EP3099848A1 - Process for localised repair of a damaged thermal barrier - Google Patents

Process for localised repair of a damaged thermal barrier

Info

Publication number
EP3099848A1
EP3099848A1 EP14828044.9A EP14828044A EP3099848A1 EP 3099848 A1 EP3099848 A1 EP 3099848A1 EP 14828044 A EP14828044 A EP 14828044A EP 3099848 A1 EP3099848 A1 EP 3099848A1
Authority
EP
European Patent Office
Prior art keywords
damaged
thermal barrier
particles
ceramic coating
equal
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
EP14828044.9A
Other languages
German (de)
French (fr)
Other versions
EP3099848B1 (en
Inventor
André Hubert Louis MALIE
Sarah Hamadi
Florence Ansart
Jean-Pierre Bonino
Hélène CERDA
Guillaume PUJOL
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.)
Safran Aircraft Engines SAS
Centre National de la Recherche Scientifique CNRS
Institut National Polytechnique de Toulouse INPT
Universite Toulouse III Paul Sabatier
Original Assignee
Safran Aircraft Engines SAS
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 Safran Aircraft Engines SAS filed Critical Safran Aircraft Engines SAS
Priority to EP20203886.5A priority Critical patent/EP3789518B1/en
Publication of EP3099848A1 publication Critical patent/EP3099848A1/en
Application granted granted Critical
Publication of EP3099848B1 publication Critical patent/EP3099848B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/005—Repairing methods or devices
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/18—Electrophoretic coating characterised by the process using modulated, pulsed, or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2220/00—Application
    • F05D2220/30—Application in turbines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/30—Manufacture with deposition of material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/40—Heat treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/90—Coating; Surface treatment
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/20—Oxide or non-oxide ceramics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/50—Intrinsic material properties or characteristics
    • F05D2300/502—Thermal properties
    • F05D2300/5023—Thermal capacity

Definitions

  • the invention relates to localized repair methods of damaged thermal barriers.
  • the blades of the high-pressure turbines of the aeronautical engines are exposed to a very aggressive environment.
  • These parts are, in general, coated with a protective coating in oxidation as well as a thermal barrier coating.
  • the thermal barrier coating thermally insulates the underlying part to maintain it at temperatures where its mechanical performance and life expectancy are acceptable.
  • CMAS calcium and magnesium aluminosilicates
  • the invention proposes, according to a first aspect, a localized repair method of a damaged thermal barrier comprising the following step:
  • a) electrophoresis treatment of a part coated with a damaged thermal barrier the part being formed of an electrically conductive material, the damaged thermal barrier comprising a ceramic material and having at least one damaged area to be repaired, the the part being present in an electrolyte comprising a suspension of particles in a liquid medium, a ceramic coating being deposited by electrophoresis in the damaged area in order to obtain a repaired thermal barrier intended to be used at temperatures greater than or equal to 1000 ° C.
  • the part is formed of an electrically conductive material and the damaged thermal barrier allows the conduction of electricity in the damaged area to be repaired and therefore the deposition of the ceramic coating by electrophoresis in this area during step a).
  • the ceramic coating obtained during step a) is formed by the deposition of the particles on the part.
  • the ceramic coating may be mainly deposited in the damaged area.
  • a ceramic coating mass greater than or equal to 50% of the total mass of the ceramic coating deposited in step a) can be deposited in the damaged area.
  • This mass of ceramic coating deposited in the damaged zone may for example be greater than or equal to 75% or even 90% of the total mass of the ceramic coating deposited in step a).
  • the ceramic coating can be deposited only in the damaged area.
  • the invention advantageously makes it possible to quickly, inexpensively and locally repair the damaged thermal barrier and thus to avoid the scrapping of partially degraded parts or the complete removal of the damaged thermal barrier.
  • the invention therefore makes it possible to extend the life of the parts and to limit the cost of restarting parts whose thermal barrier has been damaged.
  • the electrophoresis deposition process has the advantage of being usable for parts having complex geometries.
  • the repaired thermal barrier may be intended for use in an environment where the temperature on the surface of the thermal barrier is greater than or equal to 1000 ° C.
  • the part may advantageously be made of metallic material and, for example, comprise nickel.
  • the damaged thermal barrier may have a lack of material in the damaged area.
  • the particles may have an average size less than or equal to
  • average size is meant the dimension given by the statistical size distribution at half of the population, called D50.
  • the particles, in the non-agglomerated state can have an average size of between 20 nm and 1 m.
  • Such particle sizes advantageously make it possible to obtain a stable suspension.
  • the particles may or may not have been sol gelated.
  • the process may comprise, before step a), a step of forming the particles by implementing a sol-gel process. These particles can then be dispersed in the liquid medium to form the electrolyte.
  • the particles of the electrolyte may, for example, be yttria-zirconia (YSZ) particles, which may be Yttria-Stabilized Zirconia. may or may not have been obtained by sol-gel. It is still possible to use zirconium oxide particles. More generally, it is possible to use for the electrophoretic deposition any particles likely to present an electric charge within the electrolyte (thus allowing them to move during the application of the electric field).
  • YSZ yttria-zirconia
  • zirconium oxide particles More generally, it is possible to use for the electrophoretic deposition any particles likely to present an electric charge within the electrolyte (thus allowing them to move during the application of the electric field).
  • particles of the following chemical formula ZrO 2 - eOi, 5 (where Re denotes a rare earth element, for example: Gd, Sm or Er), Y 2 O 3 , Al 2 O 3 , TiO 2 or CeO 2 .
  • the particles may be formed of the same ceramic material as that present in the damaged thermal barrier.
  • the particles may be formed of a material different from the ceramic material present in the damaged thermal barrier.
  • the material constituting the particles and the ceramic material of the damaged thermal barrier are advantageously compatible thermomechanically and chemically.
  • the difference between the coefficients of thermal expansion of the ceramic material present in the damaged thermal barrier and of the material constituting the particles may in absolute value advantageously be less than or equal to 2.10 -6 K 1 .
  • the use of a different material may advantageously make it possible to provide an additional property, for example an anti-CMAS property or a heat-sensitive material, and thus to functionalize the thermal barrier while repairing it.
  • the liquid medium may, for example, be chosen from: alcohols, for example ethanol or isopropanol, ketones, for example acetylacetone, water and their mixtures.
  • the particles may be present in the liquid medium, before the start of step a), in a concentration greater than or equal to 0.1 g / l, preferably greater than or equal to 1 g / l. .
  • the thickness of the deposited ceramic coating may be greater than or equal to 50 nm, for example greater than or equal to 30 ⁇ . In an exemplary embodiment, the thickness of the deposited ceramic coating may be less than or equal to 200 ⁇ m.
  • the part may be coated with a bonding layer for attachment of the thermal barrier to the workpiece and the ceramic coating may be deposited on the bonding layer.
  • the attachment layer advantageously makes it possible to improve the attachment of the thermal barrier to the part.
  • the attachment layer may furthermore advantageously make it possible to protect the part against oxidation and corrosion.
  • the bonding layer may, for example, be metallic.
  • the thermal barrier can be directly present on the part.
  • the thermal barrier can be directly present on the part.
  • the duration of step a) may be greater than or equal to 1 minute, preferably 5 minutes.
  • a voltage greater than or equal to 1 V may be imposed during all or part of step a) between the workpiece and a counter-electrode.
  • the voltage imposed during all or part of step a) may preferably be greater than or equal to 50 V.
  • the damaged zone may, before step a), have been subjected to a stripping step.
  • Performing a stripping advantageously makes it possible to eliminate the thermal barrier residues and oxide layers that may be present and thus to improve the conductive nature of the electricity of the damaged area to be repaired in order to promote the formation of the deposit of the ceramic coating by electrophoresis.
  • the etching can be carried out mechanically, for example by sandblasting, sanding, grinding, high-pressure water jet or by laser etching.
  • the etching may be a chemical etching, for example an electrolytic pickling or etching in an acidic or basic medium.
  • the damaged thermal barrier may, at the beginning of step a), present a lack of material in the damaged area.
  • the method may comprise, after step a), a step b) consolidation by heat treatment of the deposited ceramic coating.
  • Step b) may, for example, include the submission of the part obtained after implementation of step a) at a temperature greater than or equal to 1000 ° C, for example greater than or equal to 1100 ° C.
  • the part may constitute a turbomachine blade.
  • FIG. 1 is a photograph of a turbomachine blade damaged in service
  • FIG. 2 comprises a photograph of a turbine engine blade damaged in service and illustrates, schematically and partially, the structure of a damaged thermal barrier
  • FIGS. 3A and 3B illustrate, in a schematic and partial manner, the implementation of a method according to the invention.
  • FIGS. 4A and 4B are photographs respectively representing a part before and after treatment by a method according to the invention.
  • FIG. 2 shows a part 1, for example consisting of a nickel-based superalloy coated with a bonding layer 2 on which a damaged thermal barrier 3 is present.
  • An oxide layer 2a is present between the hanger layer 2 and the thermal barrier 3 damaged.
  • Layer 2a may consist of 01-Al2O3 alumina.
  • the damaged thermal barrier 3 comprises a ceramic material and has a damaged area 4 to be repaired.
  • the damaged area 4 may have at least one undamaged adjacent area. In the illustrated example, the damaged area 4 is present between two undamaged adjacent areas 5a and 5b.
  • FIG. 3A shows the implementation of a step a) according to the invention.
  • the part 1 carrying the damaged thermal barrier 3 is present in an electrolyte 10 comprising a suspension of particles 11 in a liquid medium.
  • the particles 11 may, for example, be yttria-zirconia particles (zirconia stabilized with yttrium oxide).
  • the oxide powder (yttriated zirconia) thus obtained is then suspended in a liquid medium consisting for example of isopropanol in order to form the electrolyte 10.
  • the part 1 coated with the damaged thermal barrier 3 constitutes an electrode of the electrophoresis system with respect to which a counter electrode 20 is present.
  • the counter-electrode 20 is, for example, made of platinum. Due to the conductive nature of the part 1 and the damaged area 4, an electrophoresis deposit is made in the damaged area 4.
  • the damaged area 4 is constituted, in the illustrated example, by a region devoid of material.
  • the damaged zone includes a first region devoid of of material and a second region in which a ceramic layer is present, the thickness of the ceramic layer in the second region being low enough for the second region to be electrically conductive.
  • the damaged zone is constituted by a region in which a ceramic layer is present, the thickness of the ceramic layer being sufficiently small for this region to be electrically conductive.
  • the deposition is preferably carried out in the most conductive zones (thickness of the ceramic layer sufficiently small or total absence of ceramic layer) because the electric field will be relatively high in these areas.
  • the damaged thermal barrier 3 has a single damaged area 4 to be repaired but it is not beyond the scope of the present invention if the damaged thermal barrier has a plurality of damaged areas to repair.
  • each of the damaged areas to be repaired is electrically conductive.
  • a generator G imposes a potential difference between the part 1 and the counter-electrode 20.
  • the generator G is DC or pulsed.
  • the part 1 is polarized at a charge opposite to that of the particles 11. Due to the application of an electric field between the part 1 and the counter-electrode 20, the particles 11 move and are deposited on the part 1 to forming a ceramic coating 6.
  • the deposition of the ceramic coating 6 in the damaged zone 4 provides a repaired thermal barrier 7.
  • the deposition of the ceramic coating 6 in the damaged zone 4 induces a gradual decrease in the electrical conductivity of this zone to course of time. In fact, as the ceramic coating 6 is deposited, this zone becomes more and more insulating, which slows down or even stops the formation of the ceramic coating 6 on the part 1.
  • the ceramic coating 6 is deposited in the damaged zone 4 and covers the entire surface of the damaged zone 4.
  • the damaged thermal barrier 3 is not covered with a mask having an opening superimposed with the damaged zone 4 to to fix.
  • the ceramic coating 6 may have a thickness e greater than or equal to 50 nm, for example greater than or equal to 30 ⁇ m.
  • the thickness e of the ceramic coating 6 corresponds to its largest dimension measured perpendicularly to the surface S of the coated part 1.
  • step a After step a), a drying and then a consolidation heat treatment of the ceramic coating 6 can be performed.
  • the thermal barrier was first damaged by water jet.
  • Figure 4A shows the result obtained after damage.
  • Electrophoretic deposition was performed from a suspension of YSZ powder in isopropanol (10 g / L) at a voltage of 100V for 6 minutes.
  • a photograph of the part after treatment by the method according to the invention is given in FIG. 4B.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

The invention relates to a process for the localised repair of a damaged thermal barrier comprising the following step: a) treatment via electrophoresis of a part coated with a damaged thermal barrier, the part being formed from an electrically conductive material, the damaged thermal barrier comprising a ceramic material and having at least one damaged zone to be repaired, the part being present in an electrolyte comprising a suspension of particles in a liquid medium, a ceramic coating being deposited by electrophoresis in the damaged zone in order to obtain a repaired thermal barrier intended to be used at temperatures greater than or equal to 1000°C, the particles being formed from a material different to the ceramic material present in the damaged thermal barrier.

Description

PROCEDE DE REPARATION LOCALISEE D'UNE BARRIERE THERMIQUE  METHOD FOR LOCALIZED REPAIR OF A THERMAL BARRIER
ENDOMMAGEE  DAMAGED
Arrière-plan de l'invention Background of the invention
L'invention concerne les procédés de réparation localisée des barrières thermiques endommagées.  The invention relates to localized repair methods of damaged thermal barriers.
Les aubages des turbines haute pression des moteurs aéronautiques sont exposés à un environnement très agressif. Ces pièces sont, en général, revêtues d'un revêtement protecteur en oxydation ainsi que d'un revêtement de barrière thermique. Le revêtement de barrière thermique permet d'isoler thermiquement la pièce sous-jacente afin de la maintenir à des températures où ses performances mécaniques et sa durée de vie sont acceptables.  The blades of the high-pressure turbines of the aeronautical engines are exposed to a very aggressive environment. These parts are, in general, coated with a protective coating in oxidation as well as a thermal barrier coating. The thermal barrier coating thermally insulates the underlying part to maintain it at temperatures where its mechanical performance and life expectancy are acceptable.
Certaines zones de ce système peuvent être endommagées en service à haute température par l'érosion, l'impact de particules, l'oxydation, la corrosion et par les aluminosilicates de calcium et de magnésium (« CMAS »). Les photographies fournies aux figures 1 et 2 montrent l'aspect d'aubes endommagées en service. Ces dégradations peuvent engendrer des disparitions locales de la couche barrière thermique voire de la sous-couche conduisant à une oxydation de la pièce sous-jacente.  Some areas of this system may be damaged in high temperature service by erosion, particle impact, oxidation, corrosion, and calcium and magnesium aluminosilicates ("CMAS"). The photographs provided in Figures 1 and 2 show the appearance of damaged blades in service. These degradations can cause local disappearances of the thermal barrier layer or even the sub-layer leading to oxidation of the underlying part.
Actuellement, il est connu afin de reconstituer une barrière thermique de décaper l'intégralité du revêtement de barrière thermique (même les zones non endommagées) des pièces puis de réaliser un nouveau système barrière thermique. Des pièces dont la barrière thermique a été endommagée peuvent même dans certains cas être mises au rebut.  Currently, it is known to reconstruct a thermal barrier to etch the entire thermal barrier coating (even undamaged areas) parts and then achieve a new thermal barrier system. Parts whose thermal barrier has been damaged can in some cases even be scrapped.
Il existe un besoin pour améliorer la durée d'utilisation des pièces revêtues par des barrières thermiques. There is a need to improve the service life of parts coated with thermal barriers.
Il existe un besoin pour simplifier et diminuer le coût des procédés de réparation des barrières thermiques endommagées.  There is a need to simplify and reduce the cost of repairing damaged thermal barriers.
Il existe aussi un besoin pour disposer de nouveaux procédés de réparation des barrières thermiques endommagées. Obiet et résumé de l'invention There is also a need for new methods for repairing damaged thermal barriers. Obiet and summary of the invention
A cet effet, l'invention propose, selon un premier aspect, un procédé de réparation localisée d'une barrière thermique endommagée comportant l'étape suivante :  For this purpose, the invention proposes, according to a first aspect, a localized repair method of a damaged thermal barrier comprising the following step:
a) traitement par électrophorèse d'une pièce revêtue d'une barrière thermique endommagée, la pièce étant formée d'un matériau conducteur de l'électricité, la barrière thermique endommagée comportant un matériau céramique et présentant au moins une zone endommagée à réparer, la pièce étant présente dans un électrolyte comportant une suspension de particules dans un milieu liquide, un revêtement céramique étant déposé par électrophorèse dans la zone endommagée afin d'obtenir une barrière thermique réparée destinée à être utilisée à des températures supérieures ou égales à 1000°C.  a) electrophoresis treatment of a part coated with a damaged thermal barrier, the part being formed of an electrically conductive material, the damaged thermal barrier comprising a ceramic material and having at least one damaged area to be repaired, the the part being present in an electrolyte comprising a suspension of particles in a liquid medium, a ceramic coating being deposited by electrophoresis in the damaged area in order to obtain a repaired thermal barrier intended to be used at temperatures greater than or equal to 1000 ° C.
Dans l'invention, la pièce est formée d'un matériau conducteur de l'électricité et la barrière thermique endommagée permet la conduction de l'électricité dans la zone endommagée à réparer et donc le dépôt du revêtement céramique par électrophorèse dans cette zone lors de l'étape a). Le revêtement céramique obtenu lors de l'étape a) est formé par le dépôt des particules sur la pièce. Le revêtement céramique peut être majoritairement déposé dans la zone endommagée. En d'autres termes, une masse de revêtement céramique supérieure ou égale à 50% de la masse totale du revêtement céramique déposé lors de l'étape a) peut être déposée dans la zone endommagée. Cette masse de revêtement céramique déposée dans la zone endommagée peut par exemple être supérieure ou égale à 75%, voire à 90%, de la masse totale du revêtement céramique déposé lors de l'étape a). Dans un exemple de réalisation, le revêtement céramique peut être déposé uniquement dans la zone endommagée.  In the invention, the part is formed of an electrically conductive material and the damaged thermal barrier allows the conduction of electricity in the damaged area to be repaired and therefore the deposition of the ceramic coating by electrophoresis in this area during step a). The ceramic coating obtained during step a) is formed by the deposition of the particles on the part. The ceramic coating may be mainly deposited in the damaged area. In other words, a ceramic coating mass greater than or equal to 50% of the total mass of the ceramic coating deposited in step a) can be deposited in the damaged area. This mass of ceramic coating deposited in the damaged zone may for example be greater than or equal to 75% or even 90% of the total mass of the ceramic coating deposited in step a). In an exemplary embodiment, the ceramic coating can be deposited only in the damaged area.
L'invention permet avantageusement de réparer de manière rapide, peu coûteuse et localisée la barrière thermique endommagée et ainsi d'éviter la mise au rebut de pièces partiellement dégradées ou le décapage complet de la barrière thermique endommagée. L'invention permet, par conséquent, de prolonger la durée de vie des pièces et de limiter le coût de remise en fonctionnement des pièces dont la barrière thermique a été endommagée. The invention advantageously makes it possible to quickly, inexpensively and locally repair the damaged thermal barrier and thus to avoid the scrapping of partially degraded parts or the complete removal of the damaged thermal barrier. The invention therefore makes it possible to extend the life of the parts and to limit the cost of restarting parts whose thermal barrier has been damaged.
La possibilité d'une réparation localisée résulte de la mise en œuvre d'un dépôt par électrophorèse à la différence du procédé de dépôt en phase vapeur avec évaporation sous faisceau d'électrons (« électron beam physical vapor déposition » ; EB-PVD) ou de projection plasma (« plasma spraying » ; PS) qui ne permettent pas ou difficilement la réalisation d'une réparation localisée.  The possibility of localized repair results from the implementation of electrophoretic deposition, unlike the electron-beam vapor deposition method (EB-PVD) or plasma spraying (PS) which do not allow or difficult to achieve localized repair.
En outre, le procédé de dépôt par électrophorèse présente l'avantage d'être utilisable pour des pièces présentant des géométries complexes.  In addition, the electrophoresis deposition process has the advantage of being usable for parts having complex geometries.
La barrière thermique réparée peut être destinée à être utilisée dans un environnement où la température à la surface de la barrière thermique est supérieure ou égale à 1000°C.  The repaired thermal barrier may be intended for use in an environment where the temperature on the surface of the thermal barrier is greater than or equal to 1000 ° C.
La pièce peut avantageusement être en matériau métallique et, par exemple, comporter du nickel.  The part may advantageously be made of metallic material and, for example, comprise nickel.
Avantageusement, avant mise en œuvre de l'étape a), la barrière thermique endommagée peut présenter un manque de matière dans la zone endommagée.  Advantageously, before implementation of step a), the damaged thermal barrier may have a lack of material in the damaged area.
Dans un exemple de réalisation, les particules, éventuellement agglomérées, peuvent présenter une taille moyenne inférieure ou égale à In an exemplary embodiment, the particles, possibly agglomerated, may have an average size less than or equal to
10 pm. 10 pm
Par « taille moyenne », on désigne la dimension donnée par la distribution granulométrique statistique à la moitié de la population, dite D50.  By "average size" is meant the dimension given by the statistical size distribution at half of the population, called D50.
Par exemple, les particules, à l'état non aggloméré, peuvent avoir une taille moyenne comprise entre 20 nm et 1 m.  For example, the particles, in the non-agglomerated state, can have an average size of between 20 nm and 1 m.
De telles tailles de particules permettent avantageusement d'obtenir une suspension stable.  Such particle sizes advantageously make it possible to obtain a stable suspension.
Les particules peuvent ou non avoir été obtenues par voie sol- gel. Ainsi, dans un exemple de réalisation, le procédé peut comporter, avant l'étape a), une étape de formation des particules par mise en œuvre d'un procédé sol-gel. Ces particules peuvent ensuite être dispersées dans le milieu liquide afin de former l'électrolyte.  The particles may or may not have been sol gelated. Thus, in one exemplary embodiment, the process may comprise, before step a), a step of forming the particles by implementing a sol-gel process. These particles can then be dispersed in the liquid medium to form the electrolyte.
Les particules de l'électrolyte peuvent, par exemple, être des particules de zircone yttriée (YSZ ; « Yttria-Stabilized Zirconia ») lesquelles peuvent ou non avoir été obtenues par voie sol-gel. On peut encore utiliser des particules d'oxyde de zirconium. Plus généralement, on peut utiliser pour le dépôt par électrophorèse toutes particules susceptibles de présenter une charge électrique au sein de l'électrolyte (leur permettant ainsi de se déplacer lors de l'application du champ électrique). On peut ainsi, par exemple, utiliser des particules de formule chimique suivante : ZrO2- eOi,5 (où Re désigne un élément Terre Rare, par exemple : Gd, Sm ou Er), Y2O3, AI2O3, TiO2 ou CeO2. The particles of the electrolyte may, for example, be yttria-zirconia (YSZ) particles, which may be Yttria-Stabilized Zirconia. may or may not have been obtained by sol-gel. It is still possible to use zirconium oxide particles. More generally, it is possible to use for the electrophoretic deposition any particles likely to present an electric charge within the electrolyte (thus allowing them to move during the application of the electric field). It is thus possible, for example, to use particles of the following chemical formula: ZrO 2 - eOi, 5 (where Re denotes a rare earth element, for example: Gd, Sm or Er), Y 2 O 3 , Al 2 O 3 , TiO 2 or CeO 2 .
Dans un exemple de réalisation, les particules peuvent être formées du même matériau céramique que celui présent dans la barrière thermique endommagée.  In an exemplary embodiment, the particles may be formed of the same ceramic material as that present in the damaged thermal barrier.
En variante, les particules peuvent être formées d'un matériau différent du matériau céramique présent dans la barrière thermique endommagée. Dans ce cas, le matériau constituant les particules et le matériau céramique de la barrière thermique endommagée sont avantageusement compatibles thermomécaniquement et chimiquement. Par exemple, la différence entre les coefficients d'expansion thermique du matériau céramique présent dans la barrière thermique endommagée et du matériau constituant les particules peut en valeur absolue avantageusement être inférieure ou égale à 2.10"6 K 1. Alternatively, the particles may be formed of a material different from the ceramic material present in the damaged thermal barrier. In this case, the material constituting the particles and the ceramic material of the damaged thermal barrier are advantageously compatible thermomechanically and chemically. For example, the difference between the coefficients of thermal expansion of the ceramic material present in the damaged thermal barrier and of the material constituting the particles may in absolute value advantageously be less than or equal to 2.10 -6 K 1 .
L'utilisation d'un matériau différent peut avantageusement permettre d'apporter une propriété supplémentaire, par exemple propriété anti-CMAS ou matériau thermosensible, et ainsi de fonctionnaliser la barrière thermique tout en la réparant.  The use of a different material may advantageously make it possible to provide an additional property, for example an anti-CMAS property or a heat-sensitive material, and thus to functionalize the thermal barrier while repairing it.
Le milieu liquide peut, par exemple, être choisi parmi : les alcools, par exemple l'éthanol ou l'isopropanol, les cétones par exemple l'acétylacétone, l'eau et leurs mélanges.  The liquid medium may, for example, be chosen from: alcohols, for example ethanol or isopropanol, ketones, for example acetylacetone, water and their mixtures.
Dans un exemple de réalisation, les particules peuvent être présentes dans le milieu liquide, avant le début de l'étape a), en une concentration supérieure ou égale à 0,1 g/L, de préférence supérieure ou égale à 1 g/L.  In an exemplary embodiment, the particles may be present in the liquid medium, before the start of step a), in a concentration greater than or equal to 0.1 g / l, preferably greater than or equal to 1 g / l. .
De telles valeurs de concentration permettent avantageusement de disposer d'une suspension stable.  Such concentration values advantageously make it possible to have a stable suspension.
Dans un exemple de réalisation, l'épaisseur du revêtement céramique déposé peut être supérieure ou égale à 50 nm, par exemple supérieure ou égale à 30 μιτι. Dans un exemple de réalisation, l'épaisseur du revêtement céramique déposé peut être inférieure ou égale à 200 pm. In an exemplary embodiment, the thickness of the deposited ceramic coating may be greater than or equal to 50 nm, for example greater than or equal to 30 μιτι. In an exemplary embodiment, the thickness of the deposited ceramic coating may be less than or equal to 200 μm.
Dans un exemple de réalisation, la pièce peut être revêtue d'une couche d'accrochage permettant l'accrochage de la barrière thermique à la pièce et le revêtement céramique peut être déposé sur la couche d'accrochage.  In an exemplary embodiment, the part may be coated with a bonding layer for attachment of the thermal barrier to the workpiece and the ceramic coating may be deposited on the bonding layer.
La couche d'accrochage permet avantageusement d'améliorer l'accrochage de la barrière thermique à la pièce. La couche d'accrochage peut, en outre, avantageusement permettre de protéger la pièce contre l'oxydation et la corrosion.  The attachment layer advantageously makes it possible to improve the attachment of the thermal barrier to the part. The attachment layer may furthermore advantageously make it possible to protect the part against oxidation and corrosion.
La couche d'accrochage peut, par exemple, être métallique. The bonding layer may, for example, be metallic.
Dans une variante, la barrière thermique peut directement être présente sur la pièce. Ainsi, il est possible qu'aucune couche d'accrochage ne soit présente entre la barrière thermique et la pièce. In a variant, the thermal barrier can be directly present on the part. Thus, it is possible that no bonding layer is present between the thermal barrier and the part.
Dans un exemple de réalisation, la durée de l'étape a) peut être supérieure ou égale à 1 minute, de préférence à 5 minutes.  In an exemplary embodiment, the duration of step a) may be greater than or equal to 1 minute, preferably 5 minutes.
De telles valeurs permettent avantageusement d'améliorer le caractère couvrant et l'homogénéité du revêtement céramique formé.  Such values advantageously make it possible to improve the hiding and homogeneity of the ceramic coating formed.
Dans un exemple de réalisation, une tension supérieure ou égale à 1 V peut être imposée durant tout ou partie de l'étape a) entre la pièce et une contre-électrode. La tension imposée durant tout ou partie de l'étape a) peut, de préférence, être supérieure ou égale à 50 V.  In an exemplary embodiment, a voltage greater than or equal to 1 V may be imposed during all or part of step a) between the workpiece and a counter-electrode. The voltage imposed during all or part of step a) may preferably be greater than or equal to 50 V.
De telles valeurs permettent avantageusement d'améliorer le caractère couvrant et l'homogénéité du revêtement céramique formé.  Such values advantageously make it possible to improve the hiding and homogeneity of the ceramic coating formed.
Dans un exemple de réalisation, la zone endommagée peut, avant l'étape a), avoir été soumise à une étape de décapage.  In an exemplary embodiment, the damaged zone may, before step a), have been subjected to a stripping step.
La réalisation d'un décapage permet avantageusement d'éliminer les résidus de barrière thermique et les couches d'oxydes éventuellement présents et ainsi d'améliorer le caractère conducteur de l'électricité de la zone endommagée à réparer afin de favoriser la formation du dépôt du revêtement céramique par électrophorèse.  Performing a stripping advantageously makes it possible to eliminate the thermal barrier residues and oxide layers that may be present and thus to improve the conductive nature of the electricity of the damaged area to be repaired in order to promote the formation of the deposit of the ceramic coating by electrophoresis.
Le décapage peut être réalisé mécaniquement, par exemple par sablage, ponçage, meulage, jet d'eau haute pression ou par décapage laser. En variante, le décapage peut être un décapage chimique, par exemple un décapage électrolytique ou un décapage en milieu acide ou basique. The etching can be carried out mechanically, for example by sandblasting, sanding, grinding, high-pressure water jet or by laser etching. Alternatively, the etching may be a chemical etching, for example an electrolytic pickling or etching in an acidic or basic medium.
Après décapage, la barrière thermique endommagée peut, au début de l'étape a), présenter un manque de matière dans la zone endommagée.  After stripping, the damaged thermal barrier may, at the beginning of step a), present a lack of material in the damaged area.
Dans un exemple de réalisation, le procédé peut comporter, après l'étape a), une étape b) de consolidation par traitement thermique du revêtement céramique déposé.  In an exemplary embodiment, the method may comprise, after step a), a step b) consolidation by heat treatment of the deposited ceramic coating.
L'étape b) peut, par exemple, comporter la soumission de la pièce obtenue après mise en œuvre de l'étape a) à une température supérieure ou égale à 1000°C, par exemple supérieure ou égale à 1100°C.  Step b) may, for example, include the submission of the part obtained after implementation of step a) at a temperature greater than or equal to 1000 ° C, for example greater than or equal to 1100 ° C.
Dans un exemple de réalisation, la pièce peut constituer une aube de turbomachine.  In an exemplary embodiment, the part may constitute a turbomachine blade.
Brève description des dessins Brief description of the drawings
D'autres caractéristiques et avantages de l'invention ressortiront de la description suivante, en référence aux dessins annexés, sur lesquels :  Other characteristics and advantages of the invention will emerge from the following description, with reference to the appended drawings, in which:
- la figure 1 est une photographie d'une aube de turbomachine endommagée en service,  FIG. 1 is a photograph of a turbomachine blade damaged in service,
- la figure 2 comporte une photographie d'une aube de turbomachine endommagée en service et illustre, de manière schématique et partielle, la structure d'une barrière thermique endommagée,  FIG. 2 comprises a photograph of a turbine engine blade damaged in service and illustrates, schematically and partially, the structure of a damaged thermal barrier,
- les figures 3A et 3B illustrent, de manière schématique et partielle, la mise en œuvre d'un procédé selon l'invention, et  FIGS. 3A and 3B illustrate, in a schematic and partial manner, the implementation of a method according to the invention, and
- les figures 4A et 4B sont des photographies représentant respectivement une pièce avant et après traitement par un procédé selon l'invention.  FIGS. 4A and 4B are photographs respectively representing a part before and after treatment by a method according to the invention.
Description détaillée de modes de réalisation Detailed description of embodiments
On a représenté à la figure 2 une pièce 1 par exemple constituée d'un superalliage à base de nickel revêtue d'une couche d'accrochage 2 sur laquelle est présente une barrière thermique endommagée 3. Une couche d'oxyde 2a est présente entre la couche d'accrochage 2 et la barrière thermique 3 endommagée. La couche 2a peut être constituée d'alumine 01-AI2O3. La barrière thermique endommagée 3 comporte un matériau céramique et présente une zone endommagée 4 à réparer. FIG. 2 shows a part 1, for example consisting of a nickel-based superalloy coated with a bonding layer 2 on which a damaged thermal barrier 3 is present. An oxide layer 2a is present between the hanger layer 2 and the thermal barrier 3 damaged. Layer 2a may consist of 01-Al2O3 alumina. The damaged thermal barrier 3 comprises a ceramic material and has a damaged area 4 to be repaired.
La zone endommagée 4 peut présenter au moins une zone adjacente non endommagée. Dans l'exemple illustré, la zone endommagée 4 est présente entre deux zones adjacentes non endommagées 5a et 5b.  The damaged area 4 may have at least one undamaged adjacent area. In the illustrated example, the damaged area 4 is present between two undamaged adjacent areas 5a and 5b.
On a représenté à la figure 3A la mise en œuvre d'une étape a) selon l'invention. Comme illustré, la pièce 1 portant la barrière thermique endommagée 3 est présente dans un électrolyte 10 comportant une suspension de particules 11 dans un milieu liquide. Les particules 11 peuvent, par exemple, être des particules de zircone yttriée (zircone stabilisée par de l'oxyde d'yttrium).  FIG. 3A shows the implementation of a step a) according to the invention. As illustrated, the part 1 carrying the damaged thermal barrier 3 is present in an electrolyte 10 comprising a suspension of particles 11 in a liquid medium. The particles 11 may, for example, be yttria-zirconia particles (zirconia stabilized with yttrium oxide).
A titre d'exemple, on décrit ci-dessous les étapes de la synthèse par voie sol-gel d'une poudre de zircone yttriée destinée, dans un exemple de réalisation, à former les particules 11 :  By way of example, the steps of the sol-gel synthesis of a yttriated zirconia powder intended, in one embodiment, to form the particles 11 are described below:
- Mélange d'acétyl-acétone dans du 1-propanol et de propoxyde de zirconium (Zr(OC3H7)4), - Mixture of acetyl acetone in 1-propanol and zirconium propoxide (Zr (OC 3 H 7 ) 4 ),
- Mélange du mélange obtenu avec une solution de nitrate d'yttrium dans du 1-propanol,  Mixture of the mixture obtained with a solution of yttrium nitrate in 1-propanol,
- Mélange du mélange obtenu avec de l'eau et du 1-propanol (10 mol/L) afin d'obtenir un sol,  - Mixing of the mixture obtained with water and 1-propanol (10 mol / L) to obtain a soil,
- Mise à l'étuve du sol à une température de 50°C, - Storing the soil at a temperature of 50 ° C,
- Séchage évaporatif ou séchage supercritique, - Evaporative drying or supercritical drying,
- Calcination à l'air à une température de 700°C.  - Calcination in air at a temperature of 700 ° C.
La poudre d'oxyde (zircone yttriée) ainsi obtenue est alors mise en suspension dans un milieu liquide constitué par exemple d'isopropanol afin de former l'électrolyte 10.  The oxide powder (yttriated zirconia) thus obtained is then suspended in a liquid medium consisting for example of isopropanol in order to form the electrolyte 10.
La pièce 1 revêtue de la barrière thermique endommagée 3 constitue une électrode du système d'électrophorèse au regard de laquelle est présente une contre-électrode 20. La contre-électrode 20 est, par exemple, en platine. Du fait du caractère conducteur de la pièce 1 et de la zone endommagée 4, un dépôt par électrophorèse est réalisé dans la zone endommagée 4. La zone endommagée 4 est constituée, dans l'exemple illustré, par une région dépourvue de matière. Dans une variante non illustrée, la zone endommagée comporte une première région dépourvue de matière ainsi qu'une deuxième région dans laquelle une couche céramique est présente, l'épaisseur de la couche céramique présente dans la deuxième région étant suffisamment faible pour que cette deuxième région soit conductrice de l'électricité. En variante encore, la zone endommagée est constituée par une région dans laquelle une couche céramique est présente, l'épaisseur de la couche céramique étant suffisamment faible pour que cette région soit conductrice de l'électricité. The part 1 coated with the damaged thermal barrier 3 constitutes an electrode of the electrophoresis system with respect to which a counter electrode 20 is present. The counter-electrode 20 is, for example, made of platinum. Due to the conductive nature of the part 1 and the damaged area 4, an electrophoresis deposit is made in the damaged area 4. The damaged area 4 is constituted, in the illustrated example, by a region devoid of material. In a variant that is not illustrated, the damaged zone includes a first region devoid of of material and a second region in which a ceramic layer is present, the thickness of the ceramic layer in the second region being low enough for the second region to be electrically conductive. In another variant, the damaged zone is constituted by a region in which a ceramic layer is present, the thickness of the ceramic layer being sufficiently small for this region to be electrically conductive.
Le dépôt est réalisé préférentiellement dans les zones les plus conductrices (épaisseur de la couche céramique suffisamment faible ou absence totale de couche céramique) car le champ électrique sera relativement élevé dans ces zones.  The deposition is preferably carried out in the most conductive zones (thickness of the ceramic layer sufficiently small or total absence of ceramic layer) because the electric field will be relatively high in these areas.
On a représenté un exemple de réalisation où la barrière thermique endommagée 3 présente une unique zone endommagée 4 à réparer mais on ne sort pas du cadre de la présente invention si la barrière thermique endommagée présente une pluralité de zones endommagées à réparer. Dans ce cas, chacune des zones endommagées à réparer est conductrice de l'électricité.  There is shown an embodiment where the damaged thermal barrier 3 has a single damaged area 4 to be repaired but it is not beyond the scope of the present invention if the damaged thermal barrier has a plurality of damaged areas to repair. In this case, each of the damaged areas to be repaired is electrically conductive.
Durant l'étape a), un générateur G impose une différence de potentiel entre la pièce 1 et la contre-électrode 20. Le générateur G est à courant continu ou puisé. La pièce 1 est polarisée à une charge opposée à celle des particules 11. Du fait de l'application d'un champ électrique entre la pièce 1 et la contre-électrode 20, les particules 11 se déplacent et se déposent sur la pièce 1 pour former un revêtement céramique 6. Le dépôt du revêtement céramique 6 dans la zone endommagée 4 permet d'obtenir une barrière thermique réparée 7. Le dépôt du revêtement céramique 6 dans la zone endommagée 4 induit une diminution progressive de la conductivité électrique de cette zone au cours du temps. En effet, au fur et à mesure du dépôt du revêtement céramique 6, cette zone devient de plus en plus isolante ce qui ralentit voire stoppe la formation du revêtement céramique 6 sur la pièce 1.  During step a), a generator G imposes a potential difference between the part 1 and the counter-electrode 20. The generator G is DC or pulsed. The part 1 is polarized at a charge opposite to that of the particles 11. Due to the application of an electric field between the part 1 and the counter-electrode 20, the particles 11 move and are deposited on the part 1 to forming a ceramic coating 6. The deposition of the ceramic coating 6 in the damaged zone 4 provides a repaired thermal barrier 7. The deposition of the ceramic coating 6 in the damaged zone 4 induces a gradual decrease in the electrical conductivity of this zone to course of time. In fact, as the ceramic coating 6 is deposited, this zone becomes more and more insulating, which slows down or even stops the formation of the ceramic coating 6 on the part 1.
Comme illustré, le revêtement céramique 6 est déposé dans la zone endommagée 4 et recouvre toute la surface de la zone endommagée 4.  As illustrated, the ceramic coating 6 is deposited in the damaged zone 4 and covers the entire surface of the damaged zone 4.
Avantageusement, lors du dépôt du revêtement céramique 6, la barrière thermique endommagée 3 n'est pas recouverte d'un masque présentant une ouverture se superposant avec la zone endommagée 4 à réparer. En outre, il n'est pas nécessaire avant l'étape a) de décaper une partie de la barrière thermique endommagée 3 située en dehors de la zone endommagée 4 à réparer. Advantageously, during the deposition of the ceramic coating 6, the damaged thermal barrier 3 is not covered with a mask having an opening superimposed with the damaged zone 4 to to fix. In addition, it is not necessary before step a) to strip a portion of the damaged thermal barrier 3 located outside the damaged area 4 to be repaired.
Le revêtement céramique 6 peut présenter une épaisseur e supérieure ou égale à 50 nm, par exemple supérieure ou égale à 30 pm. L'épaisseur e du revêtement céramique 6 correspond à sa plus grande dimension mesurée perpendiculairement à la surface S de la pièce 1 revêtue.  The ceramic coating 6 may have a thickness e greater than or equal to 50 nm, for example greater than or equal to 30 μm. The thickness e of the ceramic coating 6 corresponds to its largest dimension measured perpendicularly to the surface S of the coated part 1.
Après l'étape a), un séchage puis un traitement thermique de consolidation du revêtement céramique 6 peuvent être effectués.  After step a), a drying and then a consolidation heat treatment of the ceramic coating 6 can be performed.
Exemple Example
Une pièce de superalliage base nickel revêtue d'une barrière thermique de zircone stabilisée par de l'oxyde d'yttrium (YSZ) obtenue par procédé de dépôt en phase vapeur avec évaporation sous faisceau d'électrons (« Electron beam physical vapor déposition » ; EB-PVD) a été utilisée. La barrière thermique a tout d'abord été endommagée par jet d'eau. La figure 4A montre le résultat obtenu après endommagement.  A nickel base superalloy piece coated with a zirconia thermal barrier stabilized with yttrium oxide (YSZ) obtained by electron beam vapor deposition method ("electron beam physical vapor deposition"; EB-PVD) was used. The thermal barrier was first damaged by water jet. Figure 4A shows the result obtained after damage.
Un dépôt par électrophorèse a été réalisé à partir d'une suspension de poudre YSZ dans l'isopropanol (10 g/L) à une tension de 100V pendant 6 minutes. Une photographie de la pièce après traitement par le procédé selon l'invention est donnée à la figure 4B.  Electrophoretic deposition was performed from a suspension of YSZ powder in isopropanol (10 g / L) at a voltage of 100V for 6 minutes. A photograph of the part after treatment by the method according to the invention is given in FIG. 4B.
On constate que l'on obtient un dépôt couvrant et homogène de zircone stabilisée par de l'oxyde d'yttrium dans la toute la zone endommagée.  It is found that a covering and homogeneous deposit of zirconia stabilized by yttrium oxide in the entire damaged area.
L'expression « comportant/contenant un(e) » doit se comprendre comme « comportant/contenant au moins un(e) ». The expression "containing / containing a" must be understood as "containing / containing at least one".
L'expression « compris(e) entre ... et ... » ou « allant de ... à ... » doit se comprendre comme incluant les bornes.  The expression "understood between ... and ..." or "from ... to ..." must be understood as including the boundaries.

Claims

REVENDICATIONS
Procédé de réparation localisée d'une barrière thermique endommagée (3) comportant l'étape suivante : A method of localized repair of a damaged thermal barrier (3) comprising the following step:
a) traitement par électrophorèse d'une pièce (1) revêtue d'une barrière thermique endommagée (3), la pièce étant formée d'un matériau conducteur de l'électricité, la barrière thermique endommagée (3) comportant un matériau céramique et présentant au moins une zone endommagée (4) à réparer, la pièce (1) étant présente dans un électrolyte (10) comportant une suspension de particules (11) dans un milieu liquide, un revêtement céramique (6) étant déposé par électrophorèse dans la zone endommagée (4) afin d'obtenir une barrière thermique réparée (7) destinée à être utilisée à des températures supérieures ou égales à 1000°C, les particules (11) étant formées d'un matériau différent du matériau céramique présent dans la barrière thermique endommagée (3).  a) electrophoresis treatment of a part (1) coated with a damaged thermal barrier (3), the part being formed of an electrically conductive material, the damaged thermal barrier (3) comprising a ceramic material and having at least one damaged zone (4) to be repaired, the part (1) being present in an electrolyte (10) comprising a suspension of particles (11) in a liquid medium, a ceramic coating (6) being deposited by electrophoresis in the zone damaged (4) to obtain a repaired thermal barrier (7) for use at temperatures of 1000 ° C or higher, the particles (11) being formed of a material different from the ceramic material present in the thermal barrier damaged (3).
Procédé selon la revendication 1, caractérisé en ce qu'il comporte, avant l'étape a), une étape de formation des particules (11) par mise en œuvre d'un procédé sol-gel.  Process according to claim 1, characterized in that it comprises, before step a), a step of forming the particles (11) by implementing a sol-gel process.
Procédé selon l'une quelconque des revendications 1 et 2, caractérisé en ce que les particules (11), à l'état non aggloméré, ont une taille moyenne comprise entre 20 nm et 1 pm.  Process according to either of Claims 1 and 2, characterized in that the particles (11), in the non-agglomerated state, have a mean size of between 20 nm and 1 μm.
Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les particules (11) sont présentes dans le milieu liquide, avant le début de l'étape a), en une concentration supérieure ou égale à 0,1 g/L. Process according to any one of Claims 1 to 3, characterized in that the particles (11) are present in the liquid medium, before the start of step a), in a concentration greater than or equal to 0.1 g / L.
Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la durée de l'étape a) est supérieure ou égale à 1 minute.  Process according to any one of claims 1 to 4, characterized in that the duration of step a) is greater than or equal to 1 minute.
Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que une tension supérieure ou égale à 1 V est imposée durant tout ou partie de l'étape a) entre la pièce (1) et une contre-électrode (20). Method according to any one of claims 1 to 5, characterized in that a voltage greater than or equal to 1 V is imposed during all or part of step a) between the workpiece (1) and a counter-electrode (20) .
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'épaisseur e du revêtement céramique déposé est supérieure ou égale à 30 pm. 7. Method according to any one of claims 1 to 6, characterized in that the thickness e of the deposited ceramic coating is greater than or equal to 30 pm.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la pièce (1) est revêtue d'une couche d'accrochage (2) permettant l'accrochage de la barrière thermique (3 ; 7) à la pièce (1) et en ce que le revêtement céramique (6) est déposé sur la couche d'accrochage (2).  8. Method according to any one of claims 1 to 7, characterized in that the part (1) is coated with a bonding layer (2) for the attachment of the thermal barrier (3; 7) to the piece (1) and in that the ceramic coating (6) is deposited on the fastening layer (2).
9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la zone endommagée (4) a, avant l'étape a), été soumise à une étape de décapage.  9. Method according to any one of claims 1 to 8, characterized in that the damaged zone (4) has, before step a), been subjected to a pickling step.
10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il comporte, après l'étape a), une étape b) de consolidation par traitement thermique du revêtement céramique (6) déposé.  10. Method according to any one of claims 1 to 9, characterized in that it comprises, after step a), a step b) consolidation by heat treatment of the ceramic coating (6) deposited.
11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la pièce constitue une aube de turbomachine.  11. Method according to any one of claims 1 to 10, characterized in that the part is a turbomachine blade.
EP14828044.9A 2014-01-29 2014-12-11 Process for localised repair of a damaged thermal barrier Active EP3099848B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20203886.5A EP3789518B1 (en) 2014-01-29 2014-12-11 Method for localised repair of a damaged thermal barrier

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1400224 2014-01-29
PCT/FR2014/053268 WO2015114227A1 (en) 2014-01-29 2014-12-11 Process for localised repair of a damaged thermal barrier

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP20203886.5A Division-Into EP3789518B1 (en) 2014-01-29 2014-12-11 Method for localised repair of a damaged thermal barrier
EP20203886.5A Division EP3789518B1 (en) 2014-01-29 2014-12-11 Method for localised repair of a damaged thermal barrier

Publications (2)

Publication Number Publication Date
EP3099848A1 true EP3099848A1 (en) 2016-12-07
EP3099848B1 EP3099848B1 (en) 2021-08-25

Family

ID=50976720

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14828044.9A Active EP3099848B1 (en) 2014-01-29 2014-12-11 Process for localised repair of a damaged thermal barrier
EP20203886.5A Active EP3789518B1 (en) 2014-01-29 2014-12-11 Method for localised repair of a damaged thermal barrier

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP20203886.5A Active EP3789518B1 (en) 2014-01-29 2014-12-11 Method for localised repair of a damaged thermal barrier

Country Status (7)

Country Link
US (1) US9840914B2 (en)
EP (2) EP3099848B1 (en)
CN (1) CN106414813B (en)
BR (1) BR112016017562B1 (en)
CA (1) CA2938031C (en)
RU (1) RU2678347C2 (en)
WO (1) WO2015114227A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3073866B1 (en) * 2017-11-21 2019-11-29 Safran Helicopter Engines METHOD FOR MANUFACTURING A THERMAL BARRIER ON A PIECE OF A TURBOMACHINE
CN110129859B (en) * 2018-02-08 2021-09-21 通用电气公司 Method for masking holes in and treating components
FR3099935B1 (en) * 2019-08-12 2021-09-10 Safran Aircraft Engines Process for coating a part of a turbomachine
US20230220580A1 (en) * 2022-01-12 2023-07-13 General Electric Company Formation of a barrier coating using electrophoretic deposition of a slurry

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10335406A1 (en) * 2003-08-01 2005-02-17 Mtu Aero Engines Gmbh Method of repairing thermal barrier coatings with local damage

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3416165A1 (en) * 1983-06-03 1984-12-06 VEB Thuringia Sonneberg, DDR 6412 Sonneberg Method for the electrophoretic production of a composition film
SU1730209A1 (en) * 1988-09-23 1992-04-30 Предприятие П/Я А-7555 Plant for electrophoretic coating
US5723078A (en) * 1996-05-24 1998-03-03 General Electric Company Method for repairing a thermal barrier coating
FR2827311B1 (en) * 2001-07-12 2003-09-19 Snecma Moteurs PROCESS FOR LOCAL REPAIR OF PARTS COATED WITH A THERMAL BARRIER
US20070087129A1 (en) * 2005-10-19 2007-04-19 Blankenship Donn R Methods for repairing a workpiece
US7780832B2 (en) * 2005-11-30 2010-08-24 General Electric Company Methods for applying mitigation coatings, and related articles
KR100753909B1 (en) 2006-09-09 2007-08-31 한국원자력연구원 Repair method of pitting damage or cracks of metals or alloys by using electrophoretic deposition of nanoparticles
EP2000557B1 (en) 2007-06-04 2015-04-29 United Technologies Corporation Erosion barrier for thermal barrier coatings

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10335406A1 (en) * 2003-08-01 2005-02-17 Mtu Aero Engines Gmbh Method of repairing thermal barrier coatings with local damage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2015114227A1 *

Also Published As

Publication number Publication date
CA2938031A1 (en) 2015-08-06
EP3099848B1 (en) 2021-08-25
WO2015114227A1 (en) 2015-08-06
BR112016017562A2 (en) 2017-08-08
EP3789518B1 (en) 2023-11-29
RU2016135017A3 (en) 2018-08-22
EP3789518A1 (en) 2021-03-10
CA2938031C (en) 2022-05-10
RU2016135017A (en) 2018-03-05
BR112016017562B1 (en) 2022-04-12
US20160348509A1 (en) 2016-12-01
RU2678347C2 (en) 2019-01-28
US9840914B2 (en) 2017-12-12
CN106414813A (en) 2017-02-15
CN106414813B (en) 2019-04-30

Similar Documents

Publication Publication Date Title
EP3099848B1 (en) Process for localised repair of a damaged thermal barrier
EP3077570B1 (en) Method for locally repairing thermal barriers
FR2972449A1 (en) METHOD FOR PRODUCING A THERMAL BARRIER IN A MULTILAYER SYSTEM FOR PROTECTING A METAL PIECE AND PIECE EQUIPPED WITH SUCH A PROTECTION SYSTEM
EP2882551B1 (en) Abradable coating made of a material having a low surface roughness
EP3707297B1 (en) Method for producing a thermal barrier on a part of a turbomachine
FR2946663A1 (en) Thermal coating useful in a thermomechanical part of e.g. a turbomachine and an aircraft engine, comprises a stack of two layers defining a plane and an orthogonal direction of the plane, and first and second thermal insulation layers
FR2941965A1 (en) Depositing a protection layer on a metallic piece e.g. turbine blade using mold, comprises depositing precursor coating on piece and/or inner walls of mold, and depositing piece in the mold and then mold in a compression enclosure
FR2827308A1 (en) PROCESS FOR GLOBAL REPAIR OF A PART COATED WITH A THERMAL BARRIER
WO2010092298A1 (en) Process for depositing a protective layer on a part
EP3669013B1 (en) Method for manufacturing an electrolyte for solid oxide cells by magnetron cathode sputtering
EP3619338A1 (en) Superalloy turbine part and associated method for manufacturing by bombardment with charged particles
FR3085870A1 (en) METHOD FOR ASSEMBLING A METAL PIECE AND A CERAMIC PIECE, AND ELECTRIC DEVICE, IN PARTICULAR CAPACITIVE SENSOR, CARRIED OUT BY THE METHOD
EP4436940A1 (en) Method for electrophoretically coating a ceramic matrix composite part with an environmental barrier
FR3139335A1 (en) Manufacturing process for obtaining a part coated with an electrically and thermally insulating coating
FR3085872A1 (en) METHOD FOR EXTRACTING A FOREIGN BODY NESTED IN A BLADE OF HIGH PRESSURE DISPENSER
WO2017093648A1 (en) Hybrid annular sector with touch-tolerant protective coating

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20160718

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HAMADI, SARAH

Inventor name: CERDA, HELENE

Inventor name: BONINO, JEAN-PIERRE

Inventor name: PUJOL, GUILLAUME

Inventor name: ANSART, FLORENCE

Inventor name: MALIE, ANDRE, HUBERT, LOUIS

DAX Request for extension of the european patent (deleted)
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: 20180413

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 13/22 20060101ALI20200527BHEP

Ipc: C25D 13/02 20060101AFI20200527BHEP

Ipc: F01D 5/00 20060101ALI20200527BHEP

Ipc: F01D 5/28 20060101ALI20200527BHEP

Ipc: C25D 13/12 20060101ALI20200527BHEP

Ipc: C25D 13/20 20060101ALI20200527BHEP

INTG Intention to grant announced

Effective date: 20200624

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INSTITUT NATIONAL POLYTECHNIQUE

Owner name: UNIVERSITE PAUL SABATIER - TOULOUSE III

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE

Owner name: SAFRAN AIRCRAFT ENGINES

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

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

Ref country code: AT

Ref legal event code: REF

Ref document number: 1423891

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210915

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014079715

Country of ref document: DE

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210825

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1423891

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210825

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: 20210825

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: 20210825

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: 20211125

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: 20211227

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: 20210825

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: 20210825

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: 20210825

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: 20211125

Ref country code: AT

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: 20210825

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: 20210825

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: 20210825

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: 20211126

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: 20210825

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: 20210825

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014079715

Country of ref document: DE

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

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: 20210825

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: 20210825

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: 20210825

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: 20210825

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: 20210825

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: 20210825

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: 20210825

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20220527

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: 20210825

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211231

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

Ref country code: LU

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

Effective date: 20211211

Ref country code: IE

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

Effective date: 20211211

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: 20211231

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: 20211231

Ref country code: CH

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

Effective date: 20211231

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

Ref country code: IT

Payment date: 20221122

Year of fee payment: 9

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: 20141211

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: 20210825

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

Ref country code: GB

Payment date: 20231124

Year of fee payment: 10

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

Ref country code: SE

Payment date: 20231121

Year of fee payment: 10

Ref country code: FR

Payment date: 20231122

Year of fee payment: 10

Ref country code: DE

Payment date: 20231121

Year of fee payment: 10

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: 20210825

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

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: 20210825