EP2695964B1 - Protective coating tailored to a component - Google Patents
Protective coating tailored to a component Download PDFInfo
- Publication number
- EP2695964B1 EP2695964B1 EP12179980.3A EP12179980A EP2695964B1 EP 2695964 B1 EP2695964 B1 EP 2695964B1 EP 12179980 A EP12179980 A EP 12179980A EP 2695964 B1 EP2695964 B1 EP 2695964B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chromium
- layer
- carried out
- component
- different
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
- C23C10/32—Chromising
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/38—Chromising
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/38—Chromising
- C23C10/40—Chromising of ferrous surfaces
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/48—Aluminising
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/48—Aluminising
- C23C10/50—Aluminising of ferrous surfaces
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
- C23C10/54—Diffusion of at least chromium
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
- C23C10/54—Diffusion of at least chromium
- C23C10/56—Diffusion of at least chromium and at least aluminium
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/60—After-treatment
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
Definitions
- the inch chromation can be carried out with a high chromium activity, the chemical activity being ⁇ 0.4 or 40 percent. This can be achieved, for example, by powder packing processes or gas phase chromium plating.
- the slip can be applied using physical methods such as brushing or spraying.
- the chromating in the first sub-step can be carried out at a temperature of 1000 ° C. to 1180 ° C., in particular 1050 ° C. to 1130 ° C. for a period of 1 to 20 hours, in particular 10 to 15 hours.
- the base material treated in this way for example a component of a gas turbine or an aircraft engine
- the component is packed, for example, in a powder pack with high aluminum activity (chemical activity) in the range greater than or equal to 0.15 or 15% and is thermally or thermochemically treated at temperatures of more than 1050 ° C. for a period of 2 to 14 hours.
- Gas phase alitation can also be used. Areas without alitation can remain in particular if these areas are covered accordingly.
- the aluminum activity can preferably be in the range from 0.15 to 0.35.
- the alitation and / or chrome plating described here is also suitable for the internal coating of hollow blades.
- the above method can be applied to gas turbine or aircraft engine components.
- the component can be formed from an alloy that is metallic Main component, which has the largest proportion of the alloy, with a protective layer for protection against high temperatures and aggressive media, the protective layer comprising chromium and aluminum and in particular has been produced by a method according to one of the preceding claims, and wherein the protective layer is different Has areas that differ in their composition with regard to the chromium and / or aluminum content.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung einer Schutzschicht zum Schutz eines Bauteils vor hohen Temperaturen und aggressiven Medien, wobei die Schutzschicht Aluminium und Chrom umfasst.The present invention relates to a method for producing a protective layer for protecting a component from high temperatures and aggressive media, the protective layer comprising aluminum and chromium.
In Strömungsmaschinen wie stationären Gasturbinen oder Flugtriebwerken sind Bauteile, wie beispielsweise Leit- oder Laufschaufeln, sowohl hohen Temperaturen als auch aggressiven Medien bzw. Atmosphären ausgesetzt, die unterschiedliche Schädigungen wie Partikelerosion, Korrosion und Hochtemperaturoxidation bewirken. Entsprechend ist es erforderlich, die Bauteile möglichst gegen alle diese Schädigungen zu schützen, wobei unter Umständen Kompromisse eingegangen werden müssen, da Schutzmaßnahmen, die für eine Art der Schädigung erfolgversprechend sind, selbst einer starken Schädigung durch andere Schädigungsmechanismen ausgesetzt sein können.In turbomachines such as stationary gas turbines or aircraft engines, components such as guide vanes or rotor blades are exposed to both high temperatures and aggressive media or atmospheres that cause various types of damage such as particle erosion, corrosion and high-temperature oxidation. Accordingly, it is necessary to protect the components as far as possible against all this damage, and compromises may have to be made, since protective measures that promise a type of damage can themselves be exposed to severe damage from other damage mechanisms.
Beispielsweise ist es bisher nicht in zufriedenstellendem Maße gelungen, Schutzmaßnahmen gegen verschiedene Korrosions- und Oxidationsangriffe gleichzeitig zu bewirken. So treten bei Gasturbinen oder Flugtriebwerken bei Bauteilen, die Betriebstemperaturen im Bereich von 550 bis 750 °C ausgesetzt sind, unter alkalischen oder erdalkalischen Ablagerungen Korrosions- und Sulfidationsangriffe der sogenannten Typ-2-Korrosion ein. Ein flächiger Materialangriff bei Temperaturen zwischen 750 °C und 900°C unter Anwesenheit von schwefel- und chloridhaltigen Kalium-, Natrium- und Kalziumsalzen wird als Typ-1-Korrosion bezeichnet. Bei Temperaturen über 900 °C dominiert bei Nickelbasisguss- und Kobaltbasisguss-Legierungen, die häufig für Bauteile in entsprechend heißen Bereichen einer Gasturbine oder eines Flugtriebwerks eingesetzt werden, der Oxidationsangriff.For example, it has so far not been possible to implement protective measures against various corrosion and oxidation attacks to a satisfactory extent. In the case of gas turbines or aircraft engines, components that are exposed to operating temperatures in the range from 550 to 750 ° C. are subject to corrosion and sulfidation attacks of so-called
Da es bisher nicht gelungen ist, eine einheitliche Schutzmaßnahme für die verschiedenen Schädigungsmechanismen bereitzustellen, ist bereits vorgeschlagen worden, unterschiedliche Schutzmaßnahmen in unterschiedlichen Bereichen des entsprechenden Bauteils, wie beispielsweise einer Turbinenschaufel, vorzusehen. Hierzu schlägt die
Allerdings sind die Herstellkosten für derartige, unterschiedliche Beschichtungen auf einem Bauteil sehr hoch, da die Schichten einzeln nacheinander aufgebracht werden und ein hoher Aufwand für Schutzmaßnahmen für nicht zu beschichtende Teile der Bauteile besteht.However, the manufacturing costs for such different coatings on a component are very high, since the layers are applied individually one after the other and there is a high outlay for protective measures for parts of the components which are not to be coated.
In der
Das Dokument
Es ist deshalb Aufgabe der vorliegenden Erfindung, ein Verfahren zur Herstellung einer Schutzschicht zum Schutz eines Bauteils vor hohen Temperaturen und aggressiven Medien sowie eine entsprechende Schutzschicht bereitzustellen, wobei die Schutzschicht unterschiedlichen Schädigungsmechanismen widerstehen soll. Darüber hinaus soll das Verfahren einfach durchführbar sein und die Schutzschicht einen wirksamen Schutz vor Korrosion und Oxidation bieten.It is therefore an object of the present invention to provide a method for producing a protective layer for protecting a component from high temperatures and aggressive media, and a corresponding protective layer, the protective layer being intended to withstand different damage mechanisms. In addition, the process should be easy to carry out and the protective layer should offer effective protection against corrosion and oxidation.
Diese Aufgabe wird gelöst durch ein Verfahren mit den Merkmalen des Anspruchs 1. Vorteilhafte Ausgestaltungen sind Gegenstand der abhängigen Ansprüche.This object is achieved by a method having the features of
Die Erfindung greift die Idee auf, dass unterschiedliche Schutzschichten auf einem Bauteil vorgesehen werden müssen, welches unterschiedlichen Schädigungsmechanismen unterworfen wird. Entgegen dem Stand der Technik, in dem in aufwändigen Verfahren getrennt verschiedene Schichten erzeugt werden, schlägt die vorliegende Erfindung jedoch vor, eine Aluminium und Chrom enthaltende Schicht auszubilden, die in verschiedenen Bereichen der Schutzschicht unterschiedlich ausgebildet sein kann, aber deren unterschiedliche Bereiche in gemeinsamen Herstellungsschritten hergestellt werden können. Entsprechende Aluminium-Chrom-Schichten können nämlich durch Variation des Chromanteils auf verschiedene Oxidations- und Korrosionsangriffe eingestellt werden, so dass durch Aluminium-Chrom-Schichten, die insbesondere unterschiedliche Chromanteile aufweisen, einem Bauteil wirksamer Schutz vor unterschiedlichen Schädigungsmechanismen verliehen werden kann. Gleichzeitig bieten die Aluminium-Chrom-Schichten den Vorteil, dass ihre Herstellung mit unterschiedlichen Chrom-Anteilen in lokal verschieden Bereichen in einem einzigen Arbeitsschritt erfolgen kann.The invention takes up the idea that different protective layers have to be provided on a component which is subjected to different damage mechanisms. Contrary to the prior art, in which different layers are produced separately in complex processes, the present invention proposes, however, to form a layer containing aluminum and chromium, which can be designed differently in different areas of the protective layer, but whose different areas in common production steps can be produced. Corresponding aluminum-chromium layers can be adjusted to different oxidation and corrosion attacks by varying the chromium content, so that effective protection against different damage mechanisms can be imparted to a component by aluminum-chromium layers, which in particular have different chromium components. At the same time, the aluminum-chrome layers offer the advantage that they can be manufactured with different chromium contents in locally different areas in a single work step.
Entsprechend werden erfindungsgemäße Aluminium-Chrom-Schichten dadurch hergestellt, dass in einem ersten Teilschritt eine Inchromierung der zu schützenden Bauteiloberfläche erfolgt und in einem zweiten Teilschritt eine Alitierung durchgeführt wird. Die Inchromierung und Alitierung werden in verschiedenen lokalen Bereichen der zu schützenden Bauteiloberfläche gleichzeitig, aber derart unterschiedlich durchgeführt, dass in der Schutzschicht unterschiedliche Bereiche entsprechend den unterschiedlichen Schutzanforderungen entstehen.Correspondingly, aluminum-chromium layers according to the invention are produced by chroming the component surface to be protected in a first sub-step and performing an alitation in a second sub-step. The inch chromation and alitation are carried out simultaneously in different local areas of the component surface to be protected, but in such a different way that different areas are created in the protective layer in accordance with the different protection requirements.
Die Abscheidung des Chroms im ersten Teilschritt der Inchromierung kann mittels thermochemischer Verfahren, thermophysikalischer Verfahren, physikalischer Verfahren oder elektrochemischer Verfahren erfolgen.The chromium can be deposited in the first sub-step of the inchromation by means of thermochemical processes, thermophysical processes, physical processes or electrochemical processes.
Unter thermochemischen Verfahren werden hierbei Gasdiffusionsabscheidungen verstanden, bei denen Chrom unter Einsatz von Temperatur und chemischer Reaktionen an der Bauteiloberfläche bereitgestellt wird, so dass das Chrom in das Bauteil eindiffundieren und/oder sich auf diesem ablagern kann.In this context, thermochemical processes are understood to mean gas diffusion deposits in which chromium is provided on the component surface using temperature and chemical reactions, so that the chromium can diffuse into and / or deposit on the component.
Beim PVD - Verfahren (physical vapor deposition (physikalische Dampfphasenabscheidung)) wird unter Einsatz von Temperatur eine Verdampfung mit entsprechender Abscheidung von Chrom bewirkt. Bei elektrochemischen Verfahren wird unter Anordnung eines elektrischen Potentials eine Abscheidung von Chrom aus einem Elektrolyten bewirkt. Die Abscheidung von Chrom kann auch mittels Dispersionsbeschichtung erfolgen. Eine Kombination beider letztgenannten Verfahren ist auch denkbar. Dabei kann eine Auflageschicht mittels chemischer und/oder elektrochemischer Abscheidung von Chrom und weiteren Bestandteilen, wie beispielsweise Nickel, und zusätzlich eingelagerten Partikeln hergestellt werden.In the PVD process (physical vapor deposition), evaporation with the appropriate deposition of chromium is effected using temperature. In electrochemical processes, chromium is deposited from an electrolyte by arranging an electrical potential. Chromium can also be deposited by means of a dispersion coating. A combination of the latter two methods is also conceivable. A coating layer can be made using chemical and / or electrochemical deposition of chromium and other constituents, such as nickel, and additionally embedded particles.
Das Eindiffundieren von Chrom in die Bauteiloberfläche zur Ausbildung einer chromreichen Schicht nach der Aufbringung auf die zu schützende Bauteiloberfläche kann durch eine entsprechende Wärmebehandlung erfolgen, wobei auch bei thermochemischen und thermophysikalischen Verfahren, bei denen die Aufbringung bereits bei entsprechenden hohen Temperaturen durchgeführt wird und von daher bereits ein Eindiffundieren des Chroms in der Bauteiloberfläche ermöglicht wird, zusätzlich eine weitergehende Wärmebehandlung zur weiteren Diffusion des Chroms in tiefere Bauteilbereiche durchgeführt werden kann.The diffusion of chromium into the component surface to form a chromium-rich layer after application to the component surface to be protected can be carried out by an appropriate heat treatment, even in thermochemical and thermophysical processes in which the application is already carried out at correspondingly high temperatures and therefore already a diffusion of the chromium into the component surface is made possible, in addition a further heat treatment for the further diffusion of the chromium into deeper component areas can be carried out.
In dem ersten Teilschritt der Inchromierung können zur Ausbildung der unterschiedlichen Schutzschichtbereiche in den verschiedenen Bereichen unterschiedliche Chromgehalte abgeschieden werden, indem beispielsweise Chrom enthaltende Materialien in unterschiedlichen Mengen oder mit unterschiedlichen Konzentrationen an Chrom aufgebracht werden. Die Abscheidung unterschiedlicher Chromgehalte kann so erfolgen, dass in der gebildeten Schicht mit Chromanreicherung ein Chromgehalt von 15 Gew.-% bis 100 Gew.-% vorliegen kann.In the first sub-step of the chromium plating, different chromium contents can be deposited in the different regions to form the different protective layer regions, for example by applying chromium-containing materials in different amounts or with different concentrations of chromium. Different chromium contents can be deposited in such a way that a chromium content of 15% by weight to 100% by weight can be present in the layer with chromium enrichment.
Bei der Inchromierung können auch unterschiedlichen Dicken der mit Chrom angereicherte Schichten erzeugt werden, wobei insbesondere die Schichtdicken im Bereich von 5 µm bis 150 µm variieren können.With inch chroming, different thicknesses of the layers enriched with chromium can also be produced, wherein in particular the layer thicknesses can vary in the range from 5 μm to 150 μm.
Für die Ausbildung einer ersten, äußeren Oberflächenschicht mit hohem Chromanteil kann die Inchromierung mit einer hohen Chromaktivität durchgeführt werden, wobei die chemische Aktivität ≥ 0,4 bzw. 40 Prozent sein kann. Dies kann beispielsweise durch Pulverpackverfahren oder Gasphaseninchromierung realisiert werden.For the formation of a first, outer surface layer with a high chromium content, the inch chromation can be carried out with a high chromium activity, the chemical activity being ≥ 0.4 or 40 percent. This can be achieved, for example, by powder packing processes or gas phase chromium plating.
Die Chromierung kann insbesondere durch eine Temperaturbehandlung in Anwesenheit von flüssigen, chromreichen Schlickerschichten erfolgen, wobei der Schlicker Chrom - haltige Pulver mit Aktivatoren und Bindemittel umfassen kann. Als Bindemittel kommen Alkohole oder sonstige Lösungsmittel in Betracht, während als Aktivator Halogenide eingesetzt werden können.The chroming can in particular be carried out by means of a temperature treatment in the presence of liquid, chromium-rich slip layers, the slip being able to comprise chromium-containing powder with activators and binders. Alcohols or other solvents can be used as binders, while halides can be used as activators.
Der Schlicker kann über physikalische Verfahren, wie Streichen oder Spritzen aufgebracht werden.The slip can be applied using physical methods such as brushing or spraying.
Bei Verwendung von chromhaltigem Schlicker mit Chromaktivitäten (chemischer Aktivität) von mehr als 0,4 bzw. 40% für hochchromhaltige Teilbereiche der zu erzeugenden AlCr - Schicht kann bei einer thermischen und/oder thermochemischen Behandlung in einem Temperaturbereich von 1000°C bis 1180°C, insbesondere 1050°C bis 1100 °C für Zeiten von 2 bis 20 Stunden, insbesondere 10 bis 15 Stunden, eine chromreiche Schicht mit einer Schichtdicke von 10 µm bis 150 µm und einem Chromgehalt von größer oder gleich 40 Gew.-%, insbesondere 50 Gew.-% bis 95 Gew.-% ausgebildet werden. Die Chrom-reiche Schicht weist hierbei eine äußere α - Chrom - Teilschicht und eine innere Mischkristallschicht mit im Wesentlichen Chrom und der Hauptkomponente der Legierung des beschichteten Bauteils, z.B. Nickel auf.When using chromium-containing slip with chromium activities (chemical activity) of more than 0.4 or 40% for high-chromium parts of the AlCr layer to be produced, thermal and / or thermochemical treatment can be carried out in a temperature range from 1000 ° C to 1180 ° C , in particular 1050 ° C. to 1100 ° C. for times of 2 to 20 hours, in particular 10 to 15 hours, a chromium-rich layer with a layer thickness of 10 μm to 150 μm and a chromium content of greater than or equal to 40% by weight, in particular 50 % By weight to 95% by weight are formed. The chromium-rich layer here has an outer α-chromium partial layer and an inner mixed crystal layer with essentially chromium and the main component of the alloy of the coated component, e.g. Nickel on.
Allgemein lässt sich die Chromierung im ersten Teilschritt bei einer Temperatur von 1000°C bis 1180°C, insbesondere 1050°C bis 1130°C bei einem Zeitraum von 1 bis 20 Stunden, insbesondere 10 bis 15 Stunden durchführen.In general, the chromating in the first sub-step can be carried out at a temperature of 1000 ° C. to 1180 ° C., in particular 1050 ° C. to 1130 ° C. for a period of 1 to 20 hours, in particular 10 to 15 hours.
Nach der Herstellung der chromreichen Schicht mit vorzugsweise unterschiedlichen Chromgehalten und/oder unterschiedlichen Schichtdicken in den verschiedenen Bereichen des Bauteils, die unterschiedliche AlCr - Schichten erhalten sollen, wird der so behandelte Grundwerkstoff, beispielsweise ein Bauteil einer Gasturbine oder eines Flugtriebwerks, einem Alitierverfahren unterzogen, bei dem das Bauteil beispielsweise in eine Pulverpackung mit hoher Aluminiumaktivität (chemische Aktivität) im Bereich größer oder gleich 0,15 bzw. 15 % eingepackt und bei Temperaturen von mehr als 1050°C für eine Zeit von 2 bis 14 Stunden thermisch oder thermochemisch behandelt wird. Auch Gasphasenalitieren kann verwendet werden. Es können insbesondere Bereiche ohne Alitieren verbleiben, wenn diese Bereiche entsprechend abgedeckt werden. Vorzugsweise kann die Aluminiumaktivität im Bereich von 0,15 bis 0,35 liegen. Als Pulverpackungen kommen Gemische aus Aluminiumoxidpulver, Aluminiumpulver und einem Halogenid als Aktivator, in Frage, sodass Aluminium in der Größenordnung von 10 Gew.-% bis 30 Gew.-% in die Schicht eindiffundieren kann. Auch bei der Alitierung können durch lokal unterschiedlich verwendete Aluminiumaktivitäten, lokal unterschiedliche Schutzschichten erzeugt werden. Hierbei kann entweder nur die Alitierung bei gleichmäßig erzeugten Cr - reichen Schichten örtlich unterschiedlich erfolgen oder mit der oben beschriebenen örtlich unterschiedlichen Chromierung kombiniert werden.After the production of the chromium-rich layer with preferably different chromium contents and / or different layer thicknesses in the different areas of the component that are to receive different AlCr layers, the base material treated in this way, for example a component of a gas turbine or an aircraft engine, is subjected to an alitation process the component is packed, for example, in a powder pack with high aluminum activity (chemical activity) in the range greater than or equal to 0.15 or 15% and is thermally or thermochemically treated at temperatures of more than 1050 ° C. for a period of 2 to 14 hours. Gas phase alitation can also be used. Areas without alitation can remain in particular if these areas are covered accordingly. The aluminum activity can preferably be in the range from 0.15 to 0.35. Mixtures of aluminum oxide powder, aluminum powder and a halide as activator are suitable as powder packs, so that aluminum can diffuse into the layer in the order of 10% by weight to 30% by weight. Also in the case of alitation, locally different protective layers can be generated by locally different aluminum activities. In this case, only the alitation with evenly generated Cr can suffice Layers take place locally differently or can be combined with the locally different chromating described above.
Nach dem Alitieren mit einer chemischen Aluminiumaktivität größer oder gleich 0,15 bzw. 15% kann eine zweite Alitierung mit einer niedrigeren chemischen Aluminium - Aktivität erfolgen, wobei die Aluminium - Aktivität im Bereich von 0,05 bis 0,3 gewählt werden kann. Die Auslagerungstemperatur bei diesem zweiten Alitierschritt kann größer oder gleich 1050° C und die Auslagerungszeit 3 bis 20 Stunden betragen.After the alitation with a chemical aluminum activity greater than or equal to 0.15 or 15%, a second alitation with a lower chemical aluminum activity can take place, the aluminum activity being able to be selected in the range from 0.05 to 0.3. The aging temperature in this second alitation step can be greater than or equal to 1050 ° C and the aging time can be 3 to 20 hours.
Zusätzlich kann nach dem Chromieren und Alitieren eine Diffusionsglühung bei einer Temperatur größer oder gleich 1050°C für eine Zeit von 2 bis 8 Stunden durchgeführt werden.In addition, after chromating and alitizing, diffusion annealing can be carried out at a temperature greater than or equal to 1050 ° C. for a period of 2 to 8 hours.
Vor, während oder nach dem Chromieren und/oder Alitieren kann eine Oberflächenbehandlung durch physikalische Dampfphasenabscheidung (Physical Vapor Deposition (PVD)) chemische Dampfphasenabscheidung (Chemical Vapor Deposition (CVD)), Lackieren, galvanisches Abscheiden und/oder direktes Aufbringen eines Stoffes durchgeführt werden, bei welchem eines oder mehrere Elemente aus der Gruppe, die Platin, Palladium, Hafnium, Zirkon, Yttrium und Silizium umfasst, aufgebracht werden. Damit können in die Schicht eine oder mehrere dieser Elemente eingebracht werden, um so die Schichteigenschaften zusätzlich positiv zu beeinflussen.Before, during or after chroming and / or alitizing, a surface treatment can be carried out by physical vapor deposition (PVD), chemical vapor deposition (CVD), painting, electrodeposition and / or direct application of a substance, in which one or more elements from the group comprising platinum, palladium, hafnium, zirconium, yttrium and silicon are applied. One or more of these elements can thus be introduced into the layer in order to additionally influence the layer properties.
Entsprechend können Bauteile, wie beispielsweise Turbinenschaufeln für stationäre Gasturbinen oder Flugtriebwerke, nach dem obigen Verfahren hergestellt werden, die eine Schutzschicht mit großen Bestandteilen an Chrom und Aluminium aufweisen, wobei die Schutzschicht unterschiedliche Bereiche aufweist, die sich durch ihre Zusammensetzung hinsichtlich des Chrom- und/oder Aluminiumanteils unterscheiden. Nach einem Aspekt der vorliegenden Erfindung, für den unabhängig und in Kombination mit anderen Aspekten der vorliegenden Erfindung Schutz begehrt wird, weist die Schutzschicht mindestens zwei unterschiedliche Bereiche auf, die jeweils unterschiedliche Oberflächenschichten umfassen. Die Oberflächenschicht, also die äußere Schicht des Bauteils, die in Kontakt mit der umgebenden Atmosphäre gelangt, kann entweder eine hochchromhaltige AlCr-Schicht, eine AlCr-Schicht mit mittleren Aluminiumgehalten und niedrigen Chromgehalten oder eine Schicht mit jeweils mittleren Chrom- und Aluminiumgehalten sein.Correspondingly, components, such as turbine blades for stationary gas turbines or aircraft engines, can be produced according to the above method, which have a protective layer with large constituents of chromium and aluminum, the protective layer having different areas, which are distinguished by their composition with regard to the chrome and / or or aluminum content. According to one aspect of the present invention, for which protection is desired independently and in combination with other aspects of the present invention, the protective layer has at least two different areas, each of which comprises different surface layers. The surface layer, i.e. the outer layer of the component that comes into contact with the surrounding atmosphere, can either be a high-chromium AlCr layer, an AlCr layer with medium aluminum contents and low chromium contents or a layer with medium chromium and aluminum contents.
Die beigefügten Zeichnungen zeigen in rein schematischer Weise in
- Fig. 1
- eine Turbinenschaufel und ein Temperatur-Ort-Diagramm, welches den Temperaturverlauf über der Schaufel anzeigt; und in
- Fig. 2
- ein ternäres Zustandsdiagramm aus dem System Chrom-Aluminium-Nickel, welches die Bereiche der Zusammensetzung der unterschiedlichen Schichtzusammensetzungen der vorliegenden Erfindung zeigt.
- Fig. 1
- a turbine blade and a temperature-location diagram which shows the temperature profile over the blade; and in
- Fig. 2
- a ternary state diagram from the system chromium-aluminum-nickel, which shows the ranges of the composition of the different layer compositions of the present invention.
Weitere Vorteile, Kennzeichen und Merkmale der vorliegenden Erfindung werden bei der nachfolgenden detaillierten Beschreibung eines Ausführungsbeispiels deutlich, wobei die Erfindung nicht auf dieses Ausführungsbeispiel beschränkt ist.Further advantages, characteristics and features of the present invention will become clear in the following detailed description of an exemplary embodiment, the invention being not restricted to this exemplary embodiment.
Die
Bei den in Gasturbinen oder Flugtriebwerken herrschenden Atmosphären treten bei niedrigen Temperaturen im Bereich von kleiner 900°C Korrosionsangriffe, insbesondere in Form von Sulfidation auf, während bei höheren Temperaturen über 900°C die Heißgasoxidation im Vordergrund steht. Allerdings ist insbesondere in den Übergangsbereichen mit mittleren Temperaturen ein gemischter Angriff aus Heißgasoxidation und Heißgaskorrosion, insbesondere Sulfidation, zu beobachten. Bei der Sulfidation kann je nach Temperatur, bei der die Sulfidation stattfindet, zwischen einem Sulfidationstyp 1 bei ca. 900°C und einem Sulfidationstyp 2 bei Temperaturen im Bereich von 700°C unterschieden werden.In the atmospheres prevailing in gas turbines or aircraft engines, corrosion attacks occur at low temperatures in the region of less than 900 ° C., in particular in the form of sulfidation, while hot gas oxidation is in the foreground at higher temperatures above 900 ° C. However, a mixed attack of hot gas oxidation and hot gas corrosion, in particular sulfidation, can be observed, particularly in the transition regions with medium temperatures. In sulfidation, depending on the temperature at which the sulfidation takes place, a distinction can be made between a
Um gegen die verschiedenen Oxidations- und Korrosionsangriffe geschützt zu sein, wird die Turbinenschaufel 1 mit unterschiedlichen Schutzschichten versehen, wobei im Innendeckbandbereich bzw. Außendeckbandbereich Schutzschichten auf Basis von Chrom und insbesondere hochchromhaltige AlCr-Schichten ausgebildet werden, während im Schaufelblattbereich 2 Schutzschichten auf Basis von Aluminium oder Platin - Aluminium, sowie insbesondere AlCr-Schichten mit niedrigem Chromgehalt ausgebildet werden, während in den Übergangsbereichen 5,6 Aluminium - Chrom - Schichten mit mittlerem Chromgehalt aufgebracht werden.In order to be protected against the various oxidation and corrosion attacks, the
Die Aluminium - Chrom - Schichten mit hohem Chromgehalt bilden eine erste äußere Oberflächenschicht mit Chromgehalten im Bereich von 40 bis 90 Gew.- % und Aluminiumgehalten im Bereich von 5 bis 35 Gew.-%. Je nachdem, welcher Basiswerkstoff bei der Turbinenschaufel vorliegt, finden sich in einer ersten äußeren Oberflächenschicht bis zu 55 Gew.-%, vorzugsweise bis zu 30 Gew.-%, der Hauptbestandteile des Basiswerkstoffs, insbesondere der Hauptkomponente, wie beispielsweise Nickel, Kobalt oder Eisen, je nachdem, ob es sich bei dem Grundwerkstoff des zu schützenden Bauteils um eine Nickelbasislegierung, Kobaltbasislegierung oder Eisenbasislegierung handelt.The aluminum-chromium layers with a high chromium content form a first outer surface layer with chromium contents in the range from 40 to 90% by weight and aluminum contents in the range from 5 to 35% by weight. Depending on which base material is present in the turbine blade, up to 55% by weight, preferably up to 30% by weight, of the main constituents of the base material, in particular the main component, such as, for example, nickel, cobalt or iron, are found in a first outer surface layer , depending on whether the base material of the component to be protected is a nickel-based alloy, cobalt-based alloy or iron-based alloy.
Die AlCr-Schichten mit niedrigen Chromgehalt bilden eine andere, zweite äußere Oberflächenschicht aus, die Chromgehalte im Bereich von 5 Gew.-% bis 15 Gew.-% und Aluminiumgehalte im Bereich von 5 Gew.-% bis 35 Gew.-% aufweist. Der Anteil von Komponenten der Basislegierung und insbesondere des Hauptbestandteils der Basislegierung liegt im Bereich von 50 Gew.-% bis 75 Gew.-%.The AlCr layers with a low chromium content form another, second outer surface layer which has chromium contents in the range from 5% by weight to 15% by weight and aluminum contents in the range from 5% by weight to 35% by weight. The proportion of components of the base alloy and in particular the main component of the base alloy is in the range from 50% by weight to 75% by weight.
Die Aluminium - Chrom - Schichten mit mittleren Chromgehalt bilden eine weitere, dritte äußere Oberflächenschicht aus, die Chromgehalte im Bereich von 15 Gew.-% bis 40 Gew.-%, Aluminiumgehalte von 5 Gew.-% bis 35 Gew.-%, vorzugsweise 15 Gew.-% bis 35 Gew.-%, und Anteile der Basislegierung bis 70 Gew.-% aufweist.The aluminum-chromium layers with a medium chromium content form a further, third outer surface layer, the chromium contents in the range from 15% by weight to 40% by weight, aluminum contents from 5% by weight to 35% by weight, preferably 15 wt .-% to 35 wt .-%, and shares of the base alloy up to 70 wt .-%.
In dem ternären Zustandsdiagramm der
Bei den Ausführungsbeispielen ist eine Beschichtung des gesamten Bauteils, also z.B. der Turbinenschaufel, mit einer erfindungsgemäßen Schicht aus Aluminium und Chrom beschrieben worden. Selbstverständlich ist jedoch die Kombination einer erfindungsgemäßen Schutzschicht mit Aluminium - Chrom - Schichten auch in Kombination mit anderen bekannten Schutzschichten möglich.In the exemplary embodiments, a coating of the entire component, e.g. the turbine blade, with a layer of aluminum and chrome according to the invention. Of course, however, the combination of a protective layer according to the invention with aluminum-chromium layers is also possible in combination with other known protective layers.
Bei der erfindungsgemäßen Aluminium - Chrom - Schutzschicht bedeutet der Begriff der Beschichtung nicht nur eine Auflage des abgeschiedenen Aluminiums und Chroms auf der ursprünglichen Bauteiloberfläche, sondern die Schutzschicht kann sich auch von der ursprünglichen Bauteiloberfläche aus nach innen in das Werkstoffinnere erstrecken.In the case of the aluminum-chrome protective layer according to the invention, the term coating does not only mean that the deposited aluminum and chromium are deposited on the original component surface, but the protective layer can also extend inwards from the original component surface into the interior of the material.
Zudem ist bei der Beschreibung der Ausführungsbeispiele lediglich auf die Ausbildung einer äußeren Oberflächenschicht eingegangen worden, welche jedoch lediglich eine Teilschicht des erzeugten Schutzschichtsystems sein kann, sodass in einer Richtung quer zur Bauteiloberfläche in Richtung des Werkstoffinneren weitere, in ihrer Zusammensetzung und Struktur unterschiedliche Teilschichten ausgebildet sein können.In addition, the description of the exemplary embodiments has only dealt with the formation of an outer surface layer, which, however, can only be a partial layer of the protective layer system produced, so that further partial layers with different compositions and structures are formed in a direction transverse to the component surface in the direction of the material interior can.
Die hier beschriebene Alitierung und/oder Chromierung eignet sich auch für die Innenbeschichtung von Hohlschaufeln.The alitation and / or chrome plating described here is also suitable for the internal coating of hollow blades.
Vorzugsweise kann das obige Verfahren auf Gasturbinen- oder ein Flugtriebwerksbauteile angewendet werden. Das Bauteil kann aus einer Legierung gebildet sein, die eine metallische Hauptkomponente aufweist, die den größten Anteil an der Legierung besitzt, mit einer Schutzschicht zum Schutz vor hohen Temperaturen und aggressiven Medien, wobei die Schutzschicht Chrom und Aluminium umfasst und insbesondere durch ein Verfahren nach einem der vorhergehenden Ansprüche hergestellt worden ist, und wobei die Schutzschicht unterschiedliche Bereiche aufweist, die sich durch ihre Zusammensetzung hinsichtlich des Chrom - und/oder Aluminiumanteils unterscheiden. Die Schutzschicht kann mindestens zwei unterschiedliche Bereiche mit je einer Oberflächenschicht aus der Gruppe aufweisen, die eine erste Oberflächenschicht mit einem Chromgehalt von größer oder gleich 40 Gew.-%, einem Aluminiumgehalt von 5 Gew.-% bis 35 Gew.-% und einem Anteil der Hauptkomponente des Bauteils kleiner oder gleich 55 Gew.-%, eine zweite Oberflächenschicht mit einem Chromgehalt von 5 Gew.-% bis 15 Gew.-%, einem Aluminiumgehalt von 10 Gew.-% bis 35 Gew.-% und einem Anteil der Hauptkomponente des Bauteils von 50 Gew.-% bis 75 Gew.-%, und eine dritte Oberflächenschicht mit einem Chromgehalt von 15 Gew.-% bis 40 Gew.-%, einem Aluminiumgehalt von 15 Gew.-% bis 35 Gew.-% und einem Anteil der Hauptkomponente des Bauteils kleiner oder gleich 70 Gew.-%.Preferably, the above method can be applied to gas turbine or aircraft engine components. The component can be formed from an alloy that is metallic Main component, which has the largest proportion of the alloy, with a protective layer for protection against high temperatures and aggressive media, the protective layer comprising chromium and aluminum and in particular has been produced by a method according to one of the preceding claims, and wherein the protective layer is different Has areas that differ in their composition with regard to the chromium and / or aluminum content. The protective layer can have at least two different areas, each with a surface layer from the group comprising a first surface layer with a chromium content of greater than or equal to 40% by weight, an aluminum content of 5% by weight to 35% by weight and a proportion the main component of the component is less than or equal to 55% by weight, a second surface layer with a chromium content of 5% by weight to 15% by weight, an aluminum content of 10% by weight to 35% by weight and a proportion of the Main component of the component from 50% by weight to 75% by weight, and a third surface layer with a chromium content of 15% by weight to 40% by weight, an aluminum content of 15% by weight to 35% by weight and a proportion of the main component of the component less than or equal to 70% by weight.
Bei der ersten Oberflächenschicht des Bauteils kann der Chromanteil im Bereich von 40 Gew.-% bis 90 Gew.-%, vorzugsweise größer oder gleich 50 Gew.-% und/oder der Aluminiumanteil im Bereich von 5 Gew.-% bis 25 Gew.-% und/oder der Anteil der Hauptkomponente des Bauteils kleiner oder gleich 30 Gew.-% sein. Vorzugsweise beträgt der Al-Anteil an der zweiten Oberflächenschicht 20-Gew% und 35-Gew%.In the first surface layer of the component, the chromium content can range from 40% by weight to 90% by weight, preferably greater than or equal to 50% by weight, and / or the aluminum content can range from 5% by weight to 25% by weight. -% and / or the proportion of the main component of the component to be less than or equal to 30% by weight. The Al content in the second surface layer is preferably 20% by weight and 35% by weight.
Bei der dritten Oberflächenschicht des Bauteils kann der Chromanteil im Bereich von 20 Gew.-% bis 40 Gew. und/oder der Aluminiumanteil im Bereich von 20 Gew.-% bis 35 Gew.-% sein.In the third surface layer of the component, the chromium content can be in the range from 20% by weight to 40% by weight and / or the aluminum content can be in the range from 20% by weight to 35% by weight.
Die unterschiedlichen Bereiche der Schutzschicht werden nach der Temperaturbelastung und/oder der einwirkenden Atmosphäre beim Betrieb des Bauteils ausgewählt.The different areas of the protective layer are selected according to the temperature load and / or the acting atmosphere during the operation of the component.
Das Bauteil kann eine Lauf - oder Leitschaufel einer Strömungsmaschine, insbesondere einer Gasturbine oder eines Flugtriebwerks sein, welche zumindest teilweise mit der Schutzschicht beschichtet ist, wobei insbesondere zusätzliche andere Schichtsysteme vorgesehen sein können.The component can be a rotor blade or guide blade of a turbomachine, in particular a gas turbine or an aircraft engine, which is at least partially coated with the protective layer, it being possible in particular for additional other layer systems to be provided.
Die erste Oberflächenschicht kann in Bereichen mit vorwiegender Belastung mit Sulfidation und/oder Bereichen mit Betriebstemperaturen im Bereich von 550°C bis 900°C angeordnet werden.The first surface layer can be arranged in areas with predominantly sulphidation and / or areas with operating temperatures in the range from 550 ° C to 900 ° C.
Die zweite Oberflächenschicht des Bauteils kann in Bereichen mit vorwiegender Belastung mit Oxidation und/oder Bereichen mit Betriebstemperaturen größer oder gleich 900°C angeordnet werden.The second surface layer of the component can be arranged in areas with predominant exposure to oxidation and / or areas with operating temperatures greater than or equal to 900 ° C.
Die dritte Oberflächenschicht kann in Bereichen mit kombinierter Belastung mit Oxidation und Sulfidation angeordnet werden.The third surface layer can be arranged in areas with combined exposure to oxidation and sulfidation.
Die erste Oberflächenschicht im Fuß - und/oder Deckbandbereich der Schaufel und/oder die zweite Oberflächenschicht im Blattbereich der Schaufel und/oder die dritte Oberflächenschicht im Übergangsbereich Fuß/Blatt und/oder Blatt/Deckband angeordnet sein.The first surface layer in the root and / or shroud area of the blade and / or the second surface layer in the blade area of the blade and / or the third surface layer in the transition area foot / blade and / or blade / shroud can be arranged.
Die Schichtdicke der Schutzschicht beträgt 10 µm bis 250 µm, insbesondere 40 µm bis 150 µm.The layer thickness of the protective layer is 10 µm to 250 µm, in particular 40 µm to 150 µm.
Claims (14)
- Method for producing a protective layer for protecting a component against high temperatures and aggressive media, a surface layer comprising aluminum and chromium being formed on the surface of the component to be provided with the protective layer, and a chromizing process being carried out in a first substep and an alitizing process being carried out in a second substep, characterized in that the chromizing process and/or the alitizing process is carried out simultaneously in different local regions of the component surface to be protected, but in a different manner such that the protective layer is a layer containing aluminum and chromium, is formed differently in different regions of the protective layer and has different chromium contents.
- Method according to claim 1, characterized in that, in the first substep, chromium is deposited by means of thermochemical methods or thermophysical methods or electrochemical methods.
- Method according to either claim 1 or claim 2, characterized in that, in the first substep, a heat treatment is carried out for diffusing chromium into the component surface in order to form a chromium-rich layer after application onto the component surface to be protected.
- Method according to any of the preceding claims, characterized in that, in the first substep, different chromium contents are deposited in the different regions, the chromium content in the formed layer varying in the range of from 15 wt.% to 100wt.%.
- Method according to any of the preceding claims, characterized in that, in the first substep, chromium-enriched layers of different thicknesses are deposited in the different regions, the layer thicknesses varying from 5 µm to 150 µm.
- Method according to any of the preceding claims, characterized in that, in the first substep, the chromizing process is carried out at a chemical chromium activity greater than or equal to 0.4 in order to form a first surface layer.
- Method according to claim 6, characterized in that the chromizing process is carried out using a Cr-rich slip which contains liquid phases and is applied by means of injection molding.
- Method according to either claim 6 or claim 7, characterized in that the chromizing process is carried out such that a chromium-rich layer is formed which comprises an outer α-chromium partial layer and an inner mixed-crystal layer consisting substantially of chromium, and a main component which has the largest proportion of the alloy of the coated component, the chromium content of the chromium-rich layer in particular being greater than or equal to 40 wt.%.
- Method according to any of the preceding claims, characterized in that, in the first substep, the chromizing process is carried out at a temperature of from 1000°C to 1200°C, in particular 1050°C to 1130°C, over a period of from 1 to 20 hours, in particular 10 to 15 hours.
- Method according to any of the preceding claims, characterized in that, in the second substep, the alitizing process is carried out at a temperature of from 1000°C to 1150°C, in particular 1050°C to 1150°C, preferably 1080°C to 1100°C, over a period of from 2 to 20 hours, in particular 9 to 15 hours.
- Method according to any of the preceding claims, characterized in that the chemical aluminum activity during the alitizing process is greater than or equal to 0.15, in particular in the range of from 0.15 to 0.35.
- Method according to any of the preceding claims, characterized in that, after a first alitizing step, a second alitizing process takes place at lower chemical aluminum activity, said second alitizing process taking place at a chemical aluminum activity of 0.05 to 0.3 at a temperature greater than or equal to 1050°C for a period of from 3 to 20 hours.
- Method according to any of the preceding claims, characterized in that, after the chromizing and alitizing processes, a diffusion annealing process is carried out at a temperature greater than or equal to 1050°C for a period of from 2 to 8 hours.
- Method according to any of the preceding claims, characterized in that, before, during or after the chromizing and/or alitizing process, a surface treatment is carried out by means of PVD, CVD, coating, electrodeposition and/or direct application of a substance, one or more elements from the group comprising platinum, palladium, hafnium, zirconium, yttrium and silicon being applied.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12179980.3A EP2695964B1 (en) | 2012-08-10 | 2012-08-10 | Protective coating tailored to a component |
US13/962,360 US20140044938A1 (en) | 2012-08-10 | 2013-08-08 | Process for producing a COMPONENT-MATCHED PROTECTIVE LAYER and component having such a protective layer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12179980.3A EP2695964B1 (en) | 2012-08-10 | 2012-08-10 | Protective coating tailored to a component |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2695964A1 EP2695964A1 (en) | 2014-02-12 |
EP2695964B1 true EP2695964B1 (en) | 2020-05-06 |
Family
ID=46967919
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12179980.3A Active EP2695964B1 (en) | 2012-08-10 | 2012-08-10 | Protective coating tailored to a component |
Country Status (2)
Country | Link |
---|---|
US (1) | US20140044938A1 (en) |
EP (1) | EP2695964B1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9909019B2 (en) | 2015-06-24 | 2018-03-06 | General Electric Company | Diffusion coatings for metal-based substrate and methods of preparation thereof |
US10053779B2 (en) | 2016-06-22 | 2018-08-21 | General Electric Company | Coating process for applying a bifurcated coating |
US10077494B2 (en) | 2016-09-13 | 2018-09-18 | General Electric Company | Process for forming diffusion coating on substrate |
DE102017213553A1 (en) | 2017-08-04 | 2019-02-07 | MTU Aero Engines AG | VESSEL FOR FLOW MACHINE WITH VARIOUS DIFFUSION PROTECTION LAYERS AND METHOD OF MANUFACTURING THEREOF |
CN107607577B (en) * | 2017-09-28 | 2020-04-10 | 中国煤炭地质总局水文地质局 | Thermal property testing device for stratum heat exchange capacity |
DE102018213395A1 (en) * | 2018-08-09 | 2020-02-13 | MTU Aero Engines AG | METHOD FOR PROVIDING A METALLIC SURFACE WITH A CHROME DIFFUSION PROTECTIVE LAYER |
FR3102775B1 (en) * | 2019-11-05 | 2022-04-22 | Safran | SUPERALLOY AIRCRAFT PART INCLUDING A COOLING CHANNEL |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3290126A (en) * | 1965-04-29 | 1966-12-06 | Du Pont | Protectively coated nickel or cobalt articles and process of making |
US3801357A (en) * | 1969-06-30 | 1974-04-02 | Alloy Surfaces Co Inc | Diffusion coating |
US3948689A (en) * | 1969-06-30 | 1976-04-06 | Alloy Surfaces Company, Inc. | Chromic-phosphoric acid coated aluminized steel |
GB1545584A (en) * | 1975-03-07 | 1979-05-10 | Onera (Off Nat Aerospatiale) | Processes and systems for the formation of surface diffusion alloys on perforate metal workpieces |
US4526814A (en) * | 1982-11-19 | 1985-07-02 | Turbine Components Corporation | Methods of forming a protective diffusion layer on nickel, cobalt, and iron base alloys |
US5225246A (en) * | 1990-05-14 | 1993-07-06 | United Technologies Corporation | Method for depositing a variable thickness aluminide coating on aircraft turbine blades |
US5658614A (en) * | 1994-10-28 | 1997-08-19 | Howmet Research Corporation | Platinum aluminide CVD coating method |
US20100151125A1 (en) * | 2003-08-04 | 2010-06-17 | General Electric Company | Slurry chromizing process |
GB0409486D0 (en) * | 2004-04-28 | 2004-06-02 | Diffusion Alloys Ltd | Coatings for turbine blades |
GB2421032A (en) * | 2004-12-11 | 2006-06-14 | Siemens Ind Turbomachinery Ltd | A method of protecting a component against hot corrosion |
CN101460708B (en) * | 2006-06-08 | 2013-02-27 | 西门子公司 | Coated turbine component and method of coating a turbine component |
GB2439313B (en) * | 2006-06-24 | 2011-11-23 | Siemens Ag | Method of protecting a component against hot corrosion and a component protected by said method |
-
2012
- 2012-08-10 EP EP12179980.3A patent/EP2695964B1/en active Active
-
2013
- 2013-08-08 US US13/962,360 patent/US20140044938A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
EP2695964A1 (en) | 2014-02-12 |
US20140044938A1 (en) | 2014-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2695964B1 (en) | Protective coating tailored to a component | |
DE102011055245B4 (en) | Component and method for producing and coating a component | |
DE60033345T2 (en) | Component of a gas turbine with position-dependent protective coatings | |
DE2657288C2 (en) | Coated superalloy article and its uses | |
DE69707365T2 (en) | Insulating, heat-insulating coating system | |
DE102011055246A1 (en) | Components with recessed cooling channels and method for their preparation | |
DE3104581C2 (en) | Article made of a superalloy with a covering layer and method for its manufacture | |
DE3010608A1 (en) | COATING COMPOSITION FOR NICKEL, COBALT AND IRON CONTAINING SUPER ALLOY AND SUPER ALLOY COMPONENT | |
EP2695965A2 (en) | Duplex phase CrAl coating for improved corrosion/oxidation protection | |
CH708915A2 (en) | Components with cooling multilayer structures and methods of making the same. | |
DE3030961A1 (en) | COMPONENTS OF SUPER ALLOYS WITH AN OXIDATION AND / OR SULFIDATION RESISTANT COATING AND COMPOSITION OF SUCH A COATING. | |
EP1902160B1 (en) | Ceramic heat insulating layer | |
EP2796588B1 (en) | Method for producing a high temperature protective coating | |
DE60022300T2 (en) | Articles with corrosion-resistant coatings | |
DE112008003460T5 (en) | Coated Super Alloy Objects | |
EP3015568B1 (en) | Dross and method for producing an oxidation and corrosion resistant diffusion layer | |
EP2462257A1 (en) | Blade tip coating that can be rubbed off | |
DE102009031313A1 (en) | Coating and method for coating a component | |
EP3438414B1 (en) | Blade for a flow machine with different diffusion protection layers and method for production | |
EP1959026B1 (en) | Method for formation of an aluminium diffusion layer form oxidation protection | |
EP2851455B1 (en) | Method of electroplating wear-resistant coating | |
EP1097249B1 (en) | Method for producing a plating for a metal component | |
DE102013111874A1 (en) | Manufacturing method of component for gas turbine engine involves forming grooves, each with cross-sectional are in predetermined ranged with respect to area derived from product of width of opening and depth of re-entrant shaped groove | |
EP2980263A1 (en) | Component made from a molybdenum alloy and manufacturing method for the same | |
WO2010091667A1 (en) | Coating and method for coating a workpiece |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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 |
|
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: 20140711 |
|
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 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: MTU AERO ENGINES GMBH |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: MTU AERO ENGINES AG |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20170724 |
|
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: 20191016 |
|
INTC | Intention to grant announced (deleted) | ||
INTG | Intention to grant announced |
Effective date: 20191209 |
|
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: 1266840 Country of ref document: AT Kind code of ref document: T Effective date: 20200515 |
|
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: 502012016050 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200506 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200506 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: 20200506 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: 20200906 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: 20200907 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: 20200506 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: 20200807 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: 20200806 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20200825 Year of fee payment: 9 Ref country code: FR Payment date: 20200820 Year of fee payment: 9 Ref country code: DE Payment date: 20200824 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200506 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: 20200806 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: 20200506 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: 20200506 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200506 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: 20200506 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200506 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: 20200506 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: 20200506 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: 20200506 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: 20200506 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: 20200506 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: 20200506 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502012016050 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200506 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: 20200506 |
|
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: 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: 20200506 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
26N | No opposition filed |
Effective date: 20210209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20200506 |
|
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: 20200831 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 1266840 Country of ref document: AT Kind code of ref document: T Effective date: 20200810 |
|
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: 20200810 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502012016050 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20210810 |
|
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: 20200506 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: 20200506 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: 20200506 |
|
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: 20200506 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210810 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210831 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220301 |