EP2196563A1 - Procédé pour éviter le ternissement de couches d'argent - Google Patents

Procédé pour éviter le ternissement de couches d'argent Download PDF

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Publication number
EP2196563A1
EP2196563A1 EP08021571A EP08021571A EP2196563A1 EP 2196563 A1 EP2196563 A1 EP 2196563A1 EP 08021571 A EP08021571 A EP 08021571A EP 08021571 A EP08021571 A EP 08021571A EP 2196563 A1 EP2196563 A1 EP 2196563A1
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EP
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Prior art keywords
metal
layer
silver
palladium
platinum
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EP08021571A
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German (de)
English (en)
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EP2196563B1 (fr
Inventor
Hans Ullrich Eckert
Michael Ryl
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MacDermid Enthone Inc
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Enthone Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—Multistep pretreatment with use of metal first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/161—Mercaptans
    • 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
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group 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
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • 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

Definitions

  • the present invention relates to a method for preventing the tarnishing of silver layers and silver layers with significantly improved tarnish protection.
  • Objects made of silver, or objects silvered with corresponding silver layers tend to darken on contact with air. Depending on the duration of exposure, yellowish-brown to black deposits develop on the silver surfaces.
  • the main cause of this problem is the formation of sulfides and oxides of silver by reaction with airborne organic sulfur compounds, or sulfur compounds derived from organic sources, such as food and beverages or body fluids and body fats.
  • This object is achieved with respect to the method by a method for preventing the tarnishing of silver layers, which is characterized in that on the silver layer, a layer of a metal from the group consisting of palladium, platinum, osmium and rhenium with a layer thickness of 5 nm to 100 nm is applied.
  • the layer of a metal of the group consisting of palladium, platinum, osmium and rhenium is applied to the silver layer by contacting the silver layer with an electrolyte containing ions of a corresponding metal.
  • silver layers are deposited on substrate surfaces of cyanide-containing silver electrolytes.
  • the electrolyte, with which the silver layer for depositing a metal of the group consisting of palladium, platinum, osmium and rhenium is brought into contact an acidic electrolyte, since acidic electrolytes against the eventual entry of cyanide by the upstream Silvering are insensitive.
  • the deposition of a corresponding palladium, platinum, osmium or rhenium layer or a layer containing at least one of these metals can be carried out both galvanically and de-energized.
  • the concentration of the metal of the group consisting of palladium, platinum, osmium and rhenium in the electrolyte may be between 0.5 g / l and 20 g / l, preferably between 1 g / l and 10 g / l and still more preferably between 1 g / l and 5 g / l.
  • the electrolyte which can be used according to the invention for the electrodeposition of such a layer furthermore has a conductive salt in a concentration of between 10 g / l and 200 g / l and, for improving the substrate surface, a wetting agent in a concentration of between 1 g / l and 10 g / l ,
  • Suitable conductive salts are, for example, alkanesulphonates, ammonium chloride, ammonium sulphate, ammonium sulphamate, as well as sulphates, citrates or phosphates of sodium or potassium.
  • a suitable wetting agent is, for example, the wetting agent marketed under the name TamoINM and based on naphthalene sulphonic acid condensation products.
  • a current density between 0.1 A / dm 2 and 4 A / dm 2 , preferably between 0.5 A / dm 2 and 3 A / dm 2 is set.
  • the contact time ie the time for which a corresponding current density is set between the silver layer and the counterelectrode, varies between 1 second and 60 seconds, preferably between 1 second and 10 seconds.
  • the silver layer is contacted with the corresponding electrolyte at a temperature between 20 ° C and 80 ° C.
  • the preferred temperature for contacting is in a range between 40 ° C and 60 ° C.
  • the substrate surface having a silver layer is contacted with an electrolyte comprising a metal from the group consisting of palladium, platinum, osmium and rhenium in a concentration between 0.5 g / l and 5 g / l has.
  • an electrolyte comprising a metal from the group consisting of palladium, platinum, osmium and rhenium in a concentration between 0.5 g / l and 5 g / l has.
  • the metal to be deposited in the form of a thin layer of the group consisting of palladium, platinum, osmium and rhenium in the form of a salt, such as sulphate, chloride or sulphonate, is added to the electrolyte.
  • an electrolyte for the inventive autocatalytic deposition of a thin anti-tarnish layer proves a conductive salt in a concentration between 5 g / l and 50 g / l.
  • Suitable conductive salts are, for example, sodium borate, ammonium chloride, ammonium sulfate, ammonium sulfamate, as well as sulfates, citrates or phosphates of sodium or potassium.
  • a reducing agent in a concentration between 5 g / l and 20 g / l.
  • particularly suitable reducing agents are hydrogen peroxide, hypophosphite, hydrazine, formaldehyde or borohydrocarbon compounds.
  • An electrolyte as described above for autocatalytic deposition according to the invention may have a pH in the range between pH 5 and pH 9, with a range between pH 6 and pH 8 being preferred.
  • the temperature of the electrolyte can be varied in the autocatalytic deposition in a range between 50 ° C and 80 ° C, with a range of 60 ° C to 70 ° C is preferred.
  • the electrolyte may have a wetting agent in a concentration between 0.1 ml / l and 2 ml / l.
  • Suitable wetting agents in this case are, for example, sodium lauryl ether.
  • the silver layer is brought into contact with an electrolyte which is a metal of the group consisting of palladium, platinum, osmium and rhenium in the form of a metal / metal colloid with the metal of said group as the core metal and a Has core surrounding colloidal metal.
  • an electrolyte which is a metal of the group consisting of palladium, platinum, osmium and rhenium in the form of a metal / metal colloid with the metal of said group as the core metal and a Has core surrounding colloidal metal.
  • suitable colloidal metals according to the invention are, for example, iron, tin, lead, cobalt or germanium.
  • Such metal / metal colloid systems are for example from EP 0 538 006 A1 known and are used for the metallization of plastic surfaces.
  • the silver layer Following the treatment of the silver layer with the aforementioned electrolytes, it is contacted with a treating solution comprising a reducing agent or a metal reducible by the colloidal metal.
  • hydrogen peroxide, hypophosphites, hydrazine, formaldehyde or hydrobromic compounds can be used here as reducing agents.
  • Suitable metals which are reducible by the colloidal metal are, for example, silver, gold, nickel, palladium, platinum, bismuth or mixtures of these. These metals, which can be reduced by the colloidal metal, are ionogenic in the treatment solution to be used according to the invention.
  • the metal reducible by the colloid metal can advantageously also be deposited on the silver layer.
  • the treatment solution to be used according to the invention also has suitable complexing agents to prevent precipitation of the released colloidal metals.
  • the metal / metal colloid-containing electrolyte has a metal / metal colloid with palladium as the core metal and tin as the colloidal metal, and the treatment solution has palladium in ionic form as metal reducible by the colloidal metal.
  • SAMs self-assembling molecules
  • SAMs self-assembling molecules
  • These self-organizing molecules then form on the silver layer a further layer which prevents or at least reduces the tarnishing of the silver layer.
  • another metal such as copper and / or nickel
  • the metal of the group consisting of palladium, platinum, osmium and rhenium can be deposited with the metal of the group consisting of palladium, platinum, osmium and rhenium.
  • the mechanical or electrical properties of the deposited as tarnish protection metal layer can be influenced in an advantageous manner.
  • the co-deposition of copper leads to higher ductility of the coatings and to a cost reduction by mitabedorfenen copper content.
  • the deposition of nickel also leads to a higher ductility of the layer, but at the same time reduces pore formation and improves corrosion resistance.
  • the co-deposited metal may be contained by the process of the invention in electrolytes in a concentration between 0.1 g / l and 5 g / l, preferably between 0.5 g / l and 3 g / l.
  • a current pulse is applied between the silver layer and a counterelectrode, which serves to initialize a subsequent electroless deposition of said metal on the silver layer.
  • the object according to the invention is achieved by a silver coating, which is characterized in that the silver coating also has a layer comprising a metal of the group consisting of palladium, platinum, osmium and rhenium with a layer thickness of 5 nm to 100 nm is.
  • a metal of the group consisting of copper, nickel, gold, platinum, bismuth or mixtures thereof can be deposited.
  • a layer of a self-organizing molecule such as, for example, hexadecanethiol and / or octadecanethiol, can be applied to the silver coating according to the invention.
  • FIG. 12 shows the relationship between the selected concentration of the metal of the group consisting of palladium, platinum, osmium and rhenium in an electrolyte to be used in the present invention and the current density to be set and the contact time to obtain a silver layer tarnish prevention layer according to the present invention.
  • a deposition metal concentration of 8 g / l in the electrolyte and a set mean current density of 1.5 A / dm 2 a layer thickness of 5 nm to 100 nm according to the invention can be achieved within a contact time of 1 second. The lower the set average current density, the longer the contact time must be.
  • a previously silver-coated substrate is contacted with an electrolyte containing 1 g / L of palladium sulfate, 100 g / L of an alkanesulfonate, and 3 g / L of a surfactant type TamolNM at a temperature of 40 ° C.
  • a current density of 0.5 A / dm 2 is set for a time of 5 seconds.
  • the substrate surface obtained under these conditions is mirror-polished and shows no tendency to run even after a long time.
  • a tarnish protection is applied autocatalytically.
  • the substrate with an electrolyte, which 1 g / l of palladium sulfate, 8 g / l sodium borate, 10 g / l of sodium hypophosphite and 0.5 ml / l of a wetting agent (sodium lauryl ether) at a temperature of 65 ° C and a set pH of 7.5 for 3 minutes in contact.
  • a wetting agent sodium lauryl ether
  • a previously coated with a silver layer substrate with an as in this example previously described electrolyte was brought into contact, wherein at the beginning of the deposition, a short current pulse of about 1 second at a set current density of about 0.1 A / dm 2 was created.
  • the contact time could be shortened to 1 minute. Also in this case a mirror-like substrate surface was obtained, which shows no tendency to tarnish even after a long time.
  • the substrate obtained in Example 1 and in Example 2 was contacted with an alkanephosphonic acid or an alkali phosphonic acid derivative (eg hexadecyl-, octadecylphosphonic acid, or mixtures thereof).
  • an alkanephosphonic acid or an alkali phosphonic acid derivative eg hexadecyl-, octadecylphosphonic acid, or mixtures thereof.
  • an improved start-up behavior and increased corrosion protection were achieved compared to the substrates obtained from Examples 1 and 2.
  • the treated layers showed after one Treatment with Sulfur Liver (Universal Oxide ECTH B-48) did not show any discoloration after exposure for 1 s or for 10 s exposure time, whereas untreated silver layers showed a spontaneous intense black discoloration even with a short exposure time.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
EP08021571A 2008-12-12 2008-12-12 Procédé pour éviter le ternissement de couches d'argent Ceased EP2196563B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08021571A EP2196563B1 (fr) 2008-12-12 2008-12-12 Procédé pour éviter le ternissement de couches d'argent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08021571A EP2196563B1 (fr) 2008-12-12 2008-12-12 Procédé pour éviter le ternissement de couches d'argent

Publications (2)

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EP2196563A1 true EP2196563A1 (fr) 2010-06-16
EP2196563B1 EP2196563B1 (fr) 2013-04-03

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103361682A (zh) * 2012-02-29 2013-10-23 罗门哈斯电子材料有限公司 防止银变色的方法
US10955936B2 (en) 2015-07-17 2021-03-23 Trinamix Gmbh Detector for optically detecting at least one object
EP3693494A4 (fr) * 2017-10-06 2021-06-30 C. Uyemura & Co., Ltd. Solution de déposition autocatalytique de palladium
KR20210134968A (ko) * 2019-04-09 2021-11-11 제이에프이 스틸 가부시키가이샤 랜스 노즐
EP4249646A1 (fr) 2022-03-24 2023-09-27 Rohm and Haas Electronic Materials LLC Procede d'inhibition de la formation de ternissement et de la corrosion

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GB1423609A (en) * 1973-02-26 1976-02-04 Schering Ag Process for inhibiting silver tarnishing
GB1443322A (en) * 1972-10-09 1976-07-21 Oxy Metal Industries Corp Process for obtaining a silver or silvered piece with resistance to discolouration and corrosion and the pieces obtained by carrying out said process
EP0116173A1 (fr) * 1983-02-11 1984-08-22 Allied Corporation Miroirs argentés avec un revêtement d'alliage de métal noble
EP0538006A1 (fr) 1991-10-15 1993-04-21 ENTHONE-OMI, Inc. Procédé de métallisation directe
WO1996034412A1 (fr) * 1995-04-27 1996-10-31 National Semiconductor Corporation Revetement protecteur combine pour grilles de connexions
GB2438198A (en) * 2006-05-16 2007-11-21 Andrew Hermiston Hooper Silver alloys

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GB1443322A (en) * 1972-10-09 1976-07-21 Oxy Metal Industries Corp Process for obtaining a silver or silvered piece with resistance to discolouration and corrosion and the pieces obtained by carrying out said process
GB1423609A (en) * 1973-02-26 1976-02-04 Schering Ag Process for inhibiting silver tarnishing
EP0116173A1 (fr) * 1983-02-11 1984-08-22 Allied Corporation Miroirs argentés avec un revêtement d'alliage de métal noble
EP0538006A1 (fr) 1991-10-15 1993-04-21 ENTHONE-OMI, Inc. Procédé de métallisation directe
WO1996034412A1 (fr) * 1995-04-27 1996-10-31 National Semiconductor Corporation Revetement protecteur combine pour grilles de connexions
GB2438198A (en) * 2006-05-16 2007-11-21 Andrew Hermiston Hooper Silver alloys

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103361682A (zh) * 2012-02-29 2013-10-23 罗门哈斯电子材料有限公司 防止银变色的方法
US10955936B2 (en) 2015-07-17 2021-03-23 Trinamix Gmbh Detector for optically detecting at least one object
EP3693494A4 (fr) * 2017-10-06 2021-06-30 C. Uyemura & Co., Ltd. Solution de déposition autocatalytique de palladium
US11946144B2 (en) 2017-10-06 2024-04-02 C. Uyemura & Co., Ltd. Electroless palladium plating solution
KR20210134968A (ko) * 2019-04-09 2021-11-11 제이에프이 스틸 가부시키가이샤 랜스 노즐
EP4249646A1 (fr) 2022-03-24 2023-09-27 Rohm and Haas Electronic Materials LLC Procede d'inhibition de la formation de ternissement et de la corrosion

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