EP2233611A1 - Layer system with improved corrosion resistance - Google Patents

Layer system with improved corrosion resistance Download PDF

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Publication number
EP2233611A1
EP2233611A1 EP09004162A EP09004162A EP2233611A1 EP 2233611 A1 EP2233611 A1 EP 2233611A1 EP 09004162 A EP09004162 A EP 09004162A EP 09004162 A EP09004162 A EP 09004162A EP 2233611 A1 EP2233611 A1 EP 2233611A1
Authority
EP
European Patent Office
Prior art keywords
layer
tin
nickel
deposited
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09004162A
Other languages
German (de)
French (fr)
Inventor
Klaus Wilbuer
Meik Gray
Matthias Patzelt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MTV Metallveredlung GmbH and Co KG
Original Assignee
MTV Metallveredlung GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MTV Metallveredlung GmbH and Co KG filed Critical MTV Metallveredlung GmbH and Co KG
Priority to EP09004162A priority Critical patent/EP2233611A1/en
Priority to CN201080013693.8A priority patent/CN102369310B/en
Priority to US13/260,270 priority patent/US20120135270A1/en
Priority to EP10711148A priority patent/EP2411562A1/en
Priority to PCT/EP2010/001817 priority patent/WO2010108659A1/en
Priority to RU2011141884/02A priority patent/RU2536852C2/en
Publication of EP2233611A1 publication Critical patent/EP2233611A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/31—Coating with 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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • 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
    • C23C28/021—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 including at least one metal alloy layer
    • 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
    • C23C28/025—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 with at least one zinc-based layer
    • 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
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12715—Next to Group IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12708—Sn-base component
    • Y10T428/12722—Next to Group VIII metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12729—Group IIA metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories

Definitions

  • the present invention relates to a coating system for coating a substrate surface which has improved corrosion resistance.
  • the substrates to be coated may be conductive, metallic components as well as non-conductive substrates such as plastic components.
  • the deposited metal layers can on the one hand functionally change the substrate surfaces, on the other hand decorative. While the decorative coating of substrate surfaces is usually directed only to the visual impression of the deposited metal layers, in the field of functional deposition of metal layers, a change in the mechanical and / or chemical surface properties of the substrates is intended.
  • the abrasion resistance, wear resistance, surface hardness or corrosion resistance of the surface of the substrate can be changed by deposition of suitable layers. Basically, both the galvanic deposition of layers, as well as the autocatalytic deposition of layers is known here.
  • chromium layers which are used as a coating for metal surfaces in order to improve the metal surfaces, in particular with regard to their wear resistance and corrosion resistance.
  • chromium layers which are used as a coating for metal surfaces in order to improve the metal surfaces, in particular with regard to their wear resistance and corrosion resistance.
  • These layers are also characterized by good corrosion resistance.
  • Hard chrome coatings are used, for example, in the field of design engineering for hydraulic components such as hydraulic cylinders and hydraulic pistons, for pressure rollers in the field of printing technology, or in the field of engine construction, for example for the coating of valve stems.
  • chromium (VI) is suspected of being carcinogenic and the use of chromium (VI) -containing electrolytes should therefore be avoided.
  • different approaches have been taken to deposit without the use of chromium (VI) -containing electrolytes layers having comparable mechanical and chemical properties.
  • the European patent discloses EP 0 672 763 B1 a method for coating a metal surface, wherein a nickel-phosphorus alloy layer is deposited on the metal surface in a first step, to which then a silicon layer is deposited in a vacuum chamber using an ion beam.
  • a layer system for coating a substrate surface at least consisting of a first inner layer and an outer second layer deposited on the first layer, wherein one layer is a tin-nickel alloy layer and the other layer is a layer of a metal the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals.
  • a layer system consisting of a tin-nickel alloy layer and a layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or a Alloy of at least one of these metals gives a coating which on the one hand meets the requirements placed on a hard chrome layer on the one hand in terms of their mechanical stability, on the other hand has an outstanding corrosion resistance.
  • the substrates coated according to the invention are exposed to an aqueous solution containing iron (III) chloride in acidic conditions in accordance with ASTM standard G48.
  • the coating systems according to the invention exhibit outstanding corrosion resistance of more than 72 hours, sometimes even up to 100 hours or more, under these conditions.
  • the tin-nickel alloy layer has a layer thickness of at least 1 .mu.m, preferably at least 5 .mu.m and more preferably at least 10 .mu.m.
  • the layer order in the layer system according to the invention is irrelevant.
  • P refers However, a layer system in which a layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals as a first layer on a Substrate surface is deposited, on which then a tin-nickel alloy layer is deposited.
  • the first inner layer is a bronze or nickel-phosphorus alloy layer.
  • the deposition of the tin-nickel alloy layer having a layer thickness of at least 1 micron.
  • a bronze layer or a nickel-phosphorus alloy layer may be deposited.
  • the deposition of the individual layers of the layer system can be carried out in the state-of-the-art, electroless or galvanic manner, depending on the type of layer.
  • a bronze layer as the first inner layer
  • an electrodeposition under application of a suitable deposition voltage between the substrate surface and a counter electrode and using a conventional bronze electrolyte (aqueous, copper and tin-containing electrolyte) is preferred
  • the deposition of a nickel-phosphorus, for example Alloy layer preferably autocatalytically using a corresponding reducing agent such as sodium hypophosphite having electrolyte, but can also be deposited electrolytically.
  • the deposition of the tin-nickel alloy layer to be provided according to the invention can also be carried out galvanically by applying a deposition voltage between the substrate surface and a suitable counterelectrode or by autocatalytic using suitable reducing agents.
  • the layer systems deposited according to the invention are particularly suitable for coating components in the field of hydraulic engineering, such as pressure cylinders and pressure pistons, for the coating of pressure rollers in the field of printing press technology, for the coating of plant components and components in the field of marine engineering, in particular in the field of shipbuilding and the offshore extraction of natural gas and crude oil, as well as in the field of engine construction.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)

Abstract

The layer system for coating a substrate surface, comprises a first inner layer and a second outer layer deposited on the first layer, where one layer is a zinc-nickel-alloy layer with a layer thickness of 1 mu m and the other layer is a metal layer. The second outer layer is formed by the zinc-nickel-alloy layer and the first inner layer is formed by bronze- or nickel-phosphorus-alloy layer. The layer system has a corrosion resistance according to ASTM G48 method A of 48 hours. An independent claim is included for a method for coating a substrate surface.

Description

Die vorliegende Erfindung betrifft ein Schichtsystem zur Beschichtung einer Substratoberfläche, welches eine verbesserte Korrosionsbeständigkeit aufweist.The present invention relates to a coating system for coating a substrate surface which has improved corrosion resistance.

Die Abscheidung von Metallschichten oder Metalllegierungsschichten auf der Oberfläche von Substraten ist seit sehr langer Zeit bekannt. Die zu beschichtenden Substrate können hierbei sowohl leitfähige, metallische Bauteile, als auch nicht-leitfähige Substrate wie beispielswiese Kunststoffbauteile sein. Die abgeschiedenen Metallschichten können zum einen die Substratoberflächen funktional verändern, zum anderen dekorativ. Während die dekorative Beschichtung von Substratoberflächen in der Regel lediglich auf den optischen Eindruck der abgeschiedenen Metallschichten gerichtet ist, ist im Bereich der funktionalen Abscheidung von Metallschichten eine Veränderung der mechanischen und/oder chemischen Oberflächeneigenschaften der Substrate beabsichtigt. So kann beispielsweise die Abriebfestigkeit, Verschleißfestigkeit, Oberflächenhärte oder Korrosionsbeständigkeit der Oberfläche des Substrates durch Abscheidung geeigneter Schichten verändert werden. Grundsätzlich ist hierbei sowohl die galvanische Abscheidung von Schichten, als auch die autokatalytische Abscheidung von Schichten bekannt.The deposition of metal layers or metal alloy layers on the surface of substrates has been known for a very long time. In this case, the substrates to be coated may be conductive, metallic components as well as non-conductive substrates such as plastic components. The deposited metal layers can on the one hand functionally change the substrate surfaces, on the other hand decorative. While the decorative coating of substrate surfaces is usually directed only to the visual impression of the deposited metal layers, in the field of functional deposition of metal layers, a change in the mechanical and / or chemical surface properties of the substrates is intended. Thus, for example, the abrasion resistance, wear resistance, surface hardness or corrosion resistance of the surface of the substrate can be changed by deposition of suitable layers. Basically, both the galvanic deposition of layers, as well as the autocatalytic deposition of layers is known here.

Eine wichtige Rolle im Bereich der funktionalen Beschichtungen spielen Chromschichten, welche als Beschichtung für Metalloberflächen eingesetzt werden, um die Metalloberflächen insbesondere hinsichtlich ihrer Verschleißfestigkeit und Korrosionsbeständigkeit zu verbessern. So ist beispielsweise die galvanische Abscheidung von Hartchromschichten aus entsprechenden Chromelektrolyten auf Metalloberflächen bekannt, wobei die dadurch erhaltene Hartchrombeschichtung in der Regel eine größere Härte als das Material, aus dem das zu beschichtende Substrat gefertigt ist, besitzen. Diese Schichten zeichnen sich darüber hinaus auch durch gute Korrosionsbeständigkeit aus.An important role in the field of functional coatings play chromium layers, which are used as a coating for metal surfaces in order to improve the metal surfaces, in particular with regard to their wear resistance and corrosion resistance. For example, the galvanic deposition of hard chrome layers from corresponding chromium electrolytes Metal surfaces known, wherein the resulting hard chrome coating usually have a greater hardness than the material from which the substrate to be coated is made. These layers are also characterized by good corrosion resistance.

Hartchrombeschichtungen werden beispielsweise im Bereich der Konstruktionstechnik für Hydraulikbauteile wie beispielsweise Hydraulikzylinder und Hydraulikkolben, für Druckwalzen im Bereich der Druckmaschinentechnik, oder auch im Bereich des Motorenbaus beispielsweise für die Beschichtung von Ventilschäften eingesetzt.Hard chrome coatings are used, for example, in the field of design engineering for hydraulic components such as hydraulic cylinders and hydraulic pistons, for pressure rollers in the field of printing technology, or in the field of engine construction, for example for the coating of valve stems.

Ein weiteres Anwendungsgebiet solcher Beschichtungen ist die korrosionsbeständige Ausrüstung von Bauteilen und Anlagenkomponenten im Bereich der marinen Konstruktionstechnik sowie der Offshore-Technik. Hier führt der ständige Kontakt der Bauteile und Anlagenkomponenten mit Seewasser zu drastischen korrosiven Angriffen, die es zu vermeiden gilt. Auch hier hat sich die Verwendung von Hartchromschichten als geeignet gezeigt, um die entsprechenden Bauteile und Anlagenkomponenten sowohl hinsichtlich ihrer mechanischen Belastungsanforderungen, als auch hinsichtlich ihrer Korrosionsbeständigkeit geeignet auszurüsten.Another area of application of such coatings is the corrosion-resistant finishing of components and plant components in the field of marine construction technology as well as offshore technology. Here, the constant contact of the components and plant components with seawater leads to drastic corrosive attacks, which must be avoided. Again, the use of hard chrome has been shown to be suitable to equip the appropriate components and system components both in terms of their mechanical stress requirements, as well as in terms of their corrosion resistance suitable.

Ein Nachteil der aus dem Stand der Technik bekannten Hartchromschichten ist es jedoch, dass diese in der Regel aus Chrom(VI)-haltigen Elektrolyten abgeschieden werden. Chrom(VI) steht jedoch in Verdacht, kanzerogen zu wirken und der Einsatz von Chrom(VI)-haltigen Elektrolyten sollte daher vermieden werden. Im Stand der Technik wurden daher unterschiedliche Ansätze unternommen, um unter Verzicht der Verwendung von Chrom(VI)-haltigen Elektrolyten Schichten mit vergleichbaren mechanischen und chemischen Eigenschaften abzuscheiden. So offenbart beispielsweise das europäische Patent EP 0 672 763 B1 ein Verfahren zur Beschichtung einer Metallfläche, bei welchem auf der Metalloberfläche in einem ersten Schritt eine Nickel-Phosphor-Legierungsschicht abgeschieden wird, auf welche dann eine Siliciumschicht in einer Vakuumkammer unter Verwendung eines Ionenstrahls aufgebracht wird.A disadvantage of the hard chrome layers known from the prior art, however, is that they are usually deposited from chromium (VI) -containing electrolytes. However, chromium (VI) is suspected of being carcinogenic and the use of chromium (VI) -containing electrolytes should therefore be avoided. In the prior art, therefore, different approaches have been taken to deposit without the use of chromium (VI) -containing electrolytes layers having comparable mechanical and chemical properties. For example, the European patent discloses EP 0 672 763 B1 a method for coating a metal surface, wherein a nickel-phosphorus alloy layer is deposited on the metal surface in a first step, to which then a silicon layer is deposited in a vacuum chamber using an ion beam.

Ein solches Verfahren ist jedoch sehr kostenintensiv und aufgrund der benötigten Vakuumkammer auch lediglich für entsprechend kleine Bauteile anwendbar.However, such a method is very costly and due to the required vacuum chamber also applicable only for correspondingly small components.

Es ist daher die Aufgabe der vorliegenden Erfindung, ein Schichtsystem anzugeben, welches unter Vermeidung der Verwendung Chrom(VI)-haltigen Elektrolyten als Substitut für die aus dem Stand der Technik bekannten Hartchromschichten geeignet ist und darüber hinaus auf Bauteilen beliebiger Größe abgeschieden werden kann. Des weiteren ist es die Aufgabe der vorliegenden Erfindung, ein Verfahren zur Abscheidung eines solchen Schichtsystems anzugeben.It is therefore the object of the present invention to provide a layer system, which, while avoiding the use of chromium (VI) -containing electrolytes, is suitable as a substitute for the hard chrome layers known from the prior art and, moreover, can be deposited on components of any size. Furthermore, it is the object of the present invention to provide a method for depositing such a layer system.

Gelöst wird diese Aufgabe hinsichtlich des Schichtsystems durch ein Schichtsystem zur Beschichtung einer Substratoberfläche, wenigstens bestehend aus einer ersten inneren Schicht und einer auf der ersten Schicht abgeschiedenen äußeren zweiten Schicht, wobei eine Schicht eine Zinn-Nickel-Legierungsschicht und die andere Schicht eine Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder eine Legierung wenigstens eines dieser Metalle ist.This object is achieved with regard to the layer system by a layer system for coating a substrate surface, at least consisting of a first inner layer and an outer second layer deposited on the first layer, wherein one layer is a tin-nickel alloy layer and the other layer is a layer of a metal the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals.

Es hat sich herausgestellt, dass ein Schichtsystem, bestehend aus einer Zinn-Nickel-Legierungsschicht und einer Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle eine Beschichtung ergibt, welche einerseits hinsichtlich ihrer mechanischen Stabilität die an eine Hartchromschicht gestellten Anforderungen erfüllt, zum anderen eine überragende Korrosionsbeständigkeit aufweist.It has been found that a layer system consisting of a tin-nickel alloy layer and a layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or a Alloy of at least one of these metals gives a coating which on the one hand meets the requirements placed on a hard chrome layer on the one hand in terms of their mechanical stability, on the other hand has an outstanding corrosion resistance.

Zur Überprüfung der Korrosionsbeständigkeit des Schichtsystems und insbesondere zur Beurteilung der Korrosionsbeständigkeit gegenüber Salzwasser werden die erfindungsgemäß beschichteten Substrate in Übereinstimmung mit der ASTM-Norm G48 unter sauren Bedingungen einer wässrigen, Eisen(III)-chloridhaltigen Lösung ausgesetzt. Die erfindungsgemäßen Schichtsysteme zeigen unter diesen Bedingungen eine überragende Korrosionsbeständigkeit von mehr als 72 Stunden, teilweise sogar von bis zu 100 Stunden und mehr.To test the corrosion resistance of the coating system and in particular to assess the corrosion resistance to salt water, the substrates coated according to the invention are exposed to an aqueous solution containing iron (III) chloride in acidic conditions in accordance with ASTM standard G48. The coating systems according to the invention exhibit outstanding corrosion resistance of more than 72 hours, sometimes even up to 100 hours or more, under these conditions.

In einer bevorzugten Ausführungsform der Erfindung weist die Zinn-Nickel-Legierungsschicht eine Schichtstärke von wenigstens 1 µm, vorzugsweise von wenigstens 5 µm und noch bevorzugter von wenigstens 10 µm auf.In a preferred embodiment of the invention, the tin-nickel alloy layer has a layer thickness of at least 1 .mu.m, preferably at least 5 .mu.m and more preferably at least 10 .mu.m.

Die Schichtreihenfolge im erfindungsgemäßen Schichtsystem ist unerheblich. Bevorzugt wird jedoch ein Schichtsystem, in welchem eine Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle als eine erste Schicht auf einer Substratoberfläche abgeschieden ist, auf welche dann eine Zinn-Nickel-Legierungsschicht abgeschieden wird.The layer order in the layer system according to the invention is irrelevant. Prefers However, a layer system in which a layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals as a first layer on a Substrate surface is deposited, on which then a tin-nickel alloy layer is deposited.

Ohne an diese Theorie gebunden zu sein, wird seitens der Erfinder zur Zeit davon ausgegangen, dass es zu einer elektrochemischen Stabilisierung der die einzelnen Beschichtungen im erfindungsgemäßen Schichtsystem ausbildenden Metalle kommt, wodurch das freie Korrosionspotential an der Oberfläche deutlich verbessert wird. Für diese Annahme spricht, dass Korrosionsuntersuchungen gezeigt haben, dass die jeweils einzelnen Schichten eine deutlich geringere Korrosionsbeständigkeit aufweisen, als das Schichtsystem. Darüber hinaus ist die in einer bevorzugten Ausführungsform als zweite äußere Schicht abgeschiedene Zinn-Nickel-Schicht nicht hermetisch geschlossen, sondern mikrorissig, so dass auch ein Eindiffundieren der korrosiven Medien in die Schicht und somit ein Kontakt der korrosiven Medien zur ersten inneren Schicht möglich ist. Dies scheint jedoch keinen Einfluss auf die Korrosionsbeständigkeit des Schichtsystems zu haben, was die Annahme der gegenseitigen elektrochemischen Stabilisierung der Schichten stützt.Without being bound to this theory, it is currently assumed by the inventors that electrochemical stabilization of the metals forming the individual coatings in the layer system according to the invention occurs, as a result of which the free corrosion potential at the surface is markedly improved. This assumption is supported by the fact that corrosion tests have shown that the individual layers in each case have a significantly lower corrosion resistance than the layer system. In addition, the tin-nickel layer deposited in a preferred embodiment as the second outer layer is not hermetically sealed, but microcracked, so that it is also possible to diffuse the corrosive media into the layer and thus contact the corrosive media to the first inner layer. However, this does not seem to affect the corrosion resistance of the layer system, which supports the assumption of mutual electrochemical stabilization of the layers.

In einer weiter bevorzugten Ausführung des erfindungsgemäßen Schichtsystems ist die erste innere Schicht eine Bronze oder Nickel-Phosphor-Legierungsschicht.In a further preferred embodiment of the layer system according to the invention, the first inner layer is a bronze or nickel-phosphorus alloy layer.

Hinsichtlich des Verfahrens wird die Aufgabe der Erfindung durch ein Verfahren zur Beschichtung einer Substratoberfläche, insbesondere einer Metallsubstratoberfläche, gelöst, welches wenigstens die Verfahrensschritte aufweist:

  • Abscheiden einer ersten inneren Schicht auf einer Substratoberfläche;
  • Abscheiden einer zweiten äußeren Schicht,
    wobei als eine Schicht eine Zinn-Nickel-Legierungsschicht und als andere Schicht eine Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle abgeschieden wird.
With regard to the method, the object of the invention is achieved by a method for coating a substrate surface, in particular a metal substrate surface , which has at least the method steps:
  • Depositing a first inner layer on a substrate surface;
  • Depositing a second outer layer,
    wherein as a layer a tin-nickel alloy layer and as another layer a layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these Metals is deposited.

In einer bevorzugten Ausführung des erfindungsgemäßen Verfahrens wird als eine erste Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle abgeschieden und als zweite Schicht eine Zinn-Nickel-Legierungsschicht abgeschieden.In a preferred embodiment of the method according to the invention is deposited as a first layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals and as second layer deposited a tin-nickel alloy layer.

Insbesondere bevorzugt wird die Abscheidung der Zinn-Nickel-Legierungsschicht mit einer Schichtstärke von wenigstens 1 µm.Particularly preferred is the deposition of the tin-nickel alloy layer having a layer thickness of at least 1 micron.

Als eine erste Schicht kann beispielsweise eine Bronzeschicht oder eine Nickel-Phosphor-Legierungsschicht abgeschieden werden.As a first layer, for example, a bronze layer or a nickel-phosphorus alloy layer may be deposited.

Die Abscheidung der einzelnen Schichten des Schichtsystems kann in Abhängigkeit der Art der Schicht in der im Stand der Technik üblichen außenstromlosen oder galvanischen Weise erfolgen. So wird beispielsweise bei der Abscheidung einer Bronzeschicht als erste innere Schicht eine elektrolytische Abscheidung unter Anlegung einer geeigneten Abscheidespannung zwischen der Substratoberfläche und einer Gegenelektrode und Verwendung eines üblichen Bronzeelektrolyten (wässriger, kupfer- und zinnhaltiger Elektrolyt) bevorzugt, wohingegen die Abscheidung beispielsweise einer Nickel-Phosphor-Legierungsschicht bevorzugt autokatalytisch unter Verwendung eines ein entsprechendes Reduktionsmittel wie beispielsweise Natriumhypophosphit aufweisenden Elektrolyten erfolgt, aber auch elektrolytisch abgeschieden werden kann.The deposition of the individual layers of the layer system can be carried out in the state-of-the-art, electroless or galvanic manner, depending on the type of layer. Thus, for example, in the deposition of a bronze layer as the first inner layer, an electrodeposition under application of a suitable deposition voltage between the substrate surface and a counter electrode and using a conventional bronze electrolyte (aqueous, copper and tin-containing electrolyte) is preferred, whereas the deposition of a nickel-phosphorus, for example Alloy layer preferably autocatalytically using a corresponding reducing agent such as sodium hypophosphite having electrolyte, but can also be deposited electrolytically.

Die Abscheidung der erfindungsgemäß vorzusehenden Zinn-Nickel-Legierungsschicht kann ebenfalls galvanisch unter Anlegung einer Abscheidespannung zwischen der Substratoberfläche und einer geeigneten Gegenelektrode oder autokatalytisch unter Verwendung geeigneter Reduktionsmittel erfolgen.The deposition of the tin-nickel alloy layer to be provided according to the invention can also be carried out galvanically by applying a deposition voltage between the substrate surface and a suitable counterelectrode or by autocatalytic using suitable reducing agents.

Die erfindungsgemäß abgeschiedenen Schichtsysteme eignen sich insbesondere zur Beschichtung von Bauteilen im Bereich der Hydrauliktechnik, wie beispielsweise Druckzylinder und Druckkolben, für die Beschichtung von Druckwalzen im Bereich der Druckmaschinentechnik, für die Beschichtung von Anlagenbauteilen und -komponenten im Bereich der Marinekonstruktionstechnik, insbesondere im Bereich des Schiffbaus sowie der Offshore-Gewinnung von Erdgas und Erdöl, sowie im Bereich des Motorenbaus.The layer systems deposited according to the invention are particularly suitable for coating components in the field of hydraulic engineering, such as pressure cylinders and pressure pistons, for the coating of pressure rollers in the field of printing press technology, for the coating of plant components and components in the field of marine engineering, in particular in the field of shipbuilding and the offshore extraction of natural gas and crude oil, as well as in the field of engine construction.

Das erfindungsgemäße Schichtsystem sowie das erfindungsgemäße Verfahren werden nachfolgend anhand von Beispielen näher erläutert, wobei sich die Erfindung nicht auf die nachfolgend angegebenen Beispiele beschränken lässt.The layer system according to the invention and the method according to the invention are explained in more detail below with reference to examples, wherein the invention can not be limited to the examples given below.

Claims (9)

Schichtsystem zur Beschichtung einer Substratoberfläche, wenigstens bestehend aus einer ersten inneren Schicht und einer auf der ersten Schicht abgeschiedenen äußeren zweiten Schicht, wobei eine Schicht eine Zinn-Nickel-Legierungsschicht und die andere Schicht eine Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle ist.A coating system for coating a substrate surface, at least consisting of a first inner layer and an outer second layer deposited on the first layer, one layer comprising a tin-nickel alloy layer and the other layer a layer of a metal of the group consisting of nickel, copper, tin , Molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals. Schichtsystem gemäß Anspruch 1, wobei die Zinn-Nickel-Legierungsschicht eine Schichtdicke von wenigstens 1 µm aufweist.Layer system according to claim 1, wherein the tin-nickel alloy layer has a layer thickness of at least 1 micron. Schichtsystem gemäß einem der Ansprüche 1 oder 2, wobei die äußere zweite Schicht durch die Zinn-Nickel-Legierungsschicht gebildet ist.Layer system according to one of claims 1 or 2, wherein the outer second layer is formed by the tin-nickel alloy layer. Schichtsystem gemäß einem der vorhergehenden Ansprüche, aufweisend eine Korrosionsbeständigkeit nach ASTM G48 Methode A von wenigstens 24 Stunden, vorzugsweise von wenigstens 48 Stunden.Layer system according to one of the preceding claims, having a corrosion resistance according to ASTM G48 Method A of at least 24 hours, preferably of at least 48 hours. Schichtsystem gemäß einem der vorhergehenden Ansprüche, wobei die erste innere Schicht durch eine Bronze- oder Nickel-Phosphor-Legierungsschicht gebildet ist.Layer system according to one of the preceding claims, wherein the first inner layer is formed by a bronze or nickel-phosphorus alloy layer. Verfahren zur Beschichtung einer Substratoberfläche, insbesondere einer Metallsubstratoberfläche, wenigstens aufweisend die Verfahrensschritte: - Abscheiden einer ersten inneren Schicht auf einer Substratoberfläche; - Abscheiden einer zweiten äußeren Schicht auf der ersten Schicht,
wobei als eine Schicht eine Zinn-Nickel-Legierungsschicht und als andere Schicht eine Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle abgeschieden wird. Method for coating a substrate surface, in particular a metal substrate surface, comprising at least the method steps: Depositing a first inner layer on a substrate surface; Depositing a second outer layer on the first layer,
wherein as a layer a tin-nickel alloy layer and as another layer a layer of a metal of the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these Metals is deposited. Verfahren gemäß Anspruch 6, wobei als erste Schicht eine Schicht eines Metalls der Gruppe bestehend aus Nickel, Kupfer, Zinn, Molybdän, Niob, Kobalt, Chrom, Vanadium, Mangan, Titan und Magnesium, oder einer Legierung wenigstens eines dieser Metalle abgeschieden wird und als zweite Schicht eine Zinn-Nickel-Legierungsschicht abgeschieden wird.A method according to claim 6, wherein the first layer is a layer of a metal the group consisting of nickel, copper, tin, molybdenum, niobium, cobalt, chromium, vanadium, manganese, titanium and magnesium, or an alloy of at least one of these metals is deposited and deposited as a second layer, a tin-nickel alloy layer. Verfahren gemäß einem der Ansprüche 6 oder 7, wobei die Zinn-Nickel-Legierungsschicht mit einer Schichtstärke von wenigstens 1 µm abgeschieden wird.Method according to one of claims 6 or 7, wherein the tin-nickel alloy layer is deposited with a layer thickness of at least 1 micron. Verwendung einer Beschichtung gemäß einem der Ansprüche 1 bis 5 zur korrosionsbeständigen Ausrüstung von Seewasser ausgesetzten Bauteilen und/oder Hydraulikbauteilen.Use of a coating according to any one of claims 1 to 5 for corrosion-resistant equipment of seawater exposed components and / or hydraulic components.
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RU2536852C2 (en) 2014-12-27
WO2010108659A1 (en) 2010-09-30
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US20120135270A1 (en) 2012-05-31
WO2010108659A8 (en) 2011-11-10

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