EP3312309B1 - Elektroplattiertes produkt mit einer edelmetalloberflächenschicht und verbesserter korrosionsbeständigkeit, verfahren zu dessen herstellung und verwendungen davon - Google Patents

Elektroplattiertes produkt mit einer edelmetalloberflächenschicht und verbesserter korrosionsbeständigkeit, verfahren zu dessen herstellung und verwendungen davon 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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layer
copper
copper alloy
electroplated product
alloy
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French (fr)
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EP3312309A1 (de
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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 ES16194360T priority patent/ES2805102T3/es
Priority to PT161943600T priority patent/PT3312309T/pt
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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. Galvanisch beschichtetes Produkt, umfassend
    a) ein Grundmaterial;
    b) eine erste Schicht, enthaltend oder bestehend aus Kupfer, wobei die erste Schicht auf dem Basismaterial angeordnet ist;
    c) eine zweite Schicht, enthaltend oder bestehend aus einer ersten Kupferlegierung, wobei die erste Kupferlegierung Zinn und Zink enthält;
    d) eine dritte Schicht, enthaltend oder bestehend aus einer zweiten Kupferlegierung, wobei die zweite Kupferlegierung Zinn und Zink enthält; und
    e) eine vierte Schicht, enthaltend oder bestehend aus einem Edelmetall, wobei das Edelmetall ausgewählt ist aus der Gruppe bestehend aus Gold, Silber, Platin, Ruthenium, Rhodium, Palladium, Osmium, Iridium und deren Legierungen;
    wobei
    i) die zweite Schicht auf der ersten Schicht angeordnet ist, die dritte Schicht auf der zweiten Schicht angeordnet ist und die vierte Schicht auf der dritten Schicht angeordnet ist; oder
    ii) die dritte Schicht auf der ersten Schicht angeordnet ist, die zweite Schicht auf der dritten Schicht angeordnet ist und die vierte Schicht auf der zweiten Schicht angeordnet ist;
    und wobei sich die Kupferkonzentration in der ersten Kupferlegierung von der Kupferkonzentration in der zweiten Kupferlegierung unterscheidet,
    dadurch gekennzeichnet, dass die vierte Schicht die abschließende Metallschicht des galvanisch beschichteten Produkts ist,
    und die erste Schicht eine Dicke im Bereich von >15 bis 60 µm aufweist.
  2. Galvanisch beschichtetes Produkt nach Anspruch 1, dadurch gekennzeichnet, dass die Kupferkonzentration in der zweiten Legierung höher ist als die Kupferkonzentration in der ersten Legierung.
  3. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass sich die Kupferkonzentration der ersten Kupferlegierung von der Kupferkonzentration der zweiten Kupferlegierung um einen Absolutwert von 1 bis 99 Gew.-%, vorzugsweise 5 bis 80 Gew.-%, bevorzugter 10 bis 60 Gew.-%, noch bevorzugter 15 bis 40 Gew.-%, besonders bevorzugt 20 bis 30 Gew.-%, unterscheidet.
  4. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Kupferkonzentration in der
    i) ersten Kupferlegierung ≤ 65 Gew.-%, vorzugsweise 30 bis 64 Gew.-%, bevorzugter 40 bis 60 Gew.-%, besonders bevorzugt 45 bis 55 Gew.-%, in Bezug auf das Gesamtgewicht der Kupferlegierung beträgt; und/oder
    ii) der zweiten Kupferlegierung ≥ 66 Gew.-%, vorzugsweise 66 bis 90 Gew.-%, bevorzugter 70 bis 87 Gew.-%, besonders bevorzugt 75 bis 85 Gew.-%, in Bezug auf das Gesamtgewicht der Kupferlegierung beträgt.
  5. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Zinkkonzentration in der
    i) ersten Kupferlegierung ≥ 10 Gew.-%, vorzugsweise 11 bis 35 Gew.-%, bevorzugter 12 bis 25 Gew.-%, besonders bevorzugt 15 bis 20 Gew.-%, in Bezug auf das Gesamtgewicht der Kupferlegierung beträgt; und/oder
    ii) die zweite Kupferlegierung ≤ 15 Gew.-%, vorzugsweise 2 bis 10 Gew.-%, bevorzugter 3 bis 8 Gew.-%, besonders bevorzugt 4 bis 7 Gew.-%, in Bezug auf das Gesamtgewicht der Kupferlegierung betragen kann.
  6. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Zinnkonzentration in der
    i) ersten Kupferlegierung ≥ 26 Gew.-%, vorzugsweise 26 bis 35 Gew.-%, in Bezug auf das Gesamtgewicht der Kupferlegierung betragen kann; und/oder
    ii) die zweite Kupferlegierung ≤ 25 Gew.-%, vorzugsweise 1 bis 25 Gew.-%, bevorzugter 10 bis 25 Gew.-%, besonders bevorzugt 15 bis 25 Gew.- %, in Bezug auf das Gesamtgewicht der Kupferlegierung betragen kann.
  7. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die erste Kupferlegierung und/oder die zweite Kupferlegierung Bi, Pb und/oder Sb, vorzugsweise Bi, enthält.
  8. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die vierte Schicht auf der zweiten oder dritten Schicht angeordnet ist.
  9. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass keine Schicht, enthaltend oder bestehend aus Palladium, zwischen der ersten Schicht und der vierten Schicht vorhanden ist, wobei das galvanisch beschichtete Produkt vorzugsweise kein Palladium enthält.
  10. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass keine Schicht, enthaltend oder bestehend aus Nickel, Kobalt und/oder Chrom, zwischen der ersten Schicht und der vierten Schicht vorhanden ist, wobei das galvanisch beschichtete Produkt vorzugsweise kein Nickel, Kobalt und/oder Chrom, besonders bevorzugt kein Nickel, enthält.
  11. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass auf der vierten Schicht eine organische Schutzschicht angeordnet ist, vorzugsweise eine Schicht, enthaltend oder bestehend aus einer hydrophoben Substanz, bevorzugter eine Monoschicht aus einer hydrophoben Substanz, noch bevorzugter eine Monoschicht aus einer hydrophoben Substanz, die ein Korrosionsinhibitor ist, besonders bevorzugt eine Monoschicht aus einer hydrophoben Substanz, umfassend Thiolgruppen, insbesondere eine Monoschicht aus Alkanethiol-Monomeren oder Alkanethiol-Polymeren.
  12. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Edelmetall ausgewählt ist aus der Gruppe bestehend aus Gold, Silber, Palladium und deren Legierungen, bevorzugter Gold, Palladium und deren Legierungen, besonders bevorzugt Gold.
  13. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass das Grundmaterial aus Bronze, Messing, Zamak, Alpaka, Kupferlegierung, Zinnlegierung und/oder Stahl enthält oder daraus besteht, vorzugsweise Zamak enthält oder daraus besteht.
  14. Galvanisch beschichtetes Produkt nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass die Dicke
    i) der ersten Schicht 16 bis 60 µm, vorzugsweise 20 bis 55 µm, bevorzugter 25 bis 50 µm, besonders bevorzugt 30 bis 45 µm beträgt;
    ii) der zweiten Schicht 1 bis 10 µm, vorzugsweise 2 bis 8 µm, beträgt;
    iii) der dritten Schicht 1 bis 10 µm, vorzugsweise 2 bis 4 µm beträgt; und/oder
    iv) der vierten Schicht 0,1 bis 5 µm, vorzugsweise 0,2 bis 1 µm, beträgt.
  15. Verfahren des Herstellens eines galvanisch beschichteten Produkts nach einem der vorangehenden Ansprüche, umfassend die Schritte:
    a) Galvanische Abscheidung einer Schicht, enthaltend oder bestehend aus der ersten Kupferlegierung, auf eine Kupferschicht, die auf einem Substrat angeordnet ist;
    b) Galvanische Abscheidung einer Schicht, enthaltend oder bestehend aus der zweiten Kupferlegierung, auf die Schicht von Schritt a);
    c) Galvanische Abscheidung einer Schicht, enthaltend oder bestehend aus dem Edelmetall, auf die Schicht von Schritt b),
    wobei die erste Kupferlegierungsschicht mit einer Kupferkonzentration plattiert ist, die sich von der der zweiten Kupferlegierungsschicht unterscheidet.
  16. Verwendung des galvanisch beschichteten Produkts nach einem der Ansprüche 1 bis 14 in der Schmuckindustrie, Modeindustrie, Lederindustrie, Uhrenindustrie, Brillenindustrie, Modeschmuckindustrie und/oder Türschlossindustrie.
EP16194360.0A 2016-10-18 2016-10-18 Elektroplattiertes produkt mit einer edelmetalloberflächenschicht und verbesserter korrosionsbeständigkeit, verfahren zu dessen herstellung und verwendungen davon Active EP3312309B1 (de)

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Application Number Priority Date Filing Date Title
EP16194360.0A EP3312309B1 (de) 2016-10-18 2016-10-18 Elektroplattiertes produkt mit einer edelmetalloberflächenschicht und verbesserter korrosionsbeständigkeit, verfahren zu dessen herstellung und verwendungen davon
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
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

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EP3705607A1 (de) * 2019-03-08 2020-09-09 COVENTYA S.p.A. Zusammensetzung und verfahren zum schutz von edelmetallsubstraten durch eine organische nanoschicht
EP3751356B1 (de) * 2019-03-14 2022-12-21 Richemont International S.A. Perfektionierte uhr komponente
DE102021117095A1 (de) * 2021-07-02 2023-01-05 Umicore Galvanotechnik Gmbh Bronzeschichten als Edelmetallersatz

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WO2002000958A1 (fr) * 2000-06-27 2002-01-03 Citizen Watch Co., Ltd. Article decoratif comportant une pellicule blanche et procede de production associe
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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