an electroplated nickel-less product comprises the following layers electrolytically deposited on a zamak substrate: copper layer: > 15 ⁇ m (30 - 50 ⁇ m) bronze layer (Cu-Sn-Zn alloy layer): 3 ⁇ m palladium alloy layer (nickel-free): 0.5 ⁇ m gold layer: 0.5 microns
  • the electroplated article was submitted to the synthetic sweat resistance test (performed following NFS 80772 standard with ageing).
  • Synthetic sweat is a conductive liquid. It will transport copper ions until the precious metal finishing where the opposite phenomenon happens and copper ions are reduced. This phenomenon is enhanced by the difference of corrosion potential between the substrate and the first copper layer and the presence of palladium below the gold layer due to high nobility of the final galvanic treatments. In fact, the presence of a Palladium layer between the copper layer and the gold layer enhances the copper dissolution rate.
  • An electron microscope allows the identification of the chemical composition of the surface of an article.
  • Table 1 below is a summary of the chemical composition obtained by EDS measurement located at the surface of the electroplated article before synthetic sweat interaction, on copper reduced areas and on oxidized areas. Table 1 before sweat interaction after sweat interaction unaltered areas (copper reduced areas) altered areas (oxidized areas) Au 82 wt.% 75 wt.% 0 wt.% Pd 10 wt.% 10 wt.% 0 wt.% Cu 5 wt.% 5 wt.% 5 wt.% Sn - - 2 wt.% Zn 3 wt.% 2 wt.% 55 wt.% O - 8 wt.% 38 wt.%
  • Example 10 Corrosion and abrasion resistance of an electroplated article having a substrate with high zinc content and low thickness of first copper layer
  • the ageing useful to evaluate abrasion and corrosion resistance is in line with the following parameters:
  • This example describes a sequence on zamak with a copper thickness lower than 15 ⁇ m.
  • the zamak alloy is mainly composed of zinc (around 70 - 80%). Zinc being soluble in most acids, an interaction with the synthetic sweat would directly destroy the base material.
  • This example of an electroplated nickel-less product comprises the following layers electrolytically deposited on a zinc alloy (zamak) substrate: copper layer: ⁇ 15 ⁇ m (8 - 15 ⁇ m) white bronze layer (Cu-Sn-Zn alloy layer): 3 ⁇ m yellow bronze layer (Cu-Sn-Zn alloy layer): 3 ⁇ m gold layer: 0.5 microns
  • Table 2 white bronze layer yellow bronze layer colour of the layer white yellow %Cu 46 - 49 wt.% 75 - 85 wt.% %Sn 40 - 45 wt.% 15 - 20 wt.% %Zn 10 - 15 wt.% 2 - 7 wt.% density of the alloy 8.3 g/cm 3 8.1 g/cm 3
  • Ageing of the electroplated articles was performed applying 3 minutes of TURBULA®.
  • the electroplated article was submitted to the synthetic sweat resistance test (performed following NFS 80772 standard with ageing).
  • Example 9 An improvement compared to the plating sequence in Example 9 was observed: Compared to example 9, the reduction of copper did not occur on the whole surface but rather only locally.
  • Table 3 below is a summary of the chemical composition located at the surface of the electroplated article before synthetic sweat interaction, on copper reduced areas and on oxidized areas. Table 3 before sweat interaction after sweat interaction unaltered areas (copper reduced areas) altered areas (oxidized areas) Au 95 wt.% 88 wt.% 0 wt.% Cu 3 wt.% 5 wt.% 5 wt.% Sn - - 2 wt.% Zn 2 wt.% 2 wt.% 55 wt.% O - 5 wt.% 38 wt.%
  • Example 11 Corrosion and abrasion resistance of an electroplated article having a substrate with high zinc content and high thickness of first copper layer
  • the thickness of the first copper layer is more than 15 ⁇ m.
  • the ageing useful to evaluate abrasion and corrosion resistance is in line with the following parameters:
  • This example describes a sequence on zamak with a copper thickness of more than 15 ⁇ m.
  • the zamak alloy is mainly composed of zinc (around 70 - 80%). Zinc being soluble in most acids, an interaction with the synthetic sweat would directly destroy the base material.
  • This example of an electroplated nickel-less product comprises the following layers electrolytically deposited on a zinc alloy (zamak) substrate: copper layer: > 15 ⁇ m (30 - 50 ⁇ m) white bronze layer (Cu-Sn-Zn alloy layer): 3 ⁇ m yellow bronze layer (Cu-Sn-Zn alloy layer): 3 ⁇ m gold layer: 0.5 microns
  • Table 4 white bronze layer yellow bronze layer colour of the layer white yellow %Cu 46 - 49 wt.% 75 - 85 wt.% %Sn 40 - 45 wt.% 15 - 20 wt.% %Zn 10 - 15 wt.% 2 - 7 wt.% density of the alloy 8.3 g/cm 3 8.1 g/cm 3
  • the electroplated article was submitted to the synthetic sweat resistance test (performed following NFS 80772 standard with ageing).
  • the chemical analysis of the surface of the electroplated article confirms that there are no sign of corrosion. Firstly, only the metals are detected i.e. no oxygen from corrosion is seen and the composition is unchanged. Secondly, the electron microscope (SEM) pictures before and after the corrosion test are identical and show no sign of corrosion on the surface after the synthetic sweat interaction for 24 hours.
  • Table 5 is a summary of the chemical composition located at the surface of the electroplated article before synthetic sweat interaction and after the synthetic sweat interaction.
  • Table 5 n/o no altered areas observed before sweat interaction after sweat interaction unaltered areas (copper reduced areas) altered areas (oxidized areas)
  • Au 96 wt.% 95.6 wt.% n/o Cu 2 wt.% 2.6 wt.% Sn - - Zn 2 wt.% 1.2 wt.% O - -
  • Example 10 Example 11 Substrate zamak zamak zamak First Copper layer copper: 30-50 microns copper: 8 - 15 microns copper: 30 - 50 microns Second layer white bronze alloy white bronze alloy white bronze alloy 46 - 49 wt.-% Cu 46 - 49 wt.-% Cu 46 - 49 wt.-% Cu 40 - 45 wt.-% Sn 40 - 45 wt.-% Sn 40 - 45 wt.-% Sn 10 - 15 wt.-% Zn 10 - 15 wt.-% Zn 10 - 15 wt.-% Zn 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5 microns 2.5
  • Example 9 Example 10
  • Example 11 sweat resistance negative negative positive global aspect after sweat interaction surface covered by copper reduction from the first layer local opening of holes from the substrate which lead to their oxidation local opening of holes without oxidation
  • EDS analysis of the global surface oxygen content is raised oxygen content is raised element concentration does not change EDS analysis on localized defect mainly zinc and oxygen mainly zinc and oxygen no defect

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Claims (16)

  1. Produit plaqué, comprenant
    a) un matériau de base ;
    b) une première couche comprenant du, ou constituée de, cuivre, où la première couche est disposée sur le matériau de base ;
    c) une deuxième couche comprenant un, ou constituée d'un, premier alliage de cuivre, où le premier alliage de cuivre comprend de l'étain et du zinc ;
    d) une troisième couche comprenant un, ou constituée d'un, second alliage de cuivre, où le second alliage de cuivre comprend de l'étain et du zinc ; et
    e) une quatrième couche comprenant un, ou constituée d'un, métal précieux, où le métal précieux est sélectionné dans le groupe constitué par l'or, l'argent, le platine, le ruthénium, le rhodium, le palladium, l'osmium, l'iridium et des alliages de ceux-ci ;
    où
    i) la deuxième couche est disposée sur la première couche, la troisième couche est disposée sur la deuxième couche, et la quatrième couche est disposée sur la troisième couche ; ou
    ii) la troisième couche est disposée sur la première couche, la deuxième couche est disposée sur la troisième couche, et la quatrième couche est disposée sur la deuxième couche ;
    et où la concentration en cuivre dans le premier alliage de cuivre, est différente de la concentration en cuivre dans le second alliage de cuivre,
    caractérisé en ce que
    la quatrième couche est la couche métallique de finition du produit plaqué,
    et la première couche présente une épaisseur comprise entre15 et 60 µm.
  2. Produit plaqué selon la revendication 1, caractérisé en ce que la concentration en cuivre dans le second alliage, est supérieure à la concentration en cuivre dans le premier alliage.
  3. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que la concentration en cuivre du premier alliage de cuivre, diffère de la concentration en cuivre du second alliage de cuivre, d'une valeur absolue comprise entre 1 et 99 % en poids, de préférence entre 5 et 80 % en poids, mieux entre 10 et 60 % en poids, mieux encore entre 15 et 40 % en poids, l'idéal étant entre 20 et 30 % en poids.
  4. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que la concentration en cuivre dans
    i) le premier alliage de cuivre, est ≤ 65 % en poids, de préférence compris entre 30 et 64 % en poids, mieux entre 40 et 60 % en poids, mieux encore entre 45 et 55 % en poids, par rapport au poids total de l'alliage de cuivre ; et / ou
    ii) le second alliage de cuivre, est ≥ 66 % en poids, de préférence compris entre 66 et 90 % en poids, mieux entre 70 et 87 % en poids, mieux encore entre 75 et 85 % en poids, par rapport au poids total de l'alliage de cuivre.
  5. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que la concentration en zinc dans
    i) le premier alliage de cuivre, est ≥ 10 % en poids, de préférence compris entre 11 et 35 % en poids, mieux entre 12 et 25 % en poids, mieux encore entre 15 et 20 % en poids, par rapport au poids total de l'alliage de cuivre ; et / ou
    ii) le second alliage de cuivre, peut être ≤ 15 % en poids, de préférence compris entre 2 et 10 % en poids, mieux entre 3 et 8 % en poids, mieux encore entre 4 et 7 % en poids, par rapport au poids total de l'alliage de cuivre.
  6. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que la concentration en étain dans
    i) le premier alliage de cuivre, peut être ≥ 26 % en poids, de préférence compris entre 26 et 35 en % poids, par rapport au poids total de l'alliage de cuivre ; et / ou
    ii) le second alliage de cuivre, peut être ≤ 25 % en poids, de préférence compris entre 1 et 25 % en poids, mieux entre 10 et 25 % en poids, mieux encore entre 15 et 25 % en poids, par rapport au poids total de l'alliage de cuivre.
  7. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que le premier alliage de cuivre et / ou le second alliage de cuivre comprend du Bi, du Pb et / ou du Sb, de préférence du Bi.
  8. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que la quatrième couche est disposée sur la deuxième ou sur la troisième couche.
  9. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce qu'aucune couche ne comprend du, ou n'est constituée de, palladium entre la première couche et la quatrième couche, où le produit plaqué ne comprend de préférence pas de palladium.
  10. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce qu'aucune couche ne comprend du, ou n'est constituée de, nickel, de cobalt et / ou de chrome, entre la première couche et la quatrième couche, où le produit plaqué ne comprend de préférence ni nickel, ni cobalt et / ou ni chrome, mieux encore pas de nickel.
  11. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce qu'une couche de protection organique est disposée sur la quatrième couche, de préférence une couche comprenant une, ou constituée d'une, substance hydrophobe, de préférence une monocouche d'une substance hydrophobe, mieux une monocouche d'une substance hydrophobe d'inhibition de la corrosion, mieux encore une monocouche d'une substance hydrophobe constituée de groupes thiols, en particulier une monocouche de monomères d'alcanethiols ou de polymères d'alcanethiols.
  12. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que le métal précieux est sélectionné dans le groupe constitué par l'or, l'argent, le palladium et des alliages de ceux-ci, mieux constitué par l'or, le palladium et des alliages de ceux-ci, mieux encore constitué par l'or.
  13. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que le matériau de base comprend du, ou est constitué de, bronze, laiton, zamak, alpaga, alliage de cuivre, alliage d'étain et / ou acier, de préférence il comprend du, ou est constitué de, zamak.
  14. Produit plaqué selon l'une quelconque des revendications précédentes, caractérisé en ce que l'épaisseur de
    i) la première couche, est comprise entre 16 et 60 µm, de préférence entre 20 et 55 µm, mieux entre 25 et 50 µm, mieux encore entre 30 et 45 µm ;
    ii) la deuxième couche, est comprise entre 1 et 10 µm, de préférence entre 2 et 8 µm ;
    iii) la troisième couche, est comprise entre 1 et 10 µm, de préférence entre 2 et 4 µm ; et / ou
    iv) la quatrième couche, est comprise entre 0,1 et 5 µm, de préférence entre 0,2 et 1 µm.
  15. Procédé destiné à produire un produit plaqué selon l'une quelconque des revendications précédentes, comprenant les étapes suivantes :
    a) plaquer une couche comprenant le, ou constituée du, premier alliage de cuivre sur une couche de cuivre disposée sur un substrat ;
    b) plaquer une couche comprenant le, ou constituée du, second alliage de cuivre sur la couche de l'étape a) ;
    c) plaquer une couche comprenant le, ou constituée du, métal précieux sur la couche de l'étape b) ;
    où la première couche d'alliage de cuivre est plaquée avec une concentration en cuivre différente de celle de la deuxième couche d'alliage de cuivre.
  16. Utilisation du produit plaqué selon l'une quelconque des revendications 1 à 14 dans l'industrie des bijoux, l'industrie de la mode, l'industrie du cuir, l'industrie de l'horlogerie, l'industrie des lunettes, l'industrie des bibelots et / ou l'industrie de la serrurerie.
EP16194360.0A 2016-10-18 2016-10-18 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations Active EP3312309B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PT161943600T PT3312309T (pt) 2016-10-18 2016-10-18 Produto galvanizado tendo uma camada de acabamento de metal precioso e resistência à corrosão melhorada, método para a sua produção e suas utilizações
EP16194360.0A EP3312309B1 (fr) 2016-10-18 2016-10-18 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations
ES16194360T ES2805102T3 (es) 2016-10-18 2016-10-18 Producto galvanizado que tiene una capa de acabado de metal precioso y mejor resistencia a la corrosión, método para su producción y usos del mismo

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP16194360.0A EP3312309B1 (fr) 2016-10-18 2016-10-18 Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations

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EP3312309A1 EP3312309A1 (fr) 2018-04-25
EP3312309B1 true EP3312309B1 (fr) 2020-04-29

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EP (1) EP3312309B1 (fr)
ES (1) ES2805102T3 (fr)
PT (1) PT3312309T (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3705607A1 (fr) * 2019-03-08 2020-09-09 COVENTYA S.p.A. Composition et procédé de protection de substrats de métal précieux par une nanocouche organique
EP3751356B1 (fr) * 2019-03-14 2022-12-21 Richemont International S.A. Composant horloger perfectionné
DE102021117095A1 (de) * 2021-07-02 2023-01-05 Umicore Galvanotechnik Gmbh Bronzeschichten als Edelmetallersatz

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JP4642317B2 (ja) * 2000-06-27 2011-03-02 シチズンホールディングス株式会社 白色被膜を有する装飾品
JP3638509B2 (ja) * 2000-08-09 2005-04-13 河口湖精密株式会社 時計用外装部品
JP2003096592A (ja) * 2001-09-20 2003-04-03 Kawaguchiko Seimitsu Co Ltd 時計用外装部品
CN101096769A (zh) 2006-06-26 2008-01-02 比亚迪股份有限公司 一种电镀方法
DE102012008544A1 (de) 2012-05-02 2013-11-07 Umicore Galvanotechnik Gmbh Verchromte Verbundwerkstoffe ohne Nickelschicht

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PT3312309T (pt) 2020-07-28
EP3312309A1 (fr) 2018-04-25

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