EP2851455A1 - Electroplated wear-resistant coating and method for the same - Google Patents

Electroplated wear-resistant coating and method for the same Download PDF

Info

Publication number
EP2851455A1
EP2851455A1 EP14179103.8A EP14179103A EP2851455A1 EP 2851455 A1 EP2851455 A1 EP 2851455A1 EP 14179103 A EP14179103 A EP 14179103A EP 2851455 A1 EP2851455 A1 EP 2851455A1
Authority
EP
European Patent Office
Prior art keywords
particles
weight
electrolyte
component
hard material
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.)
Granted
Application number
EP14179103.8A
Other languages
German (de)
French (fr)
Other versions
EP2851455B1 (en
Inventor
André Werner
Josef Linska
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.)
MTU Aero Engines AG
Original Assignee
MTU Aero Engines AG
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 MTU Aero Engines AG filed Critical MTU Aero Engines AG
Publication of EP2851455A1 publication Critical patent/EP2851455A1/en
Application granted granted Critical
Publication of EP2851455B1 publication Critical patent/EP2851455B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/09—Mixtures of metallic powders
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/05—Light metals
    • B22F2301/052—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic

Definitions

  • the present invention relates to a galvanically produced wear protection coating and to a corresponding process for its production.
  • turbomachines such as stationary gas turbines or aircraft engines
  • certain components are exposed to high temperatures and aggressive media, which require appropriate protection of the components, for example by coatings.
  • coatings for example, it is known to provide components in turbomachinery with various coatings serving different purposes, such as hot gas corrosion protection coatings, wear protection coatings, and the like.
  • High-temperature wear protection layers usually include hard materials that can withstand wear.
  • Such high-temperature wear protection layers are applied according to the state of the art by build-up welding or thermal spraying.
  • thermal spraying or build-up welding not all component areas of a component for the application of a corresponding high-temperature wear protective layer accessible and by locally different thermal loads on the component during thermal spraying or build-up welding may lead to undesirable inhomogeneities in the wear protection layers or the underlying base material.
  • the corresponding method should enable a homogeneous wear protection coating with good adhesion to the component to be coated and be as simple and effective as possible.
  • the invention is based on the idea that a wear protection coating, which comprises hard material particles and / or lubricant particles, can be produced by a galvanic production method, wherein the hard material particles and / or lubricant particles can be dispersed in a corresponding electrolyte bath.
  • the invention builds on the fact that it is already known to deposit hot gas corrosion layers galvanically, as for example in the documents EP 0 424 863 A1 . DE 38 15 976 A1 and the US 4,895,625 A is described. Accordingly, a wear protection coating with an MCrAl matrix in which M stands for Co and / or Ni is proposed, in which hard material particles and / or lubricant particles are embedded in the matrix.
  • the hard material particles and / or lubricant particles may be contained together in a proportion of 5% by volume to 40% by volume, in particular 10% by volume to 30% by volume, in the wear protection coating and the matrix of the wear protection coating may be 15% by weight to 50% % By weight, in particular 20% by weight to 40% by weight cobalt and / or 15% by weight to 50% by weight, in particular 20% by weight to 40% by weight nickel, 10% by weight to 30% by weight, in particular from 10% by weight to 25% by weight of chromium and from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, of aluminum.
  • composition is of course always 100 wt.% Results, wherein the ingredients are to be selected within the specified ranges and possibly additional alloying ingredients must be added. If, for example, both cobalt and nickel are provided in the matrix of the anti-wear coating, then the maximum values of the specified ranges, ie in each case 50% by weight, can not be realized since at least 10% by weight of chromium and 1% by weight of aluminum must continue to be present , However, if, for example, only cobalt is contained in the matrix, then the cobalt content can be selected in the entire specified range, since in addition to the other specified constituents chromium and aluminum, additional alloying constituents may be present.
  • the following components can be used in suitable concentrations or amounts in the process for producing a wear-resistant coating described below.
  • an electrolyte which contains cobalt and / or nickel.
  • first particles are dispersed, wherein the first particles comprise hard material particles and / or Gleitstoffp
  • second particles are dispersed in the electrolyte, the second particles comprising metal alloy particles in which the metal alloy comprises chromium and aluminum.
  • the first particles serve to introduce the hard material particles and / or lubricant particles provided in the wear protection coating to be produced, while the second particles in the form of the metal alloy particles serve to form the MCrAl matrix together with the electrolytes containing cobalt and / or nickel.
  • a suitably prepared electrolyte, in which the first and second particles are dispersed, is used for the electrodeposition of a layer on a component to be coated.
  • the electrodeposited layer thus comprises a matrix of cobalt and / or nickel corresponding to the composition of the electrolyte as well as embedded first and second particles.
  • the electrodeposited coating can be subjected to a heat treatment in which the embedded metal alloy particles are dissolved and together with the deposited matrix of cobalt and / or nickel form a corresponding MCrAl matrix in which M is formed by cobalt and / or nickel.
  • the heat treatment may be carried out at a temperature of 950 ° C to 1200 ° C, in particular 1000 ° C to 1150 ° C for 2 to 20 hours, in particular between 5 and 15 hours.
  • the heat treatment can be carried out under vacuum, whereby the component and the electrodeposited layer can be homogeneously exposed together to the corresponding temperature.
  • a local heating of the electrodeposited layer by a surface heating can be made.
  • the cobalt and / or nickel-containing electrolyte for electrodeposition may include nickel sulfate and / or cobalt sulfate. Further, sodium chloride and / or boric acid may be present in the electrolyte.
  • the metal alloy of the metal alloy particles may be formed by CrAl, CrAlY, CrAlHf, CrAlYHf, CrAlTa, CrAlYTa, CrAlSi, MoCrSiAl, CrCoAl, CrNiAl, and alloys of chromium and aluminum containing at least one or more elements selected from yttrium, hafnium, tantalum, silicon , Molybdenum, nickel and cobalt.
  • the first and second particles, ie the hard material and / or lubricant particles, and the metal alloy particles may each be provided in the electrolyte in a proportion of 50 g / l to 300 g / l, preferably a total amount of particles in the range 300 g / l up to 400 g / l should not be exceeded.
  • the first particles may have a maximum or average particle size of less than or equal to 10 .mu.m, in particular between 1 .mu.m and 5 .mu.m, while the second particles may have a maximum or average particle size of less than or equal to 15 .mu.m, in particular between 1 .mu.m and 5 .mu.m.
  • the first particles in the form of hard material particles and / or lubricant particles may have a metallic shell, in particular a shell which comprises or is formed from nickel and / or cobalt, in order to introduce the hard material particles and / or lubricant particles in the galvanic process with dispersed electrolyte improve.
  • the first particles may include lubricant particles in the form of solid lubricants, particularly in the form of hexagonal boron nitride, to reduce wear through improved sliding movement of the coating with the wear components.
  • the first particles in the form of hard material particles can be formed by oxides, in particular chromium oxide or zirconium oxide, which protect the underlying component by its hardness and thus resistance to the wear partners.
  • the invention provides the possibility of creating a wear protection coating suitable for turbomachines with an MCrAl matrix with incorporated hard material particles and / or lubricant particles, which can be applied uniformly to a component even in hard-to-reach areas without undue, in particular inhomogeneous temperature loads.
  • the Fig. 1 shows an electrolyte 3 in an electrolyte bath in which first particles 1 and second particles 2 are dispersed.
  • the electrolyte is a mixture of cobalt sulfate, nickel sulfate, boric acid and sodium chloride, for example 240 g / l cobalt sulphate, 240 g / l nickel sulphate, 35 g / l boric acid and 20 g / l sodium chloride.
  • the ph value of the electrolyte is set between 4.5 and 4.7.
  • the first particles 1, which are dispersed in the electrolyte 3, are hard material particles and / or lubricant particles.
  • the hard material particles may be formed by oxides and in the present preferred embodiment, the hard material particles are formed by chromium oxide or zirconium oxide, which are added in the form of particles having average particle sizes of 5 microns in an amount of 100 g / l to the electrolyte.
  • the first particles are formed by lubricant particles formed by a solid lubricant such as hexagonal boron nitride. The lubricant particles are also dispersed in the electrolyte with an average particle size of 5 ⁇ m at a concentration of 100 g / l.
  • the second particles 2 contained in the electrolyte 3 are metal alloy particles containing at least chromium and aluminum, especially predominantly chromium and aluminum. Predominantly, this means that the sum of the proportions of chromium and aluminum form the largest alloying constituent of the metal alloy particles, in particular make up more than 50% by weight of the metal alloy of the metal alloy particles.
  • the second particles 2 can also be dispersed in the electrolyte 3 with an average particle size of 5 microns in an amount of 200 g / l.
  • the electrolyte is brought to a temperature of 30 ° C to 70 ° C and kept in motion by suitable stirrers or the like, so that the dispersed first and second particles 1, 2 are uniformly distributed in the electrolyte 3.
  • the Fig. 2 shows the electrolyte bath Fig. 1 in a galvanic deposition of a wear protection coating according to the invention on a component 4.
  • the component is connected as a cathode to a power supply 6, while an additional anode 5 is arranged in the electrolyte bath.
  • the Fig. 3 shows the component 4 with the deposited layer 7, which has a NiCo matrix with embedded first particles 1 and second particles 2.
  • the current density in the electrodeposition may be in the range of 1 to 10 A / dm 2 .
  • the deposited layer 7 is heat-treated together with the component 4 in a temperature range of 1000 to 1150 ° C. for 5 to 15 hours under vacuum, so that the second particles 2 are made of a CrAl alloy together with the CoNi matrix of the deposited ones Layer form a CoNiCrAl matrix in which hard material particles 9a of chromium and / or zirconium oxide and lubricant particles 9b of hexagonal boron nitride are present in the CoNiCrAl matrix in order to form the wear protection coating 10 on the component 4.
  • a CrAlY alloy is used for the second particles 2, then a CoNiCrAlY matrix 8 of the wear protection coating 10 is formed.
  • the first particles 1 are provided with a metal shell of nickel and / or cobalt, which in the heat treatment step between the 3 and 4 dissolves in the matrix 8, so that the hard material particles 9a and the Gleitstoffpelle 9b are present without surrounding casing in the wear-resistant coating 10.

Abstract

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer Verschleißschutzbeschichtung auf einem Bauteil, insbesondere einem Bauteil einer Strömungsmaschine, wobei das Verfahren die folgenden Schritte umfasst: Bereitstellen eines Elektrolyten (3), der Co und/oder Ni enthält,
Dispergieren von ersten Partikeln (1) in den Elektrolyten, wobei die ersten Partikel Hartstoffpartikel und/oder Gleitstoffpartikel umfassen,
Dispergieren von zweiten Partikeln (2) in den Elektrolyten, wobei die zweiten Partikel Metalllegierungspartikel umfassen, bei denen die Metalllegierung Chrom und Aluminium aufweist,
Bereitstellen des zu beschichtenden Bauteils (4) in einem Bad des Elektrolyten, der mit ersten und zweiten Partikeln dispergiert ist, und
galvanisches Abscheiden einer Matrix aus Co und/oder Ni mit eingelagerten Metalllegierungspartikeln (2) und eingelagerten Hartstoffpartikeln und/oder Gleitstoffpartikeln (1) auf dem Bauteil.
Außerdem betrifft die Erfindung eine entsprechend hergestellte Verschleißschutzbeschichtung.

Figure imgaf001
The present invention relates to a method for producing a wear protection coating on a component, in particular a component of a turbomachine, the method comprising the following steps: providing an electrolyte (3) containing Co and / or Ni,
Dispersing first particles (1) in the electrolyte, wherein the first particles comprise hard material particles and / or lubricant particles,
Dispersing second particles (2) in the electrolyte, the second particles comprising metal alloy particles in which the metal alloy comprises chromium and aluminum,
Providing the component (4) to be coated in a bath of the electrolyte dispersed with first and second particles, and
galvanic deposition of a matrix of Co and / or Ni with embedded metal alloy particles (2) and embedded hard material particles and / or lubricant particles (1) on the component.
Moreover, the invention relates to a suitably produced wear protection coating.
Figure imgaf001

Description

HINTERGRUND DER ERFINDUNGBACKGROUND OF THE INVENTION GEBIET DER ERFINDUNGFIELD OF THE INVENTION

Die vorliegende Erfindung betrifft eine galvanisch hergestellte Verschleißschutzbeschichtung sowie ein entsprechendes Verfahren zu ihrer Herstellung.The present invention relates to a galvanically produced wear protection coating and to a corresponding process for its production.

STAND DER TECHNIKSTATE OF THE ART

In Strömungsmaschinen, wie stationären Gasturbinen oder Flugzeugtriebwerken, werden bestimmte Bauteile hohen Temperaturen und aggressiven Medien ausgesetzt, die einen entsprechenden Schutz der Bauteile beispielsweise durch Beschichtungen erfordern. Entsprechend ist es bekannt, Bauteile in Strömungsmaschinen mit verschiedenen Beschichtungen zu versehen, die unterschiedlichen Zwecken dienen, wie beispielsweise Heißgaskorosionsschutzschichten, Verschleißschutzbeschichtungen und dergleichen.In turbomachines, such as stationary gas turbines or aircraft engines, certain components are exposed to high temperatures and aggressive media, which require appropriate protection of the components, for example by coatings. Accordingly, it is known to provide components in turbomachinery with various coatings serving different purposes, such as hot gas corrosion protection coatings, wear protection coatings, and the like.

Bekannte Hochtemperaturverschleißschutzschichten umfassen üblicherweise harte Materialien, die dem Verschleiß widerstehen können. Derartige Hochtemperaturverschleißschutzschichten werden nach dem Stand der Techni durch Auftragsschweißen oder thermisches Spritzen aufgebracht. Allerdings sind durch thermisches Spritzen oder Auftragsschweißen nicht alle Bauteilbereiche eines Bauteils für die Aufbringung einer entsprechenden Hochtemperaturverschleißschutzschicht zugänglich und durch örtlich unterschiedliche thermische Belastungen des Bauteils während des thermischen Spritzens oder Auftragsschweißens kann es zu unerwünschten Inhomogenitäten im Bereich der Verschleißschutzschichten oder des darunter liegenden Grundwerkstoffs kommen.Known high-temperature wear protection layers usually include hard materials that can withstand wear. Such high-temperature wear protection layers are applied according to the state of the art by build-up welding or thermal spraying. However, by thermal spraying or build-up welding not all component areas of a component for the application of a corresponding high-temperature wear protective layer accessible and by locally different thermal loads on the component during thermal spraying or build-up welding may lead to undesirable inhomogeneities in the wear protection layers or the underlying base material.

OFFENBARUNG DER ERFINDUNGDISCLOSURE OF THE INVENTION AUFGABE DER ERFINDUNGOBJECT OF THE INVENTION

Es ist deshalb Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung einer Hochtemperaturverschleißschutzschicht, insbesondere für Bauteile von Strömungsmaschinen, sowie entsprechende Verschleißschutzschichten bereitzustellen, bei denen keine inhomogenen thermischen Belastungen des zu beschichtenden Bauteils erzeugt werden und insbesondere auch eine Beschichtung des Bauteils an schwer zugänglichen Bereichen ermöglicht wird. Darüber hinaus soll das entsprechende Verfahren eine homogene Verschleißschutzbeschichtung mit einer guten Haftfestigkeit am zu beschichtenden Bauteil ermöglichen und möglichst einfach und effektiv durchführbar sein.It is therefore an object of the present invention to provide a method for producing a high-temperature wear protection layer, in particular for components of turbomachines, as well as corresponding wear protection layers, in which no inhomogeneous thermal stresses of the component to be coated are produced and in particular allows a coating of the component in hard to reach areas becomes. In addition, the corresponding method should enable a homogeneous wear protection coating with good adhesion to the component to be coated and be as simple and effective as possible.

TECHNISCHE LÖSUNGTECHNICAL SOLUTION

Diese Aufgabe wird gelöst durch ein Verfahren mit den Merkmalen des Anspruchs 1 sowie eine Verschleißschutzbeschichtung mit den Merkmalen des Anspruchs 14. Vorteilhafte Ausgestaltungen sind Gegenstand der abhängigen Ansprüche.This object is achieved by a method having the features of claim 1 and a wear protection coating having the features of claim 14. Advantageous embodiments are the subject of the dependent claims.

Die Erfindung geht aus von der Idee, dass eine Verschleißschutzbeschichtung, welche Hartstoffpartikel und/oder Gleitstoffpartikel umfasst, durch ein galvanisches Herstellungsverfahren erzeugt werden kann, wobei die Hartstoffpartikel und/oder Gleitstoffpartikel in einem entsprechenden Elektrolytbad dispergiert sein können. Die Erfindung baut hierbei darauf auf, dass es bereits bekannt ist, Heißgaskorrosionsschichten galvanisch abzuscheiden, wie dies beispielsweise in den Dokumenten EP 0 424 863 A1 , DE 38 15 976 A1 und der US 4,895,625 A beschrieben ist. Entsprechend wird eine Verschleißschutzbeschichtung mit einer MCrAl - Matrix, bei der M für Co und/oder Ni steht, vorgeschlagen, bei welcher in der Matrix Hartstoffpartikel und/oder Gleitstoffpartikel eingelagert sind.The invention is based on the idea that a wear protection coating, which comprises hard material particles and / or lubricant particles, can be produced by a galvanic production method, wherein the hard material particles and / or lubricant particles can be dispersed in a corresponding electrolyte bath. The invention builds on the fact that it is already known to deposit hot gas corrosion layers galvanically, as for example in the documents EP 0 424 863 A1 . DE 38 15 976 A1 and the US 4,895,625 A is described. Accordingly, a wear protection coating with an MCrAl matrix in which M stands for Co and / or Ni is proposed, in which hard material particles and / or lubricant particles are embedded in the matrix.

Die Hartstoffpartikel und/oder Gleitstoffpartikel können zusammen in einem Anteil von 5 Vol.% bis 40 Vol.%, insbesondere 10 Vol.% bis 30 Vol.%, in der Verschleißschutzbeschichtung enthalten sein und die Matrix der Verschleißschutzbeschichtung kann 15 Gew.% bis 50 Gew.%, insbesondere 20 Gew.% bis 40 Gew.% Kobalt und/oder 15 Gew.% bis 50 Gew.%, insbesondere 20 Gew.% bis 40 Gew.% Nickel, 10 Gew.% bis 30 Gew.%, insbesondere 10 Gew.% bis 25 Gew.% Chrom und 1 Gew.% bis 10 Gew.%, insbesondere 2 Gew.% bis 8 Gew.% Aluminium beinhalten. Die Angaben für die Zusammensetzung sind hierbei so zu verstehen, dass die Zusammensetzung selbstverständlich immer 100 Gew.% ergibt, wobei die Bestandteile innerhalb der angegeben Bereiche zu wählen sind und eventuell weitere Legierungsbestandteile zugegeben werden müssen. Ist beispielsweise in der Matrix der Verschleißschutzbeschichtung sowohl Kobalt als auch Nickel vorgesehen, so können die Maximalwerte der angegebenen Bereiche, also jeweils 50 Gew.%, nicht verwirklicht werden, da weiterhin mindestens 10 Gew.% Chrom und 1 Gew.% Aluminium enthalten sein müssen. Ist jedoch beispielsweise lediglich Kobalt in der Matrix enthalten, so kann der Kobaltgehalt im gesamten angegebenen Bereich gewählt werden, da neben den weiteren angegebenen Bestandteilen Chrom und Aluminium zusätzliche Legierungsbestandteile enthalten sein können.The hard material particles and / or lubricant particles may be contained together in a proportion of 5% by volume to 40% by volume, in particular 10% by volume to 30% by volume, in the wear protection coating and the matrix of the wear protection coating may be 15% by weight to 50% % By weight, in particular 20% by weight to 40% by weight cobalt and / or 15% by weight to 50% by weight, in particular 20% by weight to 40% by weight nickel, 10% by weight to 30% by weight, in particular from 10% by weight to 25% by weight of chromium and from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, of aluminum. The data for the composition are to be understood in this case that the composition is of course always 100 wt.% Results, wherein the ingredients are to be selected within the specified ranges and possibly additional alloying ingredients must be added. If, for example, both cobalt and nickel are provided in the matrix of the anti-wear coating, then the maximum values of the specified ranges, ie in each case 50% by weight, can not be realized since at least 10% by weight of chromium and 1% by weight of aluminum must continue to be present , However, if, for example, only cobalt is contained in the matrix, then the cobalt content can be selected in the entire specified range, since in addition to the other specified constituents chromium and aluminum, additional alloying constituents may be present.

Um die jeweiligen Bestandteile der Verschleißschutzbeschichtung entsprechend zu erzielen, können bei dem nachfolgend angegebenen Verfahren zur Herstellung einer Verschleißschutzbeschichtung die entsprechenden Komponenten in geeigneten Konzentrationen oder Mengen eingesetzt werden.In order to achieve the respective constituents of the wear-resistant coating, the following components can be used in suitable concentrations or amounts in the process for producing a wear-resistant coating described below.

Um die MCrAl - Matrix der gewünschten Verschleißschutzbeschichtung herzustellen, wird erfindungsgemäß ein Elektrolyt bereitgestellt, der Kobalt und/oder Nickel enthält. In diesem Elektrolyten werden erste Partikel dispergiert, wobei die ersten Partikel Hartstoffpartikel und/oder Gleitstoffpartikel umfassen. Darüber hinaus werden zweite Partikel in den Elektrolyten dispergiert, wobei die zweiten Partikel Metalllegierungspartikel umfassen, bei denen die Metalllegierung Chrom und Aluminium aufweist. Die ersten Partikel dienen zur Einbringung der in der zu erzeugenden Verschleißschutzbeschichtung vorgesehenen Hartstoffpartikel und/oder Gleitstoffpartikel, während die zweiten Partikel in Form der Metalllegierungspartikel zur Ausbildung der MCrAl-Matrix zusammen mit den Kobalt und/oder Nickel enthaltenden Elektrolyten dienen.In order to produce the MCrAl matrix of the desired wear protection coating, according to the invention an electrolyte is provided which contains cobalt and / or nickel. In this electrolyte first particles are dispersed, wherein the first particles comprise hard material particles and / or Gleitstoffpartikel. In addition, second particles are dispersed in the electrolyte, the second particles comprising metal alloy particles in which the metal alloy comprises chromium and aluminum. The first particles serve to introduce the hard material particles and / or lubricant particles provided in the wear protection coating to be produced, while the second particles in the form of the metal alloy particles serve to form the MCrAl matrix together with the electrolytes containing cobalt and / or nickel.

Ein entsprechend vorbereiteter Elektrolyt, in dem die ersten und zweiten Partikel dispergiert sind, wird zur galvanischen Abscheidung einer Schicht an einem zu beschichtenden Bauteil verwendet. Die galvanisch abgeschiedene Schicht umfasst folglich eine Matrix aus Kobalt und/oder Nickel entsprechend der Zusammensetzung des Elektrolyten sowie eingelagerte erste und zweite Partikel.A suitably prepared electrolyte, in which the first and second particles are dispersed, is used for the electrodeposition of a layer on a component to be coated. The electrodeposited layer thus comprises a matrix of cobalt and / or nickel corresponding to the composition of the electrolyte as well as embedded first and second particles.

Die galvanisch abgeschiedene Beschichtung kann einer Wärmebehandlung unterzogen werden, bei der die eingelagerten Metalllegierungspartikel aufgelöst werden und zusammen mit der abgeschiedenen Matrix aus Kobalt und/oder Nickel eine entsprechende MCrAl - Matrix bilden, bei der M durch Kobalt und/oder Nickel gebildet ist.The electrodeposited coating can be subjected to a heat treatment in which the embedded metal alloy particles are dissolved and together with the deposited matrix of cobalt and / or nickel form a corresponding MCrAl matrix in which M is formed by cobalt and / or nickel.

Die Wärmebehandlung kann bei einer Temperatur von 950°C bis 1200°C, insbesondere 1000°C bis 1150°C für 2 bis 20 Stunden, insbesondere zwischen 5 und 15 Stunden, durchgeführt werden.The heat treatment may be carried out at a temperature of 950 ° C to 1200 ° C, in particular 1000 ° C to 1150 ° C for 2 to 20 hours, in particular between 5 and 15 hours.

Die Wärmebehandlung kann unter Vakuum erfolgen, wobei Bauteil und galvanisch abgeschiedene Schicht zusammen homogen der entsprechenden Temperatur ausgesetzt werden können. Alternativ kann auch eine lokale Erwärmung der galvanisch abgeschiedenen Schicht durch eine Oberflächenerwärmung vorgenommen werden.The heat treatment can be carried out under vacuum, whereby the component and the electrodeposited layer can be homogeneously exposed together to the corresponding temperature. Alternatively, a local heating of the electrodeposited layer by a surface heating can be made.

Der Kobalt und/oder Nickel enthaltende Elektrolyt für die galvanische Abscheidung kann Nickelsulfat und/oder Kobaltsulfat umfassen. Ferner kann in dem Elektrolyt Natriumchlorid und/oder Borsäure vorhanden sein.The cobalt and / or nickel-containing electrolyte for electrodeposition may include nickel sulfate and / or cobalt sulfate. Further, sodium chloride and / or boric acid may be present in the electrolyte.

Die Metalllegierung der Metalllegierungspartikel kann durch CrAl, CrAlY, CrAlHf, CrAlYHf, CrAlTa, CrAlYTa, CrAlSi, MoCrSiAl, CrCoAl, CrNiAl und durch Legierungen mit Chrom und Aluminium gebildet sein, die mindestens ein oder mehrere Elemente ausgewählt aus Yttrium, Hafnium, Tantal, Silizium, Molybdän, Nickel und Kobalt umfassen.The metal alloy of the metal alloy particles may be formed by CrAl, CrAlY, CrAlHf, CrAlYHf, CrAlTa, CrAlYTa, CrAlSi, MoCrSiAl, CrCoAl, CrNiAl, and alloys of chromium and aluminum containing at least one or more elements selected from yttrium, hafnium, tantalum, silicon , Molybdenum, nickel and cobalt.

Die ersten und zweiten Partikel, also die Hartstoff- und/oder Gleitstoffpartikel, sowie die Metalllegierungspartikel können jeweils mit einem Anteil von 50 g/l bis 300 g/l im Elektrolyt vorgesehen sein, wobei bevorzugt eine Gesamtmenge von Partikeln im Bereich 300 g/l bis 400 g/l nicht überschritten werden soll.The first and second particles, ie the hard material and / or lubricant particles, and the metal alloy particles may each be provided in the electrolyte in a proportion of 50 g / l to 300 g / l, preferably a total amount of particles in the range 300 g / l up to 400 g / l should not be exceeded.

Die ersten Partikel können eine maximale oder durchschnittliche Partikelgröße kleiner oder gleich 10 µm, insbesondere zwischen 1 µm und 5 µm aufweisen, während die zweiten Partikel eine maximale oder durchschnittliche Partikelgröße kleiner oder gleich 15 µm, insbesondere zwischen 1 µm und 5 µm, aufweisen können.The first particles may have a maximum or average particle size of less than or equal to 10 .mu.m, in particular between 1 .mu.m and 5 .mu.m, while the second particles may have a maximum or average particle size of less than or equal to 15 .mu.m, in particular between 1 .mu.m and 5 .mu.m.

Die ersten Partikel in Form von Hartstoffpartikeln und/oder Gleitstoffpartikeln können eine metallische Hülle aufweisen, insbesondere eine Hülle, die Nickel und/oder Kobalt umfasst oder aus diesen gebildet ist, um die Einbringung der Hartstoffpartikel und/oder Gleitstoffpartikel im galvanischen Prozess mit dispergiertem Elektrolyten zu verbessern.The first particles in the form of hard material particles and / or lubricant particles may have a metallic shell, in particular a shell which comprises or is formed from nickel and / or cobalt, in order to introduce the hard material particles and / or lubricant particles in the galvanic process with dispersed electrolyte improve.

Die ersten Partikel können Gleitstoffpartikel in Form von Festschmiermitteln, insbesondere in Form von hexagonalem Bornitrid, umfassen, um durch eine verbesserte gleitende Bewegung der Beschichtung mit den Verschleißpartnern den Verschleiß zu verringern.The first particles may include lubricant particles in the form of solid lubricants, particularly in the form of hexagonal boron nitride, to reduce wear through improved sliding movement of the coating with the wear components.

Die ersten Partikel in Form von Hartstoffpartikeln können durch Oxide, insbesondere Chromoxid oder Zirkonoxid, gebildet sein, welche das darunter liegende Bauteil durch ihre Härte und damit Widerstandsfähigkeit gegenüber den Verschleißpartnern schützen.The first particles in the form of hard material particles can be formed by oxides, in particular chromium oxide or zirconium oxide, which protect the underlying component by its hardness and thus resistance to the wear partners.

Insgesamt ergibt sich durch die Erfindung die Möglichkeit eine insbesondere für Strömungsmaschinen geeignete Verschleißschutzbeschichtung mit einer MCrAl - Matrix mit eingelagerten Hartstoffpartikeln und/oder Gleitstoffpartikeln zu schaffen, die ohne unzulässige, insbesondere inhomogene Temperaturbelastungen gleichmäßig an einem Bauteil auch an schwer zugänglichen Stellen aufgebracht werden kann.Overall, the invention provides the possibility of creating a wear protection coating suitable for turbomachines with an MCrAl matrix with incorporated hard material particles and / or lubricant particles, which can be applied uniformly to a component even in hard-to-reach areas without undue, in particular inhomogeneous temperature loads.

KURZBESCHREIBUNG DER FIGURENBRIEF DESCRIPTION OF THE FIGURES

Die beigefügten Zeichnungen zeigen in rein schematischer Weise in

  • Fig. 1 eine Querschnittansicht eines erfindungsgemäß dispergierten Elektrolytbades;
  • Fig. 2 eine Querschnittansicht eines erfindungsgemäß dispergierten Elektrolytbades bei der galvanischen Abscheidung einer Schicht auf einem zu beschichtenden Bauteil;
  • Fig. 3 einen Querschnitt durch ein Bauteil mit einer erfindungsgemäß abgeschiedenen Schicht; und in
  • Fig. 4 einen Querschnitt durch ein Bauteil mit einer erfindungsgemäß abgeschiedenen Verschleißschutzbeschichtung nach einer Wärmebehandlung.
The accompanying drawings show in a purely schematic manner in FIG
  • Fig. 1 a cross-sectional view of an inventively dispersed electrolyte bath;
  • Fig. 2 a cross-sectional view of an inventively dispersed electrolyte bath in the electrodeposition of a layer on a component to be coated;
  • Fig. 3 a cross section through a component with a deposited according to the invention layer; and in
  • Fig. 4 a cross section through a component with a deposited according to the invention wear protection coating after a heat treatment.

AUSFÜHRUNGSBEISPIELEmbodiment

Weitere Vorteile, Kennzeichen und Merkmale der vorliegenden Erfindung werden bei der nachfolgenden detaillierten Beschreibung eines Ausführungsbeispiels deutlich. Allerdings ist die Erfindung nicht auf dieses Ausführungsbeispiel beschränkt.Further advantages, characteristics and features of the present invention will become apparent in the following detailed description of an embodiment. However, the invention is not limited to this embodiment.

Die Fig. 1 zeigt einen Elektrolyten 3 in einem Elektrolytbad, in welchem erste Partikel 1 und zweite Partikel 2 dispergiert sind.The Fig. 1 shows an electrolyte 3 in an electrolyte bath in which first particles 1 and second particles 2 are dispersed.

Bei dem Elektrolyten handelt es sich um ein Gemisch aus Kobaltsulfat, Nickelsulfat, Borsäure und Natriumchlorid, wobei beispielsweise 240 g/l Kobaltsulfat, 240 g/l Nickelsulfat, 35 g/l Borsäure und 20 g/l Natriumchlorid eingesetzt werden können. Der ph - Wert des Elektrolyten wird zwischen 4,5 und 4,7 eingestellt.The electrolyte is a mixture of cobalt sulfate, nickel sulfate, boric acid and sodium chloride, for example 240 g / l cobalt sulphate, 240 g / l nickel sulphate, 35 g / l boric acid and 20 g / l sodium chloride. The ph value of the electrolyte is set between 4.5 and 4.7.

Die ersten Partikel 1, die in den Elektrolyten 3 dispergiert sind, sind Hartstoffpartikel und/oder Gleitstoffpartikel. Die Hartstoffpartikel können durch Oxide gebildet sein und bei dem vorliegenden bevorzugten Ausführungsbeispiel werden die Hartstoffpartikel durch Chromoxid oder Zirkonoxid gebildet, welche in Form von Partikel mit durchschnittlichen Partikelgrößen von 5 µm in einer Menge von 100 g/l dem Elektrolyten beigefügt werden. Darüber hinaus werden die ersten Partikel durch Gleitstoffpartikel gebildet, die durch einen Festschmierstoff, wie beispielsweise hexagonales Bornitrid gebildet sind. Die Gleitstoffpartikel werden ebenfalls mit einer durchschnittlichen Partikelgröße von 5 µm mit einer Konzentration von 100 g/l in dem Elektrolyten dispergiert.The first particles 1, which are dispersed in the electrolyte 3, are hard material particles and / or lubricant particles. The hard material particles may be formed by oxides and in the present preferred embodiment, the hard material particles are formed by chromium oxide or zirconium oxide, which are added in the form of particles having average particle sizes of 5 microns in an amount of 100 g / l to the electrolyte. Moreover, the first particles are formed by lubricant particles formed by a solid lubricant such as hexagonal boron nitride. The lubricant particles are also dispersed in the electrolyte with an average particle size of 5 μm at a concentration of 100 g / l.

Die zweiten Partikel 2, die in dem Elektrolyten 3 enthalten sind, sind Metalllegierungspartikel, die zumindest Chrom und Aluminium, insbesondere überwiegend Chrom und Aluminium enthalten. Überwiegend bedeutet hierbei, dass die Summe der Anteile an Chrom und Aluminium den größten Legierungsbestandteil der Metalllegierungspartikel bilden, insbesondere mehr als 50 Gew.% der Metalllegierung der Metalllegierungspartikel ausmachen.The second particles 2 contained in the electrolyte 3 are metal alloy particles containing at least chromium and aluminum, especially predominantly chromium and aluminum. Predominantly, this means that the sum of the proportions of chromium and aluminum form the largest alloying constituent of the metal alloy particles, in particular make up more than 50% by weight of the metal alloy of the metal alloy particles.

Die zweiten Partikel 2 können ebenfalls mit einer durchschnittlichen Partikelgröße von 5 µm in einer Menge von 200 g/l in den Elektrolyten 3 dispergiert werden.The second particles 2 can also be dispersed in the electrolyte 3 with an average particle size of 5 microns in an amount of 200 g / l.

Der Elektrolyt wird auf eine Temperatur von 30°C bis 70°C gebracht und durch geeignete Rührgeräte oder dergleichen in Bewegung gehalten, sodass die dispergierten ersten und zweiten Partikel 1, 2 gleichmäßig verteilt im Elektrolyten 3 vorliegen.The electrolyte is brought to a temperature of 30 ° C to 70 ° C and kept in motion by suitable stirrers or the like, so that the dispersed first and second particles 1, 2 are uniformly distributed in the electrolyte 3.

Die Fig. 2 zeigt das Elektrolytbad aus Fig. 1 bei einer galvanischen Abscheidung einer erfindungsgemäßen Verschleißschutzbeschichtung auf einem Bauteil 4. Hierbei wird das Bauteil als Kathode an eine Stromversorgung 6 angeschlossen, während eine zusätzliche Anode 5 im Elektrolytbad angeordnet wird.The Fig. 2 shows the electrolyte bath Fig. 1 in a galvanic deposition of a wear protection coating according to the invention on a component 4. In this case, the component is connected as a cathode to a power supply 6, while an additional anode 5 is arranged in the electrolyte bath.

Die Fig. 3 zeigt das Bauteil 4 mit der abgeschiedenen Schicht 7, welche eine NiCo - Matrix mit eingelagertem ersten Partikeln 1 und zweiten Partikeln 2 aufweist. Die Stromdichte bei der galvanischen Abscheidung kann im Bereich von 1 bis 10 A/dm2 liegen.The Fig. 3 shows the component 4 with the deposited layer 7, which has a NiCo matrix with embedded first particles 1 and second particles 2. The current density in the electrodeposition may be in the range of 1 to 10 A / dm 2 .

Die abgeschiedene Schicht 7 wird zusammen mit dem Bauteil 4 einer Wärmebehandlung unterzogen und zwar in einem Temperaturbereich von 1000 bis 1150°C für 5 bis 15 Stunden unter Vakuum, sodass die zweiten Partikel 2 aus einer CrAl - Legierung zusammen mit der CoNi - Matrix der abgeschiedenen Schicht eine CoNiCrAl - Matrix bilden, in der Hartstoffpartikel 9a aus Chrom - und/oder Zirkonoxid und Gleitstoffpartikel 9b aus hexagonalem Bornitrid in der CoNiCrAl - Matrix vorliegen, um die Verschleißschutzbeschichtung 10 auf dem Bauteil 4 zu bilden.The deposited layer 7 is heat-treated together with the component 4 in a temperature range of 1000 to 1150 ° C. for 5 to 15 hours under vacuum, so that the second particles 2 are made of a CrAl alloy together with the CoNi matrix of the deposited ones Layer form a CoNiCrAl matrix in which hard material particles 9a of chromium and / or zirconium oxide and lubricant particles 9b of hexagonal boron nitride are present in the CoNiCrAl matrix in order to form the wear protection coating 10 on the component 4.

Wird beispielsweise für die zweiten Partikel 2 eine CrAlY - Legierung eingesetzt, so bildet sich eine CoNiCrAlY - Matrix 8 der Verschleißschutzbeschichtung 10 aus.If, for example, a CrAlY alloy is used for the second particles 2, then a CoNiCrAlY matrix 8 of the wear protection coating 10 is formed.

Bei dem gezeigten Ausführungsbeispiel der Fig. 1 bis 4 sind die ersten Partikel 1 mit einer Metallhülle aus Nickel und/oder Kobalt versehen, welche sich beim Wärmebehandlungsschritt zwischen den Fig. 3 und 4 in der Matrix 8 auflöst, sodass die Hartstoffpartikel 9a und die Gleitstoffpartikel 9b ohne umgebende Hülle in der Verschleißschutzbeschichtung 10 vorliegen.In the embodiment shown the Fig. 1 to 4 For example, the first particles 1 are provided with a metal shell of nickel and / or cobalt, which in the heat treatment step between the 3 and 4 dissolves in the matrix 8, so that the hard material particles 9a and the Gleitstoffpartikel 9b are present without surrounding casing in the wear-resistant coating 10.

Obwohl die vorliegende Erfindung anhand des Ausführungsbeispiels detailliert beschrieben worden ist, insbesondere bezüglich der eingesetzten Werkstoffe und der Verfahrensparameter, ist es für den Fachmann selbstverständlich, dass die Erfindung nicht auf diese Werkstoffe und Verfahrensparameter bzw. allgemein die Angaben im Ausführungsbeispiel beschränkt ist, sondern dass vielmehr Abwandlungen in der Weise möglich sind, dass andere Werkstoffe eingesetzt und unterschiedliche Verfahrensparameter verwendet werden können, ohne dass der Schutzbereich der beigefügten Ansprüche verlassen wird. Insbesondere ist es möglich einzelne vorgestellte Merkmale wegzulassen oder andersartige Kombinationen von Merkmalen vorzunehmen ohne den Schutzbereich der beigefügten Ansprüche zu verlassen. Die Offenbarung der vorliegenden Anmeldung schließt sämtliche Kombinationen der vorgestellten Einzelmerkmale mit ein.Although the present invention has been described in detail with reference to the exemplary embodiment, in particular with regard to the materials used and the process parameters, it is obvious to the person skilled in the art that the invention is not limited to these materials and process parameters or in general the information in the exemplary embodiment. but that rather modifications are possible in the way that other materials can be used and different process parameters can be used without departing from the scope of the appended claims. In particular, it is possible to omit individual introduced features or to make other types of combinations of features without departing from the scope of the appended claims. The disclosure of the present application includes all combinations of the featured individual features.

Claims (16)

Verfahren zur Herstellung einer Verschleißschutzbeschichtung (10) auf einem Bauteil, insbesondere einem Bauteil einer Strömungsmaschine, wobei das Verfahren die folgenden Schritte umfasst: Bereitstellen eines Elektrolyten (3), der Co und/oder Ni enthält, Dispergieren von ersten Partikeln (1) in den Elektrolyten, wobei die ersten Partikel Hartstoffpartikel und/oder Gleitstoffpartikel umfassen, Dispergieren von zweiten Partikeln (2) in den Elektrolyten, wobei die zweiten Partikel Metalllegierungspartikel umfassen, bei denen die Metalllegierung Chrom und Aluminium aufweist, Bereitstellen des zu beschichtenden Bauteils (4) in einem Bad des Elektrolyten, der mit ersten und zweiten Partikeln dispergiert ist, und galvanisches Abscheiden einer Matrix aus Co und/oder Ni mit eingelagerten Metalllegierungspartikeln (2) und eingelagerten Hartstoffpartikeln und/oder Gleitstoffpartikeln (1) auf dem Bauteil. Method for producing a wear protection coating (10) on a component, in particular a component of a turbomachine, the method comprising the following steps: Providing an electrolyte (3) containing Co and / or Ni, Dispersing first particles (1) in the electrolyte, wherein the first particles comprise hard material particles and / or lubricant particles, Dispersing second particles (2) in the electrolyte, the second particles comprising metal alloy particles in which the metal alloy comprises chromium and aluminum, Providing the component (4) to be coated in a bath of the electrolyte dispersed with first and second particles, and galvanic deposition of a matrix of Co and / or Ni with embedded metal alloy particles (2) and embedded hard material particles and / or lubricant particles (1) on the component. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, dass
nach dem galvanischen Abscheiden einer Matrix aus Co und/oder Ni mit eingelagerten Metalllegierungspartikeln und eingelagerten Hartstoffpartikeln und/oder Gleitstoffpartikeln auf dem Bauteil das Bauteil einer Wärmebehandlung unterzogen wird.Method according to claim 1,
characterized in that
after the galvanic deposition of a matrix of Co and / or Ni with embedded metal alloy particles and embedded hard material particles and / or lubricant particles on the component, the component is subjected to a heat treatment. Verfahren nach Anspruch 2,
dadurch gekennzeichnet, dass
die Wärmebehandlung bei einer Temperatur von 950°C bis 1200°C, insbesondere 1000°C bis 1150°C für 2 bis 20 h, insbesondere zwischen 5 und 15 h erfolgt.Method according to claim 2,
characterized in that
the heat treatment at a temperature of 950 ° C to 1200 ° C, in particular 1000 ° C to 1150 ° C for 2 to 20 h, in particular between 5 and 15 h. Verfahren nach Anspruch 2 oder 3,
dadurch gekennzeichnet, dass
die Wärmebehandlung unter Vakuum erfolgt.Method according to claim 2 or 3,
characterized in that
the heat treatment is carried out under vacuum. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
der Elektrolyt (3) NiSO4 und/oder CoSO4 umfasst.Method according to one of the preceding claims,
characterized in that
the electrolyte (3) comprises NiSO 4 and / or CoSO 4 . Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
der Elektrolyt (3) NaCl und/oder H3BO3 umfasst.Method according to one of the preceding claims,
characterized in that
the electrolyte (3) comprises NaCl and / or H 3 BO 3 . Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die Metalllegierung der Metalllegierungspartikel (2) eine Zusammensetzung aufweist, die ausgewählt ist aus der Gruppe, die CrAl, CrAlY, CrAlHf, CrAlYHf, CrAlTa, CrAlYTa, CrAlSi, MoCrSiAl, CrCoAl, CrNiAl und Legierungen mit Cr und Al umfasst, die mindestens ein oder mehrere Elemente ausgewählt aus Y, Hf, Ta, Si, Mo, Ni und Co umfassen.Method according to one of the preceding claims,
characterized in that
the metal alloy of the metal alloy particles (2) has a composition selected from the group consisting of CrAl, CrAlY, CrAlHf, CrAlYHf, CrAlTa, CrAlYTa, CrAlSi, MoCrSiAl, CrCoAl, CrNiAl, and alloys of Cr and Al having at least one or more several elements selected from Y, Hf, Ta, Si, Mo, Ni and Co include. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die ersten und zweiten Partikel (1, 2) jeweils mit einem Anteil von 50 g/l bis 300 g/l im Elektrolyt vorgesehen sind.Method according to one of the preceding claims,
characterized in that
the first and second particles (1, 2) are each provided with a proportion of 50 g / l to 300 g / l in the electrolyte. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die ersten Partikel (1) eine maximale oder durchschnittliche Partikelgröße kleiner oder gleich 10 µm, insbesondere zwischen 1 µm und 5 µm aufweisen.Method according to one of the preceding claims,
characterized in that
the first particles (1) have a maximum or average particle size of less than or equal to 10 μm, in particular between 1 μm and 5 μm. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die zweiten Partikel (2) eine maximale oder durchschnittliche Partikelgröße kleiner oder gleich 15 µm, insbesondere zwischen 1 µm und 5 µm aufweisen.Method according to one of the preceding claims,
characterized in that
the second particles (2) have a maximum or average particle size of less than or equal to 15 μm, in particular between 1 μm and 5 μm. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die ersten Partikel (1) eine metallische Hülle aufweisen, insbesondere eine Hülle, die Ni und/oder Co umfasst oder aus diesen gebildet ist.Method according to one of the preceding claims,
characterized in that
the first particles (1) have a metallic shell, in particular a shell which comprises or is formed from Ni and / or Co. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die Gleitstoffpartikel (1) Feststoffschmiermittel, insbesondere hexagonales Bornitrid umfassen.Method according to one of the preceding claims,
characterized in that
the lubricant particles (1) comprise solid lubricant, in particular hexagonal boron nitride. Verfahren nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, dass
die Hartstoffpartikel (1) Oxide, insbesondere Chromoxid oder Zirkonoxid umfassen.Method according to one of the preceding claims,
characterized in that
the hard material particles (1) comprise oxides, in particular chromium oxide or zirconium oxide. Verschleißschutzbeschichtung mit einer Matrix, die Co und/oder Ni sowie Cr und Al umfasst und in welche Hartstoffpartikel (9a) und/oder Gleitstoffparikel (9b) eingelagert sind, wobei die Verschleißschutzbeschichtung nach einem Verfahren nach einem der vorhergehenden Ansprüche hergestellt worden ist.Wear-resistant coating with a matrix comprising Co and / or Ni and Cr and Al and in which hard material particles (9a) and / or Gleitstoffparikel (9b) are embedded, wherein the anti-wear coating has been prepared by a method according to any one of the preceding claims. Verschleißschutzbeschichtung nach Anspruch 14,
dadurch gekennzeichnet, dass
die Hartstoffpartikel (9a) und/oder Gleitstoffpartikel (9b) mit einem Anteil von 5 Vol.% bis 40 Vol.%, insbesondere 10 Vol.% bis 30 Vol.% in der Verschleißschutzbeschichtung enthalten sind.Wear protection coating according to claim 14,
characterized in that
the hard material particles (9a) and / or lubricant particles (9b) are contained in the wear protection coating in a proportion of 5% by volume to 40% by volume, in particular 10% by volume to 30% by volume. Verschleißschutzbeschichtung nach Anspruch 14 oder 15,
dadurch gekennzeichnet, dass
die Matrix (8) 15 Gew.% bis 50 Gew.%, insbesondere 20 Gew.% bis 40 Gew.% Co und/oder 15 Gew.% bis 50 Gew.%, insbesondere 20 Gew.% bis 40 Gew.% Ni, 10 Gew.% bis 30 Gew.%, insbesondere 10 Gew.% bis 25 Gew.% Cr und 1 Gew.% bis 10 Gew.%, insbesondere 2 Gew.% bis 8 Gew.% Al beinhaltet.Wear protection coating according to claim 14 or 15,
characterized in that
the matrix (8) 15% by weight to 50% by weight, in particular 20% by weight to 40% by weight of Co and / or 15% by weight to 50% by weight, in particular 20% by weight to 40% by weight Ni , 10% by weight to 30% by weight, in particular 10% by weight to 25% by weight of Cr and 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight of Al.
EP14179103.8A 2013-09-18 2014-07-30 Method of electroplating wear-resistant coating Active EP2851455B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102013218687.8A DE102013218687A1 (en) 2013-09-18 2013-09-18 Galvanized wear protection coating and method therefor

Publications (2)

Publication Number Publication Date
EP2851455A1 true EP2851455A1 (en) 2015-03-25
EP2851455B1 EP2851455B1 (en) 2019-03-13

Family

ID=51292808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14179103.8A Active EP2851455B1 (en) 2013-09-18 2014-07-30 Method of electroplating wear-resistant coating

Country Status (3)

Country Link
US (1) US10428437B2 (en)
EP (1) EP2851455B1 (en)
DE (1) DE102013218687A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016221871A1 (en) * 2016-11-08 2018-05-09 Siemens Aktiengesellschaft A gas turbine engine component and method of making an erosion protected gas turbine engine component
CN110396710A (en) * 2019-08-08 2019-11-01 温州中牙模具有限公司 A kind of wear-resisting screw plate and its production technology

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2928580T3 (en) 2015-11-10 2022-11-21 Oerlikon Surface Solutions Ag Pfaeffikon Turbine clearance control coatings and procedure
CN107849700B (en) * 2015-12-01 2021-05-11 株式会社Ihi Sliding member having abrasion-resistant coating and method for forming abrasion-resistant coating
FR3085172B1 (en) * 2018-08-22 2021-03-05 Safran Aircraft Engines ABRADABLE COATING FOR TURBOMACHINE ROTATING BLADES

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1982000162A1 (en) * 1980-07-02 1982-01-21 Kedward E Composite electrodeposited coating and method of forming the same
DE3815976A1 (en) 1988-05-10 1989-11-23 Mtu Muenchen Gmbh METHOD FOR PRODUCING GALVANICALLY SEPARATED HOT GAS CORROSION LAYERS
EP0484115A1 (en) * 1990-11-01 1992-05-06 General Electric Company Abrasive turbine blade tips
WO1999024647A1 (en) * 1997-11-06 1999-05-20 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
EP1408197A1 (en) * 2001-06-13 2004-04-14 Mitsubishi Heavy Industries, Ltd. Method for forming abrasion-resistant layer for moving blade, abrasion-resistant layer and method for regeneration thereof, and gas turbine
DE102006016995A1 (en) * 2006-04-11 2007-10-18 Mtu Aero Engines Gmbh Component with an armor
WO2008034774A2 (en) * 2006-09-21 2008-03-27 Siemens Aktiengesellschaft Method for producing a layer on a carrier
EP2096194A2 (en) * 2008-02-19 2009-09-02 Parker-Hannifin Corporation Protective coating for metallic seals
DE102010040469B3 (en) * 2010-09-09 2012-01-12 Federal-Mogul Wiesbaden Gmbh Laminated material for sliding elements, process for its production and use

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2182055B (en) * 1985-10-28 1989-10-18 Baj Ltd Improvements relating to electrodeposited coatings
GB2241506A (en) * 1990-02-23 1991-09-04 Baj Ltd Method of producing a gas turbine blade having an abrasive tip by electrodepo- sition.
US5536022A (en) * 1990-08-24 1996-07-16 United Technologies Corporation Plasma sprayed abradable seals for gas turbine engines
ATE223518T1 (en) * 1994-03-17 2002-09-15 Westaim Corp LOW FRICTION COATINGS BASED ON COBALT ON TITANIUM
US6916529B2 (en) * 2003-01-09 2005-07-12 General Electric Company High temperature, oxidation-resistant abradable coatings containing microballoons and method for applying same
US7320832B2 (en) * 2004-12-17 2008-01-22 Integran Technologies Inc. Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate
JP4608347B2 (en) * 2005-03-29 2011-01-12 ヤンマー株式会社 Exhaust gas purification device
US8034153B2 (en) * 2005-12-22 2011-10-11 Momentive Performances Materials, Inc. Wear resistant low friction coating composition, coated components, and method for coating thereof
TWI361471B (en) * 2007-07-16 2012-04-01 Via Tech Inc Transmission line structure and signal transmission structure
DE102007057197A1 (en) * 2007-11-28 2008-06-19 Daimler Ag Gearchange fork for lorry, includes tribological coating on wearing surfaces, formed by wear-resistant ceramic and solid lubricant
US7998604B2 (en) * 2007-11-28 2011-08-16 United Technologies Corporation Article having composite layer
US8790789B2 (en) * 2008-05-29 2014-07-29 General Electric Company Erosion and corrosion resistant coatings, methods and articles
DE102010024224B4 (en) * 2010-06-18 2016-08-18 MTU Aero Engines AG Method and device for applying a dispersion layer with a matrix material and solid particles
US20120099971A1 (en) * 2010-10-25 2012-04-26 United Technologies Corporation Self dressing, mildly abrasive coating for clearance control

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1982000162A1 (en) * 1980-07-02 1982-01-21 Kedward E Composite electrodeposited coating and method of forming the same
DE3815976A1 (en) 1988-05-10 1989-11-23 Mtu Muenchen Gmbh METHOD FOR PRODUCING GALVANICALLY SEPARATED HOT GAS CORROSION LAYERS
US4895625A (en) 1988-05-10 1990-01-23 Mtu Motoren-Und Turbinen-Union Muenchen Gmbh Method for producing a galvanically deposited protection layer against hot gas corrosion
EP0424863A1 (en) 1988-05-10 1991-05-02 Mtu Motoren- Und Turbinen-Union MàœNchen Gmbh Process for electrolytically depositing a metal layer resisting corrosion by hot gases
EP0484115A1 (en) * 1990-11-01 1992-05-06 General Electric Company Abrasive turbine blade tips
WO1999024647A1 (en) * 1997-11-06 1999-05-20 Chromalloy Gas Turbine Corporation Method for producing abrasive tips for gas turbine blades
EP1408197A1 (en) * 2001-06-13 2004-04-14 Mitsubishi Heavy Industries, Ltd. Method for forming abrasion-resistant layer for moving blade, abrasion-resistant layer and method for regeneration thereof, and gas turbine
DE102006016995A1 (en) * 2006-04-11 2007-10-18 Mtu Aero Engines Gmbh Component with an armor
WO2008034774A2 (en) * 2006-09-21 2008-03-27 Siemens Aktiengesellschaft Method for producing a layer on a carrier
EP2096194A2 (en) * 2008-02-19 2009-09-02 Parker-Hannifin Corporation Protective coating for metallic seals
DE102010040469B3 (en) * 2010-09-09 2012-01-12 Federal-Mogul Wiesbaden Gmbh Laminated material for sliding elements, process for its production and use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016221871A1 (en) * 2016-11-08 2018-05-09 Siemens Aktiengesellschaft A gas turbine engine component and method of making an erosion protected gas turbine engine component
CN110396710A (en) * 2019-08-08 2019-11-01 温州中牙模具有限公司 A kind of wear-resisting screw plate and its production technology

Also Published As

Publication number Publication date
DE102013218687A1 (en) 2015-04-02
US20150075327A1 (en) 2015-03-19
US10428437B2 (en) 2019-10-01
EP2851455B1 (en) 2019-03-13

Similar Documents

Publication Publication Date Title
EP2851455B1 (en) Method of electroplating wear-resistant coating
EP2619348B1 (en) Layered composite material for sliding elements, method for producing same and use thereof
EP2902526B1 (en) Multi-layer sliding bearing
WO2016023790A2 (en) Composite material for a sliding bearing
DE2758618A1 (en) HIGH TEMPERATURE-RESISTANT, ABRASION-RESISTANT COATING COMPOSITION
DE3535548A1 (en) METAL PROTECTIVE COATING
CH667469A5 (en) PROCESS FOR APPLYING PROTECTIVE LAYERS.
EP2796588B1 (en) Method for producing a high temperature protective coating
DE102017100086B4 (en) SUPERALLOY COMPOSITE PREFORMS AND THEIR APPLICATIONS
EP2294656A1 (en) Component with a layer into which cnt (carbon nanotubes) are incorporated and a method for the manufacture of said component
EP2695964B1 (en) Protective coating tailored to a component
DE69838341T2 (en) IMPROVING THE EQUALITY OF A COATING DURING ALUMINUM OXIDE DIPING
DE102010007624B4 (en) Separator for a fuel cell and method for its production
DE2935537A1 (en) TIT ALLOY AND THEIR USE AS ELECTRODE SUBSTRATE MATERIAL
DE102008046817A1 (en) Coated sliding element, particularly coated sliding bearing for use in internal combustion engines, comprises surface having metal or metal alloy layer and reaction layer
WO2008154979A2 (en) Method for producing a sliding element coated in a structured manner and sliding element thus obtained
EP1900842A1 (en) Pack diffusion on an interlayer
EP2840166B1 (en) Intermetallic anti-wear protective coating for titanium materials
DE102007001374B4 (en) Anodized substrate layer with electrodeposition by electrochemical deposition and method for its production
EP1900708B1 (en) Heat insulation material with high cyclical temperature rating
DE102011089131A1 (en) Diffusion coating process and chromium layer made therewith
DE102007049041A1 (en) Sliding bearing with sliding and inlet layer and its manufacturing process
DE10251457B4 (en) Sliding element with composite cladding film
DE2608637C3 (en) Process for making alloys
WO2008154978A2 (en) Method for producing a sliding element coated with silver in a structured manner, and sliding element obtained by said method

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140730

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

R17P Request for examination filed (corrected)

Effective date: 20150813

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20151201

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20181126

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1107771

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190315

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502014011088

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190313

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190613

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190614

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190613

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190713

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014011088

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190713

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

26N No opposition filed

Effective date: 20191216

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190731

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190731

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190730

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1107771

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140730

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190313

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230724

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230724

Year of fee payment: 10

Ref country code: DE

Payment date: 20230720

Year of fee payment: 10