EP3710610B1 - Superlegierung auf nickelbasis, einkristalline schaufel und turbomaschine - Google Patents

Superlegierung auf nickelbasis, einkristalline schaufel und turbomaschine Download PDF

Info

Publication number
EP3710610B1
EP3710610B1 EP18821710.3A EP18821710A EP3710610B1 EP 3710610 B1 EP3710610 B1 EP 3710610B1 EP 18821710 A EP18821710 A EP 18821710A EP 3710610 B1 EP3710610 B1 EP 3710610B1
Authority
EP
European Patent Office
Prior art keywords
superalloy
nickel
superalloys
rhenium
chromium
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
Application number
EP18821710.3A
Other languages
English (en)
French (fr)
Other versions
EP3710610A1 (de
Inventor
Jérémy RAME
Virginie JAQUET
Joël DELAUTRE
Jean-Yves Guedou
Pierre Caron
Odile Lavigne
Didier Locq
Mikael PERRUT
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.)
Office National dEtudes et de Recherches Aerospatiales ONERA
Safran SA
Original Assignee
Office National dEtudes et de Recherches Aerospatiales ONERA
Safran SA
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 Office National dEtudes et de Recherches Aerospatiales ONERA, Safran SA filed Critical Office National dEtudes et de Recherches Aerospatiales ONERA
Publication of EP3710610A1 publication Critical patent/EP3710610A1/de
Application granted granted Critical
Publication of EP3710610B1 publication Critical patent/EP3710610B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • 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
    • 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
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
    • 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
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
    • F05D2300/132—Chromium
    • 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
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/17—Alloys
    • F05D2300/175—Superalloys
    • 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
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/17—Alloys
    • F05D2300/177—Ni - Si alloys
    • 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
    • F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
    • F05D2300/607—Monocrystallinity

Definitions

  • This presentation relates to nickel-based superalloys for gas turbines, in particular for stationary blades, also called distributors or rectifiers, or vanes of a gas turbine, for example in the field of aeronautics.
  • nickel-based superalloys for single-crystal blades have undergone significant changes in chemical composition, with the aim in particular of improving their creep properties at high temperature while maintaining resistance to the very aggressive environment in which these superalloys are used.
  • metallic coatings adapted to these alloys have been developed in order to increase their resistance to the aggressive environment in which these alloys are used, in particular the resistance to oxidation and the resistance to corrosion.
  • a ceramic coating of low thermal conductivity, performing a thermal barrier function can be added to reduce the temperature at the surface of the metal.
  • a complete protection system has at least two layers.
  • the first layer also called sub-layer or bonding layer
  • the first layer is deposited directly on the part to be protected in nickel-based superalloy, also called substrate, for example a blade.
  • the deposition step is followed by a step of diffusion of the underlayer in the superalloy.
  • the deposition and the diffusion can also be carried out during a single step.
  • the second layer is a ceramic coating comprising for example yttria zirconia, also called “YSZ” according to the English acronym for " Yttria Stabilized Zirconia” or “YPSZ” in accordance with the English acronym for “Yttria Partially Stabilized Zirconia” and having a porous structure.
  • This layer can be deposited by various processes, such as evaporation under an electron beam (“EB-PVD” in accordance with the English acronym for “Electron Beam Physical Vapor Deposition”), thermal spraying (“APS” in accordance with the English acronym for “Atmospheric Plasma Spraying” or “SPS” in accordance with the English acronym for “Suspension Plasma Spraying”), or any other process making it possible to obtain a porous ceramic coating with low thermal conductivity.
  • EB-PVD electron beam
  • APS in accordance with the English acronym for “Atmospheric Plasma Spraying” or “SPS” in accordance with the English acronym for “Suspension Plasma Spraying”
  • any other process making it possible to obtain a porous ceramic coating with low thermal conductivity.
  • inter-diffusion phenomena occur on a microscopic scale between the nickel-based superalloy of the substrate and the metal alloy of the underlayer.
  • These phenomena of inter-diffusion, associated with the oxidation of the underlayer modify in particular the chemical composition, the microstructure and consequently the mechanical properties of the underlayer from the manufacture of the coating, then during the use of dawn in the turbine.
  • These inter-diffusion phenomena also modify the chemical composition, the microstructure and consequently the mechanical properties of the superalloy of the substrate under the coating.
  • a secondary reaction zone can thus form in the superalloy under the sub-layer to a depth of several tens, or even hundreds, of micrometers.
  • the mechanical characteristics of this ZRS are clearly inferior to those of the superalloy of the substrate.
  • There ZRS formation is undesirable because it leads to a significant reduction in the mechanical strength of the superalloy.
  • foundry defects are liable to form in the parts, such as blades, during their manufacture by directional solidification. These defects are generally parasitic grains of the "Freckle" type, the presence of which can cause premature failure of the part in service. The presence of these defects, related to the chemical composition of the superalloy, generally leads to the rejection of the part, which leads to an increase in the cost of production.
  • US5366695 describes superalloys not comprising ruthenium.
  • This presentation aims to propose compositions of nickel-based superalloys for the manufacture of single-crystal components, presenting increased performance in terms of service life and mechanical resistance and making it possible to reduce the costs of production of the part (reduced scrap rate) compared to existing alloys.
  • These superalloys exhibit superior high temperature creep resistance than existing alloys while showing good microstructural stability within the bulk of the superalloy (low susceptibility to PTC formation), good microstructural stability under the coating underlayer of the thermal barrier (low sensitivity to the formation of ZRS), good resistance to oxidation and corrosion while avoiding the formation of parasitic grains of the "Freckle" type.
  • the present disclosure relates to a nickel-based superalloy comprising, in mass percentages, 4.0 to 5.5% rhenium, 1.0 to 3.0 ruthenium, 2.0 to 14.0% cobalt, 0.30-1.00% molybdenum, 3.0-5.0% chromium, 2.5-4.0% tungsten, 4.5-6.5% aluminum, 0.50 to 1.50% titanium, 8.0 to 9.0% tantalum, 0.15 to 0.30% hafnium, preferably 0.16 to 0.30% hafnium, preferably 0.17 to 0 .30% hafnium, preferably 0.18 to 0.30% hafnium, preferably 0.08 to 0.12% silicon, even more preferably 0.10% silicon, even more preferably 0.20 to 0.30% hafnium, 0.05 to 0.15% silicon, the remainder consisting of nickel and inevitable impurities.
  • This superalloy is intended for the manufacture of monocrystalline gas turbine components, such as fixed or moving blades.
  • the creep resistance is improved compared to existing superalloys, in particular at temperatures which can go up to 1200°C.
  • This alloy therefore has improved creep resistance at high temperature. This alloy also exhibits improved corrosion and oxidation resistance.
  • These superalloys have a density less than or equal to 9.00 g/cm 3 (gram per cubic centimeter).
  • a single-crystal nickel-based superalloy part is obtained by a process of directed solidification under a thermal gradient in the lost-wax foundry.
  • the single-crystal nickel-based superalloy comprises an austenitic matrix with a face-centered cubic structure, nickel-based solid solution, known as the gamma (“ ⁇ ”) phase.
  • This matrix contains gamma prime hardening phase precipitates (“ ⁇ '”) of ordered cubic structure L1 2 of the Ni 3 Al type.
  • the assembly (matrix and precipitates) is therefore described as a ⁇ / ⁇ ' superalloy.
  • this composition of the nickel-based superalloy allows the implementation of a heat treatment which redissolves the ⁇ ′ phase precipitates and the ⁇ / ⁇ ′ eutectic phases which are formed during the solidification of the superalloy. It is thus possible to obtain a monocrystalline nickel-based superalloy containing ⁇ ′ precipitates of controlled size, preferably between 300 and 500 nanometers (nm), and containing a small proportion of ⁇ / ⁇ ′ eutectic phases.
  • the heat treatment also makes it possible to control the volume fraction of the ⁇ ′ phase precipitates present in the single-crystal nickel-based superalloy.
  • the percentage by volume of the ⁇ ' phase precipitates can be greater than or equal to 50%, preferably greater than or equal to 60%, even more preferably equal to 70%.
  • the major addition elements are cobalt (Co), chromium (Cr), molybdenum (Mo), rhenium (Re), ruthenium (Ru), tungsten (W), aluminum (Al), titanium (Ti) and tantalum (Ta).
  • the minor addition elements are hafnium (Hf) and silicon (Si), for which the maximum mass content is less than 1% by mass.
  • Unavoidable impurities include sulfur (S), carbon (C), boron (B), yttrium (Y), lanthanum (La) and cerium (Ce). Unavoidable impurities are defined as those elements which are not intentionally added to the composition and which are added with other elements.
  • tungsten, chromium, cobalt, rhenium, ruthenium or molybdenum makes it possible to reinforce the austenitic matrix ⁇ of face-centered cubic crystal structure (fcc) by hardening in solid solution.
  • Rhenium (Re) makes it possible to slow down the diffusion of chemical species within the superalloy and to limit the coalescence of ⁇ ' phase precipitates during service at high temperature, a phenomenon which leads to a reduction in mechanical strength. Rhenium thus makes it possible to improve the creep resistance at high temperature of the nickel base superalloy.
  • too high a concentration of rhenium can lead to the precipitation of PTC intermetallic phases, for example ⁇ phase, P phase or ⁇ phase, which have a negative effect on the mechanical properties of the superalloy. Too high a rhenium concentration can also cause the formation of a secondary reaction zone in the superalloy under the underlayer, which has a negative effect on the mechanical properties of the superalloy.
  • the addition of ruthenium makes it possible in particular to displace part of the rhenium in the ⁇ ' phase and to limit the formation of PTC.
  • the simultaneous addition of silicon and hafnium makes it possible to improve the resistance to hot oxidation of nickel-based superalloys by increasing the adhesion of the layer of alumina (Al 2 O 3 ) which forms on the surface. high temperature superalloy.
  • This layer of alumina forms a passivation layer on the surface of the nickel-based superalloy and a barrier to the diffusion of oxygen coming from the exterior towards the interior of the nickel-based superalloy.
  • hafnium without also adding silicon or conversely add silicon without also adding hafnium and still improve the resistance to hot oxidation of the superalloy.
  • chromium or aluminum makes it possible to improve the resistance to oxidation and to corrosion at high temperature of the superalloy.
  • chromium is essential for increasing the hot corrosion resistance of nickel-based superalloys.
  • too high a chromium content tends to reduce the solvus temperature of the ⁇ ' phase of the nickel-based superalloy, i.e. the temperature above which the ⁇ ' phase is completely dissolved in the ⁇ matrix, which is undesirable.
  • the chromium concentration is between 3.0 to 5.0% by mass in order to maintain a high solvus temperature of the ⁇ ' phase of the nickel-based superalloy, for example greater than or equal to 1250° C. but also to avoid the formation of topologically compact phases in the ⁇ matrix highly saturated with alloying elements such as rhenium, molybdenum or tungsten.
  • cobalt which is an element close to nickel and which partially substitutes for nickel, forms a solid solution with the nickel in the ⁇ matrix.
  • Cobalt makes it possible to reinforce the ⁇ matrix, to reduce susceptibility to PTC precipitation and ZRS formation in the superalloy under the protective coating.
  • too high a cobalt content tends to reduce the solvus temperature of the ⁇ ' phase of the nickel-based superalloy, which is undesirable.
  • the addition of ruthenium makes it possible to reinforce the ⁇ matrix and to reduce the sensitivity of the superalloy to the formation of PTC.
  • the addition of ruthenium makes it possible in particular to displace part of the rhenium in the ⁇ ' phase and to limit the formation of PTC.
  • the addition of ruthenium can also have a beneficial effect on the adhesion of the ceramic coating.
  • refractory elements such as molybdenum, tungsten, rhenium or tantalum makes it possible to slow down the mechanisms controlling the creep of nickel-based superalloys and which depend on the diffusion of chemical elements in the superalloy.
  • a very low sulfur content in a nickel-based superalloy increases the resistance to oxidation and hot corrosion as well as the spalling resistance of the thermal barrier.
  • a low sulfur content less than 2 ppm by mass (part per million by mass), or even ideally less than 0.5 ppm by mass, makes it possible to optimize these properties.
  • Such a mass content of sulfur can be obtained by producing a low-sulphur mother casting or by a desulfurization process carried out after casting. In particular, it is possible to maintain a low sulfur content by adapting the process for producing the superalloy.
  • Nickel-based superalloys are understood to mean superalloys in which the mass percentage of nickel is predominant. It is understood that nickel is therefore the element whose mass percentage in the alloy is the highest.
  • the superalloy may comprise, in mass percentages, 4.5 to 5.5% rhenium, 1.0 to 3.0 ruthenium, 3.0 to 5.0% cobalt, 0.30 to 0.80% molybdenum, 3.0-4.5% chromium, 2.5-4.0% tungsten, 4.5-6.5% aluminum, 0.50-1.50% titanium, 8.0 to 9.0% tantalum, 0.15 to 0.30% hafnium, preferably 0.17 to 0.30% hafnium, even more preferably 0.20 to 0.30% hafnium, 0.05 to 0.15% silicon, the balance consisting of nickel and inevitable impurities.
  • the superalloy may comprise, in mass percentages, 4.0 to 5.5% rhenium, 1.0 to 3.0 ruthenium, 3.0 to 13.0% cobalt, 0.40 to 1.00% molybdenum, 3.0-4.5% chromium, 2.5-4.0% tungsten, 4.5-6.5% aluminum, 0.50-1.50% titanium, 8.0 to 9.0% tantalum, 0.15 to 0.30% hafnium, preferably 0.17 to 0.30% hafnium, even more preferably 0.20 to 0.30% hafnium, 0.05 to 0.15% silicon, the balance consisting of nickel and inevitable impurities.
  • the superalloy may comprise, in mass percentages, 4.0 to 5.0% rhenium, 1.0 to 3.0 ruthenium, 11.0 to 13.0% cobalt, 0.40 to 1.00% molybdenum, 3.0-4.5% chromium, 2.5-4.0% tungsten, 4.5-6.5% aluminum, 0.50-1.50% titanium, 8.0 to 9.0% tantalum, 0.15 to 0.30% hafnium, preferably 0.17 to 0.30% hafnium, even more preferably 0.20 to 0.30% hafnium, 0.05 to 0.15% silicon, the balance consisting of nickel and inevitable impurities.
  • the superalloy may comprise, in mass percentages, 5.0% rhenium, 2.0 ruthenium, 4.0% cobalt, 0.50% molybdenum, 4.0% chromium, 3.0% tungsten, 5.4% aluminum, 1.00% titanium, 8.5% tantalum, 0.25% hafnium, 0.10% silicon, balance being nickel and unavoidable impurities.
  • the superalloy may comprise, in mass percentages, 5.0% rhenium, 2.0 ruthenium, 4.0% cobalt, 0.50% molybdenum, 4.0% chromium, 3.5% tungsten, 5.4% aluminum, 0.90% titanium, 8.5% tantalum, 0.25% hafnium, 0.10% silicon, the balance being made up of nickel and inevitable impurities.
  • the superalloy may comprise, in mass percentages, 4.4% rhenium, 2.0 ruthenium, 4.0% cobalt, 0.70% molybdenum, 4.0% chromium, 3.0% tungsten, 5.4% aluminum, 1.00% titanium, 8.5% tantalum, 0.25% hafnium, 0.10% silicon, balance being nickel and unavoidable impurities.
  • the superalloy may comprise, in mass percentages, 4.4% rhenium, 2.0 ruthenium, 12.0% cobalt, 0.70% molybdenum, 4.0% chromium, 3.0% tungsten, 5.4% aluminum, 1.00% titanium, 8.5% tantalum, 0.25% hafnium, 0.10% silicon, the balance consisting of nickel and inevitable impurities.
  • the superalloy may comprise, in mass percentages, 5.0% rhenium, 2.0 ruthenium, 4.0% cobalt, 0.50% molybdenum, 3.5% chromium, 3.5% tungsten, 5.4% aluminum, 0.90% titanium, 8.5% tantalum, 0.25% hafnium, 0.10% silicon, the balance being made up of nickel and inevitable impurities.
  • the superalloy may comprise, in mass percentages, 4.4% rhenium, 2.0 ruthenium, 12.0% cobalt, 0.70% molybdenum, 3.5% chromium, 3.5% tungsten, 5.4% aluminum, 0.90% titanium, 8.5% tantalum, 0.25% hafnium, 0.10% silicon, the balance being made up of nickel and inevitable impurities.
  • This presentation also relates to a single-crystal blade for a turbomachine comprising a superalloy as defined above.
  • This blade therefore has an improved resistance to creep at high temperature.
  • the blade may include a protective coating comprising a metal underlayer deposited on the superalloy and a ceramic thermal barrier deposited on the metal underlayer.
  • the composition of the nickel-based superalloy Thanks to the composition of the nickel-based superalloy, the formation of a secondary reaction zone in the superalloy resulting from interdiffusion phenomena between the superalloy and the underlayer is avoided, or limited.
  • the metallic underlayer can be an alloy of the MCrAlY type or an alloy of the nickel aluminide type.
  • the ceramic thermal barrier can be a yttria-zirconia-based material or any other ceramic (zirconia-based) coating with low thermal conductivity.
  • the dawn may have a structure oriented along a ⁇ 001> crystallographic direction.
  • This orientation generally gives the blade the optimum mechanical properties.
  • This presentation also relates to a turbomachine comprising a blade as defined above.
  • Nickel-based superalloys are intended for the manufacture of single-crystal blades by a directed solidification process in a thermal gradient.
  • the use of a monocrystalline seed or of a grain selector at the start of solidification makes it possible to obtain this monocrystalline structure.
  • the structure is oriented for example along a crystallographic direction ⁇ 001> which is the orientation which generally confers the optimum mechanical properties on the superalloys.
  • As-solidified nickel-based single-crystal superalloys have a dendritic structure and consist of ⁇ ' Ni 3 (Al, Ti, Ta) precipitates dispersed in a ⁇ matrix of face-centered cubic structure, nickel-based solid solution. These ⁇ ' phase precipitates are distributed heterogeneously in the volume of the single crystal due to chemical segregations resulting from the solidification process. Furthermore, ⁇ / ⁇ ' eutectic phases are present in the inter-dendritic regions and constitute preferential crack initiation sites. These ⁇ / ⁇ ' eutectic phases are formed at the end of solidification.
  • the ⁇ / ⁇ ' eutectic phases are formed to the detriment of the fine precipitates (size less than a micrometer) of the ⁇ ' hardening phase.
  • These ⁇ ' phase precipitates constitute the main source of hardening of nickel-based superalloys.
  • the presence of residual ⁇ / ⁇ ' eutectic phases does not make it possible to optimize the hot creep resistance of the nickel-based superalloy.
  • the first heat treatment is a microstructure homogenization treatment which aims to dissolve the ⁇ ′ phase precipitates and to eliminate the ⁇ / ⁇ ′ eutectic phases or to significantly reduce their volume fraction.
  • This treatment is carried out at a temperature above the solvus temperature of the ⁇ ' phase and below the starting melting temperature of the superalloy (T solidus ). Quenching is then carried out at the end of this first heat treatment to obtain a fine and homogeneous dispersion of the ⁇ ' precipitates.
  • Tempering heat treatments are then carried out in two stages, at temperatures below the solvus temperature of the ⁇ ' phase. During a first step, to make the ⁇ ′ precipitates grow and obtain the desired size, then during a second step, to increase the volume fraction of this phase to about 70% at room temperature.
  • turbofan engine 10 comprises, from upstream to downstream according to the circulation of the air flow, a fan 12, a compressor low pressure 14, a high pressure compressor 16, a combustion chamber 18, a high pressure turbine 20, and a low pressure turbine 22.
  • the high pressure turbine 20 comprises a plurality of moving vanes 20A rotating with the rotor and stator vanes 20B (fixed vanes) mounted on the stator.
  • the stator of the turbine 20 comprises a plurality of stator rings 24 arranged opposite the moving blades 20A of the turbine 20.
  • a moving blade 20A or a stator 20B for a turbomachine comprising a superalloy as defined previously coated with a protective coating comprising a metal sub-layer
  • a turbomachine can in particular be a turbojet engine such as a turbofan engine 10.
  • the turbomachine can also be a single-flow turbojet engine, a turboprop engine or a turboshaft engine.
  • Example 6 Six nickel-based monocrystalline superalloys of this presentation (Ex 1 to Ex 6) were studied and compared to six commercial monocrystalline superalloys CMSX-4 (Ex 7), CMSX-4PlusC (Ex 8), René N6 (Ex 9), CMSX-10 (Ex 10), MC-NG (Ex 11) and TMS-138 (Ex 12).
  • the chemical composition of each of the single-crystal superalloys is given in table 1, the Ex 9 composition also comprising 0.05% by mass of carbon (C) and 0.004% by mass of boron (B), the Ex 10 composition also comprising in addition to 0.10% by mass of niobium (Nb).
  • the densities calculated for the alloys of the disclosure and for the reference alloys are less than 9.00 g/cm 3 (see table 2).
  • Table 2 presents different parameters for Ex 1 to Ex 12 superalloys.
  • Table 2 Estimated density (1) (g/cm 3 ) Measured density (g/cm 3 ) NFP RGP M d Ex 1 8.89 - 0.96 0.380 0.98 Ex 2 - - 0.91 0.376 - Ex 3 8.85 - 1.05 0.380 0.98 Ex 4 8.83 - 1.05 0.380 0.98 Ex 5 8.91 8.8 0.91 0.376 0.98 Ex 6 8.86 - 1.00 0.376 0.98 Ex 7 8.71 - 0.65 0.358 0.99 Ex 8 8.91 - 0.68 0.371 0.99 Ex 9 8.87 - 0.69 0.256 0.98 Ex 10 8.99 - 0.67 0.299 0.96 Ex 11 8.75 8.75 0.55 0.232 0.97 Ex 12 8.88 - 0.61 0.215 0.97
  • NFP % Your + 1.5 % Off + 0.5 %MB ⁇ 0.5 % % You ) / % W + 1.2 % D )
  • %Cr, %Ni, ...%X are the contents, expressed in mass percentages, of the superalloy elements Cr, Ni, ..., X.
  • the NFP parameter makes it possible to quantify the sensitivity to the formation of parasitic grains of the "Freckles” type during the directed solidification of the part (document US 5,888,451 ). To avoid the formation of “Freckles” type faults, the NFP parameter must be greater than or equal to 0.7.
  • the intrinsic mechanical strength of the ⁇ ' phase increases with the content of elements replacing the aluminum in the Ni 3 Al compound, such as titanium, tantalum and part of the tungsten.
  • the ⁇ ' phase compound can therefore be written as Ni 3 (Al, Ti, Ta, W).
  • Table 3 presents the Md values for the different elements of the superalloys.
  • Table 3 Element md Element md You 2,271 Off 3.02 CR 1,142 Your 2,224 Co 0.777 W 1,655 Neither 0.717 D 1,267 Number 2,117 HAVE 1.9 Mo 1.55 Whether 1.9 Ru 1.006
  • the sensitivity to PTC formation is determined by the parameter M d, according to the New PHACOMP method which was developed by Morinaga et al. ( Morinaga et al., New PHACOMP and its application to alloy design, Superalloys 1984, edited by M Gell et al., The Metallurgical Society of AIME, Warrendale, PA, USA (1984) pp. 523-532 ). According to this model, the sensitivity of superalloys to the formation of PTC increases with the value of the parameter M d.
  • the superalloys Ex 1 to Ex 12 present values of the parameter M d substantially equal. These superalloys therefore exhibit similar sensitivities to the formation of PTC, sensitivities which are relatively low.
  • ThermoCalc software (Ni25 database) based on the CALPHAD method was used to calculate the solvus temperature of the ⁇ ' phase at equilibrium.
  • ThermoCalc software (Ni25 database) based on the CALPHAD method was used to calculate the volume fraction (in volume percentage) of ⁇ ' phase at equilibrium in Ex 1 to Ex 12 superalloys at 950°C, 1050° C and 1200°C.
  • Ex 1 to Ex 6 superalloys contain volume fractions of ⁇ ' phase greater than or comparable to the volume fractions of ⁇ ' phase of commercial superalloys Ex 7 to Ex 12.
  • ThermoCalc software (Ni25 database) based on the CALPHAD method was used to calculate the volume fraction (in volume percentage) of phase ⁇ at equilibrium in Ex 1 to Ex 12 superalloys at 950°C and 1050°C (see Table 5).
  • ThermoCalc software (Ni25 database) based on the CALPHAD method was used to calculate chromium content (in mass percentage) in the equilibrium ⁇ phase in Ex 1 to Ex 12 superalloys at 950°C, 1050° C and 1200°C.
  • the chromium concentrations in the ⁇ phase for the Ex 1 to Ex 6 superalloys are comparable to the chromium concentrations in the ⁇ phase for the commercial superalloys Ex 7 to Ex 12, which is favorable good resistance to corrosion and hot oxidation.
  • Creep tests were carried out on Ex 2, Ex 7, Ex 9 and Ex 10 superalloys. Creep tests are carried out at 1200°C and 80 MPa according to standard NF EN ISO 204 of August 2009 (Guide U125_J) .
  • Table 6 presents the results of the creep tests in which the superalloys were loaded (80 MPa) at 1200°C. The results represent the time in hours (h) to the rupture of the specimen. Table 6 Breaking time (hour) Ex 2 63 Ex 7 7 Ex 9 9 Ex 10 59
  • the Ex 2 superalloy exhibits better creep behavior than the Ex 7 and Ex 9 superalloys.
  • the Ex 10 superalloy also exhibits good creep properties.
  • a specimen of the superalloy tested (pawn having a diameter of 20 mm and a height of 1 mm) is subjected to thermal cycling, each cycle of which includes a rise to 1150°C in less than 15 min (minutes), a plateau at 1150° C for 60 min and turbine cooling of the specimen for 15 min.
  • the thermal cycle is repeated until a loss in mass of the specimen equal to 20 mg/cm 2 (milligrams per square centimeters) is observed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (14)

  1. Superlegierung auf Nickelbasis, umfassend, in Ma%, 4,0 bis 5,5 % Rhenium, 1,0 bis 3,0 % Ruthenium, 2,0 bis 14,0 % Kobalt, 0,30 bis 1,00 % Molybdän, 3,0 bis 5,0 % Chrom, 2,5 bis 4,0 % Wolfram, 4,5 bis 6,5 % Aluminium, 0,50 bis 1,50 % Titan, 8,0 bis 9,0 % Tantal, 0,15 bis 0,30 % Hafnium, 0,05 bis 0,15 % Silicium, wobei das Komplement von Nickel und unvermeidbaren Verunreinigungen gebildet ist.
  2. Superlegierung nach Anspruch 1, umfassend 4,5 bis 5,5 % Rhenium, 3,0 bis 5,0 % Kobalt, 0,30 bis 0,80 % Molybdän und 3,0 bis 4,5 % Chrom.
  3. Superlegierung nach Anspruch 1, umfassend 3,0 bis 13,0 % Kobalt, 0,40 bis 1,00 % Molybdän und 3,0 bis 4,5 % Chrom.
  4. Superlegierung nach Anspruch 3, umfassend 4,0 bis 5,0 % Rhenium und 11,0 bis 13,0 % Kobalt.
  5. Superlegierung nach Anspruch 3, umfassend 5,0 % Rhenium, 2,0 % Ruthenium, 4,0 % Kobalt, 0,50 % Molybdän, 4,0 % Chrom, 3,0 % Wolfram, 5,4 % Aluminium, 1,00 % Titan, 8,5 % Tantal, 0,25 % Hafnium und 0,10 % Silicium.
  6. Superlegierung nach Anspruch 3, umfassend 4,4 % Rhenium, 2,0 % Ruthenium, 4,0 % Kobalt, 0,70 % Molybdän, 4,0 % Chrom, 3,0 % Wolfram, 5,4 % Aluminium, 1,00 % Titan, 8,5 % Tantal, 0,25 % Hafnium und 0,10 % Silicium.
  7. Superlegierung nach Anspruch 4, umfassend 4,4 % Rhenium, 2,0 % Ruthenium, 12,0 % Kobalt, 0,70 % Molybdän, 4,0 % Chrom, 3,0 % Wolfram, 5,4 % Aluminium, 1,00 % Titan, 8,5 % Tantal, 0,25 % Hafnium und 0,10 % Silicium.
  8. Superlegierung nach Anspruch 3, umfassend 5,0 % Rhenium, 2,0 % Ruthenium, 4,0 % Kobalt, 0,50 % Molybdän, 3,5 % Chrom, 3,5 % Wolfram, 5,4 % Aluminium, 0,90 % Titan, 8,5 % Tantal, 0,25 % Hafnium und 0,10 % Silicium.
  9. Superlegierung nach Anspruch 3, umfassend 5,0 % Rhenium, 2,0 Ruthenium, 4,0 % Kobalt, 0,50 % Molybdän, 4,0 % Chrom, 3,5 % Wolfram, 5,4 % Aluminium, 0,90 % Titan, 8,5 % Tantal, 0,25 % Hafnium und 0,10 % Silicium.
  10. Superlegierung nach Anspruch 4, umfassend 4,4 % Rhenium, 2,0 % Ruthenium, 12,0 % Kobalt, 0,70 % Molybdän, 3,5 % Chrom, 3,5 % Wolfram, 5,4 % Aluminium, 0,90 % Titan, 8,5 % Tantal, 0,25 % Hafnium und 0,10 % Silicium.
  11. Einkristalline Schaufel (20A, 20B) für Turbomaschine, umfassend eine Superlegierung nach einem der Ansprüche 1 bis 10.
  12. Schaufel (20A, 20B) nach Anspruch 11, umfassend eine Schutzbeschichtung, die eine Metallunterschicht aufweist, die auf der Superlegierung aufgebracht ist und eine keramische Wärmebarriere, die auf der Metallunterschicht aufgebracht ist.
  13. Schaufel (20A, 20B) nach Anspruch 11 oder 12, die eine Struktur aufweist, die in einer Kristallographierichtung <001> ausgerichtet ist.
  14. Turbomaschine, umfassend eine Schaufel (20A, 20B) nach einem der Ansprüche 11 bis 13.
EP18821710.3A 2017-11-14 2018-11-14 Superlegierung auf nickelbasis, einkristalline schaufel und turbomaschine Active EP3710610B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1760679A FR3073527B1 (fr) 2017-11-14 2017-11-14 Superalliage a base de nickel, aube monocristalline et turbomachine
PCT/FR2018/052839 WO2019097162A1 (fr) 2017-11-14 2018-11-14 Superalliage a base de nickel, aube monocristalline et turbomachine

Publications (2)

Publication Number Publication Date
EP3710610A1 EP3710610A1 (de) 2020-09-23
EP3710610B1 true EP3710610B1 (de) 2023-04-05

Family

ID=61750233

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18821710.3A Active EP3710610B1 (de) 2017-11-14 2018-11-14 Superlegierung auf nickelbasis, einkristalline schaufel und turbomaschine

Country Status (7)

Country Link
US (2) US11396685B2 (de)
EP (1) EP3710610B1 (de)
JP (1) JP7305660B2 (de)
CN (1) CN111630195A (de)
CA (1) CA3081896A1 (de)
FR (1) FR3073527B1 (de)
WO (1) WO2019097162A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3073527B1 (fr) * 2017-11-14 2019-11-29 Safran Superalliage a base de nickel, aube monocristalline et turbomachine
FR3097879B1 (fr) * 2019-06-28 2021-05-28 Safran Aircraft Engines Procede de fabrication d’une piece en superalliage monocristallin
FR3101643B1 (fr) * 2019-10-08 2022-05-06 Safran Piece d'aeronef en superalliage comprenant du rhenium et/ou du ruthenium et procede de fabrication associe
FR3108365B1 (fr) 2020-03-18 2022-09-09 Safran Helicopter Engines Aube pour turbomachine comprenant un revetement anticorrosion, turbomachine comprenant l’aube et procede de depot du revetement sur l’aube
FR3125067B1 (fr) * 2021-07-07 2024-01-19 Safran Superalliage a base de nickel, aube monocristalline et turbomachine
FR3138451A1 (fr) * 2022-07-28 2024-02-02 Safran Procédé d’application de revêtement et aube de turbine avec revêtement appliqué suivant ce procédé

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1212020A (en) * 1981-09-14 1986-09-30 David N. Duhl Minor element additions to single crystals for improved oxidation resistance
US5151249A (en) * 1989-12-29 1992-09-29 General Electric Company Nickel-based single crystal superalloy and method of making
US5270123A (en) 1992-03-05 1993-12-14 General Electric Company Nickel-base superalloy and article with high temperature strength and improved stability
US5366695A (en) 1992-06-29 1994-11-22 Cannon-Muskegon Corporation Single crystal nickel-based superalloy
US5482789A (en) 1994-01-03 1996-01-09 General Electric Company Nickel base superalloy and article
DE19624055A1 (de) * 1996-06-17 1997-12-18 Abb Research Ltd Nickel-Basis-Superlegierung
US6015630A (en) * 1997-04-10 2000-01-18 The University Of Connecticut Ceramic materials for thermal barrier coatings
JPH11310839A (ja) * 1998-04-28 1999-11-09 Hitachi Ltd 高強度Ｎｉ基超合金方向性凝固鋳物
FR2780982B1 (fr) 1998-07-07 2000-09-08 Onera (Off Nat Aerospatiale) Superalliage monocristallin a base de nickel a haut solvus
EP1054072B1 (de) 1999-05-20 2003-04-02 ALSTOM (Switzerland) Ltd Nickel-Basis-Superlegierung
US6444057B1 (en) 1999-05-26 2002-09-03 General Electric Company Compositions and single-crystal articles of hafnium-modified and/or zirconium-modified nickel-base superalloys
US7473326B2 (en) * 2002-03-27 2009-01-06 National Institute For Materials Science Ni-base directionally solidified superalloy and Ni-base single crystal superalloy
US6929868B2 (en) * 2002-11-20 2005-08-16 General Electric Company SRZ-susceptible superalloy article having a protective layer thereon
RU2293782C1 (ru) 2005-08-15 2007-02-20 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Никелевый жаропрочный сплав для монокристаллического литья и изделие, выполненное из него
US8926897B2 (en) * 2005-09-27 2015-01-06 National Institute For Materials Science Nickel-base superalloy excellent in the oxidation resistance
JP5146867B2 (ja) * 2006-08-18 2013-02-20 独立行政法人物質・材料研究機構 高温耐久性に優れた耐熱部材
JP5177559B2 (ja) 2006-09-13 2013-04-03 独立行政法人物質・材料研究機構 Ｎｉ基単結晶超合金
US20090123722A1 (en) * 2007-11-08 2009-05-14 Allen David B Coating system
US8449262B2 (en) 2009-12-08 2013-05-28 Honeywell International Inc. Nickel-based superalloys, turbine blades, and methods of improving or repairing turbine engine components
US20130202913A1 (en) 2010-10-19 2013-08-08 Kyoko Kawagishi Ni-BASED SUPERALLOY COMPONENT HAVING HEAT-RESISTANT BOND COAT LAYER FORMED THEREIN
CN102732750B (zh) * 2011-04-08 2015-06-10 中国科学院金属研究所 一种低成本、低密度镍基单晶高温合金
US9518311B2 (en) 2014-05-08 2016-12-13 Cannon-Muskegon Corporation High strength single crystal superalloy
GB2540964A (en) 2015-07-31 2017-02-08 Univ Oxford Innovation Ltd A nickel-based alloy
DE102016202837A1 (de) 2016-02-24 2017-08-24 MTU Aero Engines AG Wärmebehandlungsverfahren für Bauteile aus Nickelbasis-Superlegierungen
FR3073527B1 (fr) * 2017-11-14 2019-11-29 Safran Superalliage a base de nickel, aube monocristalline et turbomachine

Also Published As

Publication number Publication date
RU2020119485A (ru) 2021-12-15
US11725261B2 (en) 2023-08-15
BR112020009498A2 (pt) 2020-11-03
US11396685B2 (en) 2022-07-26
JP2021503043A (ja) 2021-02-04
CA3081896A1 (fr) 2019-05-23
US20220364208A1 (en) 2022-11-17
US20210246533A1 (en) 2021-08-12
RU2020119485A3 (de) 2021-12-15
EP3710610A1 (de) 2020-09-23
FR3073527B1 (fr) 2019-11-29
CN111630195A (zh) 2020-09-04
JP7305660B2 (ja) 2023-07-10
WO2019097162A1 (fr) 2019-05-23
FR3073527A1 (fr) 2019-05-17

Similar Documents

Publication Publication Date Title
EP3710610B1 (de) Superlegierung auf nickelbasis, einkristalline schaufel und turbomaschine
EP3532648B1 (de) Superlegierung auf der basis von nickel, einkristalline turbinenschaufel und strömungsmaschine
EP3710611B1 (de) Superlegierung auf nickelbasis, einkristallschaufel und turbomaschine
EP3802895B1 (de) Superlegierung auf nickelbasis, einkristalline schaufel und turbomaschine
WO2023281205A1 (fr) Superalliage a base de nickel, aube monocristalline et turbomachine
WO2022269158A1 (fr) Superalliage a base de nickel, aube monocristalline et turbomachine
WO2024047315A1 (fr) Superalliage a base de nickel, aube monocristalline et turbomachine
WO2022269177A1 (fr) Superalliage a base de nickel, aube monocristalline et turbomachine
FR3121453A1 (fr) Superalliage a base de nickel, aube monocristalline et turbomachine
WO2024209156A1 (fr) Superalliage a base de nickel, aube monocristalline et turbomachine
EP3911774B1 (de) Nickelbasislegierung mit hoher mechanischer festigkeit bei hoher temperatur
EP3918101B1 (de) Superlegierung auf nickelbasis mit mit hoher mechanischer festigkeit und hoher beständigkeit gegen umwelteinflüsse bei hoher temperatur und mit geringer dichte
FR3117506A1 (fr) Procede de fabrication d&#39;une piece en superalliage monocristallin
FR3117507A1 (fr) Procede de fabrication d&#39;une piece en superalliage monocristallin
WO2020260645A1 (fr) Procédé de fabrication d&#39;une pièce en superalliage monocristallin

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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: 20200518

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

DAV Request for validation of the european patent (deleted)
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: 20210901

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: 20230102

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

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1558298

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230415

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018048139

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

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: 20230405

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1558298

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230405

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: 20230405

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: 20230405

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: 20230807

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: 20230705

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: 20230405

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: 20230405

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: 20230405

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: 20230405

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: 20230405

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: 20230405

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: 20230805

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: 20230405

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: 20230706

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: 20230405

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

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: 20230405

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018048139

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: 20230405

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

Ref country code: GB

Payment date: 20231019

Year of fee payment: 6

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: 20230405

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: 20230405

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: 20230405

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: 20230405

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: 20230405

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: 20230405

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

Ref country code: FR

Payment date: 20231019

Year of fee payment: 6

Ref country code: DE

Payment date: 20231019

Year of fee payment: 6

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

26N No opposition filed

Effective date: 20240108

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: 20230405

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: 20230405

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: 20230405

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: 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: 20230405

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: 20231114

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

Ref country code: CH

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

Effective date: 20231130

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: 20230405

Ref country code: LU

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

Effective date: 20231114

Ref country code: CH

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

Effective date: 20231130

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20231130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: IE

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

Effective date: 20231114

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: 20231130