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EP2588644B1 - Couches de métal noble/métal pouvant subir des contraintes tribologiques - Google Patents

Couches de métal noble/métal pouvant subir des contraintes tribologiques Download PDF

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Publication number
EP2588644B1
EP2588644B1 EP11738647.4A EP11738647A EP2588644B1 EP 2588644 B1 EP2588644 B1 EP 2588644B1 EP 11738647 A EP11738647 A EP 11738647A EP 2588644 B1 EP2588644 B1 EP 2588644B1
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EP
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Prior art keywords
noble metal
bath
layer
substrate
nickel
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EP11738647.4A
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German (de)
English (en)
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EP2588644A1 (fr
Inventor
Stefan Koppe
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Schauenburg Ruhrkunststoff GmbH
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Schauenburg Ruhrkunststoff GmbH
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    • 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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1671—Electric field
    • 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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • 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
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver

Definitions

  • the invention relates to a method for producing tribologically resilient noble metal / metal layers. These are layers with a thickness of up to 50 ⁇ m.
  • the invention also relates to substrates with such a coating and their use.
  • Noble metal-containing metal layers are well known in the art. As a rule, these layers consist of at least one noble metal in a mixture or alloy with at least one less noble metal than the noble metal. Such layers make it possible to improve the properties of the less noble metal layer. This improvement may be in corrosion resistance, hardness, conductivity or biocidal properties. At the same time, a lower noble metal content makes the production of the layers more cost-effective. The layers also partly retain the advantageous properties of the less noble metal layers.
  • the layers can be deposited either by galvanic or electroless methods.
  • noble metal ions are usually added to the known baths for the electroless deposition of a metal. That I
  • the precious metal is much easier to reduce, it is deposited together with the metal as a mixture.
  • Pure noble metal layers which are deposited without current, are often soft and do not show sufficient abrasion resistance. Contour resolution or fidelity and depth dispersion are not sufficient for complete and unadulterated coverage of tissue or slit structures.
  • hard metals for example cobalt
  • the layers are not free from pores and are soon infiltrated or detached.
  • the font DE 10 2006 020 988 A1 describes, for example, the production of noble metal-containing nickel layers.
  • the font GB 1 222 969 describes the electrodeposition of a metal from a bath, which is also suitable for the electroless deposition of the same metal.
  • the object of the invention is to overcome the disadvantages of the prior art and to provide a method by which precious metal-containing metal layers can be obtained, which in particular have advantageous tribological properties.
  • the method should allow to coat nets or screens.
  • the layers must be produced without pores in order to prevent infiltration, especially when used in fluids.
  • a noble metal / metal layer is a layer in which the proportion of noble metal in wt .-% is higher than the proportion of metal. The reverse applies to a metal / precious metal layer.
  • a bath for electroless deposition of a metal layer which additionally contains at least one kind of noble metal ions.
  • Such electroless plating baths are known to those skilled in the art. It is a bath, which consists of z. B. an aqueous solution of a salt of a metal, which is to be deposited on the substrate by reduction of the salt. The reduction takes place without current through a reducing agent. In this case usually begins a deposition only when certain conditions, usually selected from pH and / or temperature of the bath.
  • electroless methods are often autocatalytic systems. This means that the deposited metal layer catalyzes the further deposition of metal. The thickness of the deposited layer can be controlled over the duration of the deposition.
  • a reducing agent for electroless deposition.
  • electrolessly deposited metals are nickel, copper, palladium, silver or gold.
  • aldehydes z.
  • formaldehyde formic acid, borohydride compounds, for example alkylamine boranes, dimethyl, diethylaminoborane or sodium borohydride, furthermore hydroxylamine, hydrazine, hydroxycarboxylic acids, their salts or thiourea or derivatives thereof, phosphorus compounds, for example hypophosphites such as sodium hypophosphite, are used.
  • a reducing gas such as hydrogen, can be passed through the bath.
  • metal / reductant systems are copper / formaldehyde, gold / formaldehyde, palladium / hypophosphite, silver / hypophosphite, nickel / borohydrides and nickel / hypophosphite.
  • the proportions of metal and reducing agent in the bath depend on the metal and reducing agent used. Thus, the proportion of metal between 0.01 and 20 g / l and the content of reducing agent between 5 and 50 g / l.
  • the solvent of the bath is preferably water. However, it is also possible to add or add organic solvents if the solubility of the bath constituents in water is not sufficiently high.
  • the organic solvents may also be added proportionally. Suitable organic solvents are, in particular, lower alcohols. Preferably, only water is used as the solvent.
  • the metal salts used are usually the corresponding chlorides, sulfates, carbonates, acetates or nitrates. It is also possible to use mixtures of metal salts with different cations and / or anions.
  • the bath can also contain other additives.
  • additives for example, oxocarboxylic acids or complexing agents, which prevent the decomposition of the bath.
  • the bath may also contain complexing agents for the ions of the metal salts to reduce the amount of free metal ions.
  • these may be carboxylic acids, amines, alkylamines, amino acids, phosphonates, cyanates, isocyanates, thiocyanates, ethers or thioethers.
  • citric acid chelating ligands such as ethylenediaminetetraacetic acid, 1,3-diaminopropane, 1,2-bis- ⁇ -aminopropylamino) ethane, 2-diethylaminoethylamine and diethylenetriamine or polyethylene glycols.
  • the bath additionally contains at least one kind of noble metal ions.
  • noble metal ions are ions of metals, which according to the series of voltages have a greater reduction potential than the other metal salts for electroless deposition in the bath.
  • the noble metal ions are preferably selected from the group comprising silver, gold, palladium, platinum, rhodium and copper.
  • silver in addition, the biocidal effect of silver-containing surfaces can be exploited.
  • the noble metals are preferably added as salts or solutions of their salts.
  • Suitable salts are chlorides, sulfates, carbonates, acetates, nitrates, sulfonates, sulfites, alkyl sulfonates, thioalkane carboxylates, mercaptoalkanesulfonates, phosphates or phosphonates.
  • the counterions may preferably have alkyl groups or aryl groups, which in turn may advantageously be partially fluorinated. Most preferably, the counterions are trifluoromethanesulfonate, methanesulfonate and / or toluenesulfonate.
  • They may also be salts in which the noble metal ions are complexed with ligands or chelate ligands, such as ethylenediamine, polyethylene glycols or thioethanol derivatives, such as 2,2-ethylene-di-thiodiethanol.
  • ligands or chelate ligands such as ethylenediamine, polyethylene glycols or thioethanol derivatives, such as 2,2-ethylene-di-thiodiethanol.
  • Examples of preferred salts of the noble metals are copper sulfate, HAuCl 4 , palladium sulfate, palladium nitrate and palladium acetate, platinum chloride, rhodium chloride, silver nitrate and silver methanesulfonate.
  • the bath preferably contains a content of noble metal ions between 0.1 g / l and 3 g / l, preferably between 0.1 g / l and 2 g / l, particularly preferably between 0.1 g / l and 1.8 g / l, most preferably between 0.1 and 1 g / l.
  • the precious metal is preferably added as the salt solution of a noble metal salt.
  • At least one complexing agent for the noble metal ions can be added to the bath in order to reduce the amount of free noble metal ions. This suppresses the precipitation and nonspecific deposition of the noble metal on less noble metals. At the same time, such complexing agents can also reduce the amount of precious metal needed.
  • the at least one complexing agent is an acid-stable complexing agent.
  • complexing agents are in the case of silver, for example under the name Slotoloy SNA 33 (company Schlötter) available.
  • Preferred complexing agents are those in the specification WO 01/92606 A1 on pages 7 to 9 and preferably in EP 1 285 104 B1 in the paragraphs [0025] to [0027] described organic sulfur compounds, which are hereby incorporated by reference.
  • Z is exclusively an oxygen atom, at least one of the radicals X, Y, R 1 , R 2 and R 3 contains at least one sulfur atom.
  • alkylene groups are alkylene groups having 1 to 10, preferably 1 to 5, carbon atoms, e.g. As methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene and tert-butylene groups.
  • substituents of the alkylene groups are -OH, -SH, -SR 4 , wherein R 4 is an alkyl group having 1 to 10 carbon atoms, e.g. A methyl, ethyl, n-propyl or iso-propyl group, is -OR 4 , -NH 2 , NHR 4 and NR 4 2 (where the two substituents R 4 may be the same or different).
  • the sulfur-containing radicals X and / or Y may be an SH group and / or the sulfur-containing Radicals R 1 , R 2 and / or R 3 may, for.
  • Example represent an alkylene radical which is substituted with an SH group or with an SR 4 group.
  • the at least one complexing agent is preferably added in an amount such that the molar ratio of the complexing agent (s) to the noble metal ions (molar amount of all complexing agents: molar amount of noble metal ions) is at least 1, preferably 5: 1 to 1: 1, particularly preferably 1, 5: 1.
  • conductive salts known from galvanic deposition can be added. These are usually alkali metal or alkaline earth metal salts, for example hydroxides, chlorides, bromides, nitrates, fluoroborates, for example potassium hydroxide, potassium chloride, sodium chloride, lithium chloride, lithium bromide or lithium hexafluoroborate. These salts are preferably present in the bath in an amount of 0.1 g / l to 1 g / l, preferably 0.4 g / l to 0.8 g / l.
  • the bath for electroless deposition of a metal layer is preferably a bath for depositing a chemically nickel layer, preferably a nickel / phosphorus and / or nickel / boron layer.
  • a chemically nickel layer preferably a nickel / phosphorus and / or nickel / boron layer.
  • the metal salt used is a nickel salt and the reducing agent hypophosphites and / or borates.
  • a substrate is introduced into the bath.
  • the substrate is preferably a conductive substrate.
  • the conductivity can also be achieved by applying a conductive layer to the substrate.
  • Preferred metallic substrates are copper, bronze, aluminum, steel, in particular stainless steel.
  • Non-metallic substrates are for example plastics, such as polypropylene, polyethylene, polycarbonates, polyimides, polyamides or nylon. The decisive factor is that they survive the conditions of the deposition. These non-metallic substrates are preferably coated with a metallic layer.
  • Nitase it may be necessary to clean, degrease and / or activate the surface of the substrate prior to performing the process. This can be done, for example, by applying a thin metal layer, for example by a so-called “nickel strike” done. This is also known as stopper or sticky nickel. A thin nickel film is deposited on the surface.
  • the substrate is preferably a mesh, sieve or grid, preferably with a mesh size of less than 1 mm, particularly preferably less than 500 ⁇ m. But there are also much finer networks with a mesh size of less than 100 microns, preferably less than 50 microns possible.
  • the wire thickness is over 5 microns, preferably over 10 microns, for example between 50 microns and 1000 microns.
  • the inventive method also allows the coating of such networks, screens or grids, which enclose a cavity, such as filter elements, V-filter. Due to shielding effects such structures can not be coated on the inside with galvanic processes.
  • a voltage is applied between the substrate and an electrode.
  • an electrode As an example, a graphite, nickel or silver electrode can be used. Preferred is a graphite electrode.
  • the ratio of the area of the anode in the bath and the projected workpiece surface is between 1: 0.5 and 1: 2, preferably 1: 1 (with a deviation of +/- 10%).
  • the bath may be necessary to bring the bath before applying the voltage to a certain temperature and / or a certain pH.
  • the bath is brought to a temperature of about 50 ° C.
  • the process can also be carried out at temperatures between 15 ° C and 90 ° C. In this case, especially at a high content of noble metal ions, the temperature should not be too high, since the electrolyte decomposes otherwise. Preference is given to temperatures of below 70 ° C, preferably between 30 ° C and 70 ° C, more preferably between 50 ° C and 70 ° C.
  • the pH of the bath is preferably in the acidic range below of pH 6, preferably between 4.0 and 5.0, more preferably between 4.2 and 4.6.
  • a voltage is applied between an electrode and the substrate.
  • the electrode is connected anodically and the substrate is cathodically connected. It may be necessary to vary the voltage over time, for example increasingly, decreasing or periodically.
  • the voltage generates an auxiliary electric field.
  • the voltage is applied so that a current density between 0.01 and 3 A / dm 2 , preferably between 0.1 and 1 A / dm 2 , more preferably between 0.1 and 0.7 A / dm 2 , is set , This current density is significantly lower than the usual current density in galvanic processes.
  • a layer thickness of 1 to 5 microns can already be obtained within 1 to 5 minutes.
  • layer thicknesses of 0.1 ⁇ m to 5 ⁇ m, preferably 0.1 ⁇ m to 1 ⁇ m, are preferred.
  • the resulting layers show a noble metal content of more than 60% by weight, preferably more than 80% by weight, particularly preferably more than 90% by weight.
  • the substrate prior to carrying out the process, is coated with a chemically nickel layer.
  • the substrate is introduced before carrying out the process in a chemical nickel bath and electrolessly deposited a chemical nickel layer.
  • the adhesion of the deposited with current support coating on the substrate is significantly improved.
  • Such a bath contains the already described components of a chemical nickel bath. These are at least one nickel salt and a reducing agent in the stated quantitative ranges.
  • the bath may also contain complexing agents for nickel ions in the ranges indicated.
  • the rate of electroless deposition is essentially determined by the temperature and / or the pH of the bath.
  • the conditions are determined by the metal / reducing agent system used.
  • the temperature is preferably above 50 ° C, preferably above 70 ° C, more preferably between 80 and 90 ° C, most preferably between 86 ° C and 90 ° C, z. At 88 ° C.
  • the pH is preferably between 4.0 and 6.0, preferably between 4.2 and 4.6, very particularly preferably 4.4.
  • the previously deposited chemical nickel layer has a noble metal content of up to 30% by weight.
  • a bath already described for the process according to the invention is preferably used.
  • the content of noble metal ions is preferably lower by a factor of 10 to 20.
  • this chemically nickel layer has a content of noble metal of up to 30 wt .-%, preferably between 1 and 10 wt .-%.
  • the content of noble metal is between 0.01 to 0.1 g / l, preferably between 0.01 and 0.06 g / l, more preferably between 0.01 and 0.05 g / l or 0.01 and 0 , 04 g / l.
  • the bath additionally contains at least one complexing agent for the noble metal ions, as already described for the other bath.
  • at least one complexing agent for the noble metal ions as already described for the other bath.
  • acid-resistant complexing agents are preferred.
  • Such are in the case of silver, for example, under the name Slotoloy SNA 33 (company Schlötter) available.
  • the at least one complexing agent is preferably added in an amount such that the molar ratio of the complexing agent (s) to the noble metal ions (molar amount of all complexing agents: molar amount of noble metal ions) is at least 1, preferably 10: 1 to 1: 1, particularly preferably 3: 1 amounts to.
  • the stability of the bath in the electroless deposition can be increased.
  • a deposition of a high content of noble metal in the deposited layer is achieved at a significantly reduced content of noble metal ions.
  • the previously deposited layer contains the same noble metal as the layer deposited in the method according to the invention. This significantly improves the adhesion of the layer deposited in steps a) to c) on the substrate. In addition, the noble metal content of this first layer gives better conductivity, which improves the deposition on this layer in steps a) to c).
  • noble metal doping in the first layer allows the use of very low field strengths in voltage-enhanced deposition, likely due to the conductivity of the noble metal. Despite in comparison to the galvanic deposition very low field strength can Contour-accurate, deep-scattering deposition with a noble metal content of over 90 wt .-% can be achieved. This layer has at the same time a high abrasion resistance and in the case of silver a good depot effect.
  • the method for producing the first layer can also be used per se for the production of noble metal-containing metal layers.
  • the precious metal is at least one bath, preferably in both baths, silver.
  • the precious metal is at least one bath, preferably in both baths, silver.
  • the noble metal in both layers is silver, particularly preferred in both layers is the noble metal silver and the metal nickel, or nickel / phosphorus.
  • the invention also relates to a coating on a substrate which has on the surface a noble metal / nickel layer which has a noble metal content of more than 60% by weight, preferably more than 80% by weight, particularly preferably more than 90% by weight ,
  • the noble metal / nickel layer is a noble metal / nickel / phosphorus layer or noble metal / nickel / boron layer, preferably a noble metal / nickel / phosphorus layer.
  • the content of phosphorus in the respective layer is 0.1% by weight to 30% by weight, preferably between 0.1% by weight and 10% by weight, particularly preferably 0.1% by weight. to 3 wt .-%, based on the proportion of nickel and phosphorus in the respective layer.
  • This layer is preferably obtained by the above-described electroless method.
  • the Layer on the surface has a thickness of 0.1 .mu.m to 5 .mu.m, preferably from 0.1 .mu.m to 1 .mu.m, while the underlying layer has a thickness of 0.5 to 50 .mu.m, preferably from 0.5 .mu.m to 15 has ⁇ m.
  • the nickel / noble metal layer is a nickel / phosphorus / noble metal or nickel / boron / noble metal layer, preferably a nickel / phosphorus / noble metal layer.
  • the content of phosphorus in the layer at 10 wt .-% to 30 wt .-% based on the proportion of nickel and phosphorus in the respective layer.
  • the noble metal is silver.
  • the coating has biocidal properties. Due to the multilayer structure with the layer with the highest silver content at the surface, these properties are particularly pronounced. In addition, the multilayer structure of the coating gives a particularly good adhesion to the substrate, since the different layers are structurally well matched.
  • the coating may also contain additional layers.
  • the two described layers preferably form the two uppermost layers of the coating. However, this may include, for example, further chemical nickel layers or also nickel layers, for example from a previous activation of the surface by a nickel strike.
  • the coating is produced by the method of steps a) to c), wherein before a noble metal-containing chemically nickel layer, preferably with the method also described, was deposited.
  • the invention also relates to a coated substrate, obtainable by the process according to the invention or with a coating according to the invention.
  • the coated substrate is a mesh, sieve, filter, fabric or sponge.
  • the substrate has at least one cavity completely or partially enclosed by a net, sieve, filter, fabric or sponge.
  • Examples of such substrates are filter elements, filter cartridges or V-filters.
  • the invention also relates to the use of the coated substrate in the automotive sector, sanitary area, jewelry area, drinking water area, in wastewater treatment, drinking water treatment, filtration of fluids, in cooling water circuits, in chemical plant engineering or in electrical engineering.
  • the coated substrate may be used in an application selected from the group of filters, valves, restrictors, radial and / or filter elements, filter screens, V-filters, architecture, decoration, machinery and equipment of the chemical industry, finishing in the electrical industry ,
  • area information always includes all - not mentioned - intermediate values and all imaginable subintervals.
  • a first aqueous nickel electroless bath containing nickel in a range of 1 to 15 g / l and a first Content of reducing agent in a range of 20 to 50 g / l ready, this bath stirred well and then sets the pH to a value in the range of 4.0 to 6.0 or 4.5 to 5.0.
  • a pH in the range of 4.2 to 4.6, preferably 4.4 is set.
  • the pH can be adjusted, for example, by adding ammonia solution or hydrochloric acid or sulfuric acid.
  • the nickel ions of the bath are generally present as solutions of the salts nickel chloride, nickel sulfate, nickel carbonate and / or nickel acetate.
  • the nickel content is usually in a range of 3 to 10 g / l.
  • a phosphorus or boron compound is preferably used as the reducing agent in the bath.
  • the reducing agent in the bath is preferably a hypophosphite.
  • the reducing agent is sodium hypophosphite and / or potassium hypophosphite.
  • boron compound dimethylaminoborane, diethylaminoborane or sodium borohydride can be used.
  • the reducing agent is normally present in a concentration ranging from 32 to 42 g / l in the bath.
  • the bath also contains at least one complexing agent which is in particular selected from the group consisting of monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, ammonia and alkanolamines.
  • the complexing agent is in a concentration in a range of 1 to 15 g / l in the bath. Complexing agents complex nickel ions and thus prevent excessively high concentrations of free nickel ions. This stabilizes the solution and suppresses the precipitation of, for example, nickel phosphite.
  • the bath also contains at least one accelerator which is in particular selected from the group comprising fluorides, borides and / or anions of mono- and dicarboxylic acids.
  • the accelerator is usually in one Concentration in a range of 0.001 to 1 g / l in the bath before. Accelerators can, for example, activate hypophosphite ions and thus accelerate the deposition.
  • At least one stabilizer is present, which is in particular selected from the group consisting of lead, tin, arsenic, molybdenum, cadmium, thallium ions and / or thiourea.
  • the stabilizer is usually present in a concentration ranging from 0.01 to 250 mg / L in the bath.
  • Stabilizers can prevent the decomposition of the solution by masking catalytically active reaction nuclei.
  • the bath usually also contains at least one pH buffer, which is in particular a sodium salt of a complexing agent and / or the associated corresponding acid.
  • the buffer is usually present in a concentration in the range of 0.5 to 30 g / l in the bath.
  • the bath also contains at least one pH regulator, which is in particular selected from the group of sulfuric acid, hydrochloric acid, sodium hydroxide, sodium carbonate and / or ammonia.
  • the pH regulator is advantageously present in a concentration in a range of 1 to 30 g / l in the bath. pH regulators make it possible to readjust the pH of the bath.
  • the bath may also contain at least one wetting agent which is in particular selected from the group of ionic and / or nonionic surfactants.
  • the wetting agent is preferably present in a concentration in a range of 0.001 to 1 g / l in the bath. Wetting agents increase the wetting of the surface to be nickeled and allow the production of very uniform layers.
  • This first electroless nickel bath additionally contains 0.01 to 0.1 g / l, preferably between 0.01 and 0.06 g / l, particularly preferably between 0.01 and 0.05 g / l or 0.01 and 0, 04 g / l of silver or silver ions.
  • the silver is preferred to the bath as a solution a silver salt added. It may be necessary to add the solution very slowly.
  • silver salt silver nitrate, silver acetate or a silver salt of a sulfonic or thiocarboxylic acid such as silver methanesulfonate may be used.
  • the bath preferably additionally contains at least one complexing agent for silver ions in order to stabilize the bath.
  • at least one complexing agent for silver ions in order to stabilize the bath.
  • acid-resistant complexing agents are preferred.
  • Such are in the case of silver, for example, under the name Slotoloy SNA 33 (company Schlötter) available.
  • the organic sulfur compounds preferred as complexing agents have already been described.
  • the at least one complexing agent is preferably added in an amount such that the molar ratio of the complexing agent (s) to the noble metal ions (molar amount of all complexing agents: molar amount of noble metal ions) is at least 1, preferably 10: 1 to 1: 1, particularly preferably 3: 1 amounts to.
  • a substrate is introduced and at a temperature between 80 and 95 ° C, preferably 80 ° C and 90 ° C, preferably between 86 ° C and 90 ° C, particularly preferably at 88 ° C, a chemical nickel layer with a Silver content of up to 30 wt .-%, preferably between 1 to 10 wt .-%, deposited.
  • the thickness of this layer is between 0.5 .mu.m and 50 .mu.m, preferably between 0.5 .mu.m and 15 .mu.m.
  • the dosage can be done by single additions or continuously.
  • the metered addition is controlled by measuring the electrochemical potential between the electrolyte and a reference electrode.
  • the surface of the substrate is pretreated, for example by a nickel strike.
  • a nickel strike may be formed, for example, by treating the surface with a mixture of inorganic acids, nickel chloride, citric acid and acetic acid while applying a voltage.
  • the surface is cleaned and at the same time a thin, 10 nm to 1 micron thick nickel layer deposited on the substrate.
  • Such a nickel strike is preferably carried out in the case of metallic substrates.
  • the compositions are known to the person skilled in the art.
  • the substrate After depositing the first layer, the substrate is introduced into a second bath.
  • This bath also corresponds to a bath for electroless deposition of nickel, which also contains additional silver.
  • the bath preferably contains, based on the silver ions, a content of silver between 0.1 g / l and 3 g / l, preferably between 0.1 g / l and 2 g / l, particularly preferably between 0.1 and 1.8 g / l, most preferably between 0.1 and 1 g / l.
  • the silver is preferably added as a salt solution of a silver salt.
  • the bath can still contain at least one conductive salt.
  • These are usually inorganic salts. These are generally alkali metal or alkaline earth metal salts, for example hydroxides, chlorides, bromides, nitrates, fluoroborates, for example potassium hydroxide, potassium chloride, sodium chloride, lithium chloride, lithium bromide or lithium hexafluoroborate.
  • the conductive salts are added in the amount for a content of 0.1 to 1 g / l, preferably between 0.4 to 0.8 g / l.
  • Such conductive salts are also available as commercial solutions.
  • An example of such a batch solution is Arguna CF (Umicore).
  • the substrates can be transferred directly from one bath to the other bath.
  • a voltage is applied between the substrate and an electrode.
  • the electrode is connected anodically and the substrate is cathodically connected.
  • the voltage generates an auxiliary electric field.
  • the voltage is applied so that a current density between 0.01 and 3 A / dm 2 , preferably between 0.1 and 1 A / dm 2 , more preferably between 0.1 and 0.7 A / dm 2 , is set , This current density is significantly lower than the usual current density in galvanic processes.
  • the deposition is preferably carried out at a temperature between 21 ° C and 90 ° C.
  • the temperature is usually below the critical temperature for the nickel bath, i. below 70 ° C, preferably between 30 ° C and 70 ° C, more preferably between 50 ° C and 70 ° C.
  • the pH of the bath is preferably in the acidic range below pH 6, preferably between 4.0 and 5.0, more preferably between 4.2 and 4.6.
  • a layer begins to deposit on the substrate, which majority consists of silver, preferably with a silver content of over 60 wt .-%, more preferably with a silver content of about 80 wt .-%, most preferably from about 90% by weight.
  • This deposition is preferably carried out for up to 5 minutes.
  • layers with a thickness of up to 5 .mu.m preferably up to 1 .mu.m, particularly preferably between 0.1 .mu.m and 1 .mu.m, are obtained.
  • the first deposited silver-containing nickel layer significantly improves the adhesion of this second layer.
  • the better conductivity favors the noble metal-containing nickel layer in combination with the simultaneously running electroless deposition uniform deposition even with substrates that are not to be coated with purely galvanic process.
  • Such substrates are in particular nets or screens, which are used in filter elements. These are cavities which are completely or partially enclosed by such sieve or net surfaces. Due to shielding effects, these substrates can not be evenly coated on the inside with purely galvanic processes. With the method according to the invention it is possible to apply a uniform layer both on the inside and on the outside of the substrate.
  • FIG. 1 shows a schematic representation of a filter element which can be coated by the method according to the invention, in particular with a nickel / silver layer.
  • the filter element consists of a cylindrical filter body 10. This consists of a net-like structure, which is a cylinder forms. The two ends of the cylinder are closed with caps 12. On these caps also connection openings can be attached.
  • the filter element may also have fastening means for seals. Together with the caps 12, the filter body encloses a cavity.
  • the preferred material for the filter element is stainless steel, eg 1.4404, 1.4301, 1.4571 Material designation according to AISI.
  • FIG. 2 shows the schematic sequence of a preferred embodiment of the invention.
  • the substrate surface is cleaned and optionally pretreated with a nickel strike (200).
  • the substrate is introduced into a first bath.
  • This bath is a bath for the electroless deposition of a metal / noble metal layer, as already described.
  • a first layer is electrolessly deposited on the substrate (220).
  • This layer is a metal / noble metal layer, wherein the layer has a noble metal content of up to 30 wt .-%.
  • the deposition is carried out without current to obtain a uniform coating of the substrate.
  • the substrate is placed in a second bath, optionally after purification steps (230).
  • This bath is - as already described - a bath for electroless deposition of a metal layer, which also contains precious metal ions.
  • a voltage is applied between the substrate and an electrode (240). This leads to the deposition of a noble metal / metal layer. This is a Layer which has a content of noble metal of over 60 wt .-%.
  • the coating is carried out until a layer with a thickness of up to 5 ⁇ m, preferably up to 1 ⁇ m, is obtained.
  • the metal layer is a nickel / phosphorus layer and the noble metal is silver.
  • the metal layer is a nickel / phosphorus layer and the noble metal is silver.
  • the substrate coated in this way with at least two layers shows a particularly high tribological stability and is very well suited for filter elements in fluids, for example in cooling water circuits.
  • FIG. 3 shows a construction of a preferred embodiment of the invention.
  • a substrate 314
  • a chemical nickel / phosphorus / silver layer 32) with a silver content of ⁇ 10 wt .-% with a thickness between 0.5 and 15 microns arranged.
  • a silver / nickel / phosphor cover layer with a silver content of> 90 wt .-% and a thickness between 0.1 .mu.m and 1 .mu.m.
  • FIG. 4 shows shots of an uncoated screen / filter element as in FIG. 1 shown in different magnification.
  • the scale is 200 ⁇ m in each case.
  • the thickness of the horizontal wires is about 150 ⁇ m and 160 ⁇ m.
  • the measured mesh sizes are between 85 ⁇ m and 143 ⁇ m.
  • FIG. 5 shows light micrographs of the same screen / filter element FIG. 4 after application of a coating according to the invention with a nickel / silver and a silver / nickel layer, as in FIG. 3 shown.
  • the scale is 200 ⁇ m in each case.
  • the thickness of the horizontal wires is now about 160 microns and 170 microns.
  • the measured mesh sizes are between 40 ⁇ m and 120 ⁇ m. It can be seen clearly a uniform coating of the substrate. When used in cooling circuits over several weeks, such coated filters show a biocidal effect, without the coating detaching.
  • silver in the form of silver methanesulfonate corresponding to a silver content of 0.025 g / l and an acid-resistant silver complexing agent (eg, Slotoloy SNA 33, manufactured by Schlötter) in an amount corresponding to 0.2 ml / l.
  • an acid-resistant silver complexing agent eg, Slotoloy SNA 33, manufactured by Schlötter
  • the pH of the bath is adjusted to 4.4 with H 2 SO 4 .
  • the bath is heated to 88 ° C and introduced a substrate made of stainless steel.
  • the consumption of silver ions is compensated by continuous addition of silver methanesulfonate. This can be done by controlling the dosage by measuring the electrochemical potential between the electrolyte and a reference electrode.
  • a non-porous, non-porous, chemical-nickel-silver alloy layer having a silver content of 1-10% by weight is deposited on the stainless steel.
  • a higher silver content is not available as the silver content in relation to the nickel content in the bath can not be increased further.
  • Higher contents of silver lead to a Temperature from about 70 ° C to complete destabilization of the electrolyte (spontaneous self-precipitation). It is not possible to avoid this effect by increasing the levels of stabilizers or complexing agents without stopping the nickel-phosphorus reduction. In this respect, the ranges given in DE 10 2006 020 988 A1 of noble metal and noble metal content of the layer for silver are not possible in this way.
  • the thus coated substrate was then provided with a silver / nickel layer according to the following specifications.
  • nickel or silver electrodes preferably graphite electrodes, introduced and applied an electrical voltage, wherein the introduced electrodes are connected anodically and the workpiece / substrate cathodically.
  • the area of the anode corresponds approximately to the projected workpiece surface (ie a ratio of 1: 1).
  • the current density of the auxiliary field is between 0.1 and 1 A / dm 2 . This is a significantly lower current density than conventional galvanic silver depositions. This is usually 30 to 100 A / dm 2 .
  • the layer, or the combination of the nickel / silver and silver / nickel layer, has a high abrasion resistance and depot effect with respect to the silver.
  • the coating obtained in the two-stage process still showed a biocidal effect and excellent stability even after continuous operation over several months in a cooling circuit.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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Claims (14)

  1. Procédé pour déposer des couches métalliques sur un substrat, comprenant les étapes suivantes :
    a) tout d'abord, mise à disposition d'un premier bain pour le dépôt auto-catalytique d'une couche métallique, qui contient en outre au moins un type d'ions de métaux nobles ;
    b) introduction du substrat dans le premier bain ;
    c) dépôt auto-catalytique d'ions de métaux et de métaux nobles, du premier bain sur le substrat, pour former une première couche métal/métal noble, ayant une teneur en métaux nobles allant jusqu'à 30 % en poids ;
    d) puis introduction du substrat dans un deuxième bain pour dépôt auto-catalytique d'une couche métallique, qui contient en outre au moins un type d'ions de métaux nobles, ou abandon du substrat dans le premier bain ;
    e) puis application d'une tension électrique entre une anode immergée dans le bain et le substrat monté en cathode ; et
    f) dépôt électrolytique d'une deuxième couche de métal noble/métal sur la première couche sur le substrat, la deuxième couche de métal noble/métal ayant une teneur en métaux nobles supérieure à 60 % en poids.
  2. Procédé selon la revendication précédente, caractérisé en ce que, pour ce qui concerne au moins l'un des bains pour les dépôts auto-catalytiques d'une couche métallique, il s'agit d'un bain pour le dépôt d'une couche de nickel chimique.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que les ions de métaux nobles sont choisis dans le groupe contenant l'argent, l'or, le palladium, le platine, le rhodium et le cuivre.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que la tension est appliquée à une température du bain inférieure à 70°C.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'au moins l'un des bains contient encore au moins un agent complexant pour les ions de métaux nobles.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que la teneur du bain en ions de métaux nobles est comprise entre 0,1 et 3 g/l.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'on applique une tension correspondant à une densité de courant comprise entre 0,01 et 3 A/dm2.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que, pour ce qui concerne le premier bain pour le dépôt auto-catalytique d'une couche métallique, il s'agit d'un bain pour le dépôt d'une couche de nickel chimique.
  9. Procédé selon la revendication 8, caractérisé en ce que le métal noble, est, dans les deux couches, l'argent.
  10. Revêtement sur un substrat, caractérisé en ce que le revêtement présente sur sa surface une couche de métal noble/nickel/phosphore ou une couche de métal noble/nickel/bore, qui présente une teneur en métaux nobles supérieure à 90 % en poids.
  11. Revêtement selon la revendication 10, caractérisé en ce que le métal noble est l'argent.
  12. Substrat revêtu, obtenu par un procédé selon les revendications 1 à 9.
  13. Substrat revêtu selon l'une des revendications 10, 11 ou 12, caractérisé en ce que le substrat est un filet, un tamis, un filtre, un tissu ou une éponge.
  14. Utilisation d'un substrat revêtu selon l'une des revendications 10 à 13 dans le domaine automobile, dans le domaine sanitaire, dans le domaine de la décoration, dans le domaine de l'eau potable ou dans le traitement de l'eau potable, pour le traitement des eaux résiduaires, pour filtrer des fluides, dans les circuits d'eau de refroidissement, dans la construction d'installations chimiques ou en électrotechnique.
EP11738647.4A 2010-06-30 2011-06-30 Couches de métal noble/métal pouvant subir des contraintes tribologiques Active EP2588644B1 (fr)

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