EP3911774A1 - Superalliage a base de nickel a tenue mecanique elevee a haute temperature - Google Patents
Superalliage a base de nickel a tenue mecanique elevee a haute temperatureInfo
- Publication number
- EP3911774A1 EP3911774A1 EP20706569.9A EP20706569A EP3911774A1 EP 3911774 A1 EP3911774 A1 EP 3911774A1 EP 20706569 A EP20706569 A EP 20706569A EP 3911774 A1 EP3911774 A1 EP 3911774A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- superalloy
- nickel
- chromium
- aluminum
- rhenium
- 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
Links
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
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
- C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2204/00—End product comprising different layers, coatings or parts of cermet
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
- F05B2280/00—Materials; Properties thereof
- F05B2280/10—Inorganic materials, e.g. metals
- F05B2280/1074—Alloys not otherwise provided for
- F05B2280/10741—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
- F05D2300/13—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
- F05D2300/17—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
- the present invention relates to the general field of nickel-based superalloys for turbomachines, in particular for fixed blades, also called distributors or rectifiers, or mobile blades, or even ring segments.
- Nickel-based superalloys are generally used for the hot parts of turbomachines, that is, the parts of turbomachines located downstream of the combustion chamber.
- nickel-based superalloys combine high creep resistance at temperatures between 650 ° C and 1200 ° C, as well as resistance to oxidation and corrosion.
- the resistance to high temperatures is mainly due to the microstructure of these materials, which is composed of a g-Ni matrix of face-centered cubic crystal structure (CFC) and ordered hardening precipitates y'-Ni3AI of structure L1 2 .
- CFC face-centered cubic crystal structure
- a protective coating can be deposited on the part.
- the protective coating may also have a thermal insulating role to reduce the temperature seen by the superalloy substrate on which the protective coating is deposited.
- the protective coating is generally composed of a first layer, and a second layer deposited on the first layer.
- the first layer generally called the tie layer or sub-layer, is deposited on the superalloy.
- the first layer is commonly composed of an aluminoforming alloy.
- the second layer is a porous ceramic coating.
- parasitic grains of the “Freckle” type may form. These parasitic grains are liable to cause the part to break prematurely.
- the object of the present invention is to provide compositions of nickel-based superalloys which make it possible to improve the adhesion between the superalloy and the protective coating.
- Another object of the present invention is to provide compositions of nickel-based superalloys which make it possible to improve the mechanical characteristics, and in particular the resistance to creep.
- Another object of the present invention is to provide superalloy compositions which has good resistance to the environment, and in particular resistance to corrosion and resistance to oxidation.
- the present also aims to provide superalloy compositions which has a reduced density.
- the invention provides a nickel-based superalloy comprising, in percentages by weight, 4 to 6% aluminum, 5 to 8% cobalt, 6 to 9% chromium, 0.1 to 0.9. % hafnium, 2 to 4% molybdenum, 5 to 7% rhenium, 5 to 7% tantalum, 2 to 5% tungsten, 0 to 0.1% silicon, the remainder being nickel and impurities inevitable.
- a nickel-based alloy is defined as an alloy in which the percentage by mass of nickel is predominant.
- Unavoidable impurities are defined as those elements which are not intentionally added to the composition and which are supplied with other elements.
- inevitable impurities mention may in particular be made of carbon (C) and sulfur (S).
- the nickel-based superalloy according to the invention has good microstructural stability at temperature, thus making it possible to obtain high mechanical characteristics at temperature.
- the nickel-based superalloy according to the invention makes it possible to improve the resistance of a protective coating on said superalloy thanks to the absence of titanium (Ti).
- the nickel-based superalloy according to the invention has high resistance to corrosion and oxidation.
- the nickel-based superalloy according to the invention reduces the susceptibility to the formation of foundry defects.
- the nickel-based superalloy according to the invention makes it possible to have a density of less than 8.9 g. cm 3 .
- the superalloy may comprise, in percentages by weight, 4.5 to 5.5% aluminum, 5 to 8% cobalt, 6.5 to 8.5% chromium, 0.1 to 0, 6% hafnium, 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 to 4.5% tungsten, 0 at 0.1% silicon, the remainder being nickel and inevitable impurities.
- the superalloy may comprise, in percentages by mass, 4.5 to 5.5% aluminum, 5 to 8% cobalt, 6.5 to 8.5% chromium, 0.1 to 0.6% hafnium, 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 to 4.5% tungsten, the remainder being consisting of nickel and unavoidable impurities.
- silicon is an unavoidable impurity.
- the superalloy can also comprise, in percentages by mass, 4.5 to 5.5% aluminum, 5 to 8% cobalt, 6.5 to 8.5% chromium, 0.2 to 0.5% hafnium , 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 to 4.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy may comprise, in percentages by weight, 4.5 to 5.5% aluminum, 6 to 8% cobalt, 6.5 to 7.5% chromium, 0.1 to 0, 6% hafnium, and preferably 0.2 to 0.5%, 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 3.5 to 4.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy can also comprise, in percentages by mass, 4.5 to 5.5% aluminum, 6 to 8% cobalt, 6.5 to 7.5% chromium, 0.1 to 0 , 6% hafnium, and preferably 0.2 to 0.5%, 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum , 2.5 to 3.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy may further comprise, in percentages by weight, 4.5 to 5.5% aluminum, 5 to 7% cobalt, 6.5 to 7.5% chromium, 0.1 to 0.6% of hafnium, and preferably 0.2 to 0.5%, 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 3.5% tungsten, the remainder being nickel and the inevitable impurities.
- the superalloy may comprise, in percentages by weight, 4.5 to 5.5% aluminum, 6 to 8% cobalt, 7.5 to 8.5% chromium, 0.1 to 0, 6% hafnium, and preferably 0.2 to 0.5%, 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 to 3.5% tungsten, the remainder being nickel and inevitable impurities.
- the invention provides a nickel-based superalloy turbomachine part according to any one of the preceding characteristics.
- the part may be an element of an aircraft turbomachine turbine, for example a high-pressure turbine or a low-pressure turbine, or else a compressor element, and in particular a high-pressure compressor.
- the turbine or compressor part may be a blade, said blade possibly being a moving blade or a fixed blade, or else a ring sector.
- the turbomachine part comprises a thermal protective coating formed of a bonding layer deposited on the superalloy to nickel base, and a thermal barrier layer deposited on the tie layer.
- the turbomachine part is monocrystalline, preferably with a crystalline structure oriented in a crystallographic direction ⁇ 001>.
- the invention provides a method of manufacturing a nickel-based superalloy turbomachine part according to any one of the preceding characteristics by foundry.
- the method comprises depositing a thermal protective coating on the part in nickel-based superalloy according to the following steps:
- the superalloy according to the invention comprises a nickel base with which major addition elements are associated.
- Major addition elements include: cobalt Co, chromium Cr, molybdenum Mo, tungsten W, aluminum Al, tantalum Ta, titanium Ti, and rhenium Re.
- the superalloy can also include minor addition elements, which are addition elements whose maximum percentage in the superalloy does not exceed 1% by weight percent.
- Minor addition elements include: hafnium Hf and silicon Si.
- the nickel-based superalloy comprises, in percentages by mass, 4 to 6% aluminum, 5 to 8% cobalt, 6 to 9% chromium, 0.1 to 0.9% hafnium, 2 to 4% of molybdenum, 5 to 7% rhenium, 5 to 7% tantalum, 2 to 5% tungsten, 0 to 0.1% silicon, the remainder being nickel and inevitable impurities.
- the nickel-based superalloy may also advantageously comprise, in percentages by weight, 4 to 6% aluminum, 5 to 8% cobalt, 6 to 9% chromium, 0.1 to 0.9% hafnium, 2-4% molybdenum, 5-7% rhenium, 5-7% tantalum, 2-5% tungsten, the remainder being nickel and unavoidable impurities.
- silicon is an inevitable impurity.
- the nickel-based superalloy can also advantageously comprise, in percentages by weight, 4.5 to 5.5% aluminum, 5 to 8% cobalt, 6.5 to 8.5% chromium, 0.1 0.6% hafnium, 2.5-3.5% molybdenum, 5.5-6.5% rhenium, 5.5-6.5% tantalum, 2.5-4.5% tungsten, 0 to 0.1% silicon, the remainder being nickel and inevitable impurities.
- the nickel-based superalloy can also advantageously comprise, in percentages by weight, 4.5 to 5.5% aluminum, 5 to 8% cobalt, 6.5 to 8.5% chromium, 0.1 0.6% hafnium, 2.5-3.5% molybdenum, 5.5-6.5% rhenium, 5.5-6.5% tantalum, 2.5-4.5% tungsten, the remainder being nickel and inevitable impurities.
- silicon is an inevitable impurity.
- the nickel-based superalloy can also advantageously comprise, in percentages by mass, 4.5 to 5.5% aluminum, 5 to 8% cobalt, 6.5 to 8.5% chromium, 0.2 0.5% hafnium, 2.5-3.5% molybdenum, 5.5-6.5% rhenium, 5.5-6.5% tantalum, 2.5-4.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy can also advantageously comprise, in percentages by weight, 4.5 to 5.5% aluminum, 6 to 8% cobalt, 6.5 to 7.5% chromium, 0.1 to 0, 6% hafnium (and preferably 0.2 to 0.5%), 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum , 3.5 to 4.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy may comprise, in weight percentages, 4.5 to 5.5% aluminum, 6 to 8% cobalt, 6.5 to 7.5% chromium, 0.1 to 0.6 % hafnium (and preferably 0.2 to 0.5%), 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 to 3.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy can also advantageously comprise, in percentages by mass, 4.5 to 5.5% aluminum, 5 to 7% cobalt, 6.5 to 7.5% chromium, 0.1 to 0, 6% hafnium (and preferably 0.2 to 0.5%), 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum , 2.5 to 3.5% tungsten, the remainder being nickel and inevitable impurities.
- the superalloy may comprise, in percentages by weight, 4.5 to 5.5% aluminum, 6 to 8% cobalt, 7.5 to 8.5% chromium, 0.1 to 0.6 % hafnium (and preferably 0.2 to 0.5%), 2.5 to 3.5% molybdenum, 5.5 to 6.5% rhenium, 5.5 to 6.5% tantalum, 2.5 to 3.5% tungsten, the remainder being nickel and inevitable impurities.
- Cobalt, chromium, tungsten, molybdenum and rhenium participate mainly in the hardening of phase g, the austenitic matrix of CFC structure.
- Aluminum and tantalum promote the precipitation of the y 'phase, the hardening phase Ni 3 (Al, Ti, Ta) with an ordered cubic structure L1 2 .
- rhenium slows down diffusive processes, limits the coalescence of the g ’phase, thus improving creep resistance at high temperature.
- the rhenium content should not be too high so as not to negatively impact the other mechanical properties of the superalloy part.
- the refractory elements of molybdenum, tungsten, rhenium and tantalum also make it possible to slow down the mechanisms controlled by diffusion, thus improving the creep resistance of the superalloy part.
- chromium and aluminum improve resistance to oxidation and corrosion at high temperature, especially around 900 ° C for corrosion, and around 1,100 ° C for oxidation. .
- Hafnium also makes it possible to optimize the resistance to hot oxidation of the superalloy by increasing the adhesion of the layer of alumina Al 2 O 3 which forms on the surface of the superalloy at high temperature in an oxidizing medium.
- Silicon can also make it possible to optimize the resistance to hot oxidation of the superalloy. Furthermore, chromium and cobalt make it possible to reduce the temperature of solvus g 'of the superalloy.
- Cobalt is an element chemically close to nickel which partly replaces nickel to form a solid solution in phase g, thus making it possible to reinforce matrix g, to reduce the sensitivity to precipitation of topologically compact phases, in particular m phases , P, R, et s, and lavas, and reduce susceptibility to secondary reaction zone (ZRS) formation.
- ZRS secondary reaction zone
- the fact that the superalloy does not include titanium is beneficial for the strength and life of a thermal protective coating deposited on the superalloy.
- Such a superalloy composition makes it possible to improve the mechanical strength properties at high temperature (650 ° C-1200 ° C) of the parts made from said superalloy.
- such a superalloy composition makes it possible to obtain a minimum breaking stress of 290 MPa at 950 ° C for 110Oh, as well as a minimum breaking stress of 150Mpa at 1050 ° C for 550h, and as well as a breaking stress minimum of 55MPa at 1200 ° C for 51 Ohm.
- Such mechanical properties are in particular due to a microstructure comprising a phase g and a phase g ′, and a maximum content of topologically compact phases of 6%, in molar percentage.
- Topologically compact phases include m, P, R, and s phases, as well as Laves.
- the microstructure can also include the following carbides: MC, M 6 C, M 7 C 3 , and M 23 C 6
- Such a superalloy composition also makes it possible to obtain high resistance to oxidation and to corrosion of parts made from said superalloy. Resistance to corrosion and oxidation is obtained by ensuring a minimum of 9.5%, in atomic percentage, of aluminum in phase g at 1200 ° C, and a minimum of 7.5%, in atomic percentage , chromium in phase g at 1200 ° C, thus ensuring the formation of a protective layer of alumina on the surface of the material.
- such a superalloy composition makes it possible to simplify the process for manufacturing the part.
- Such a simplification is ensured by obtaining a difference of at least 10 ° K between the solvus temperature of the precipitates g 'and the solidus temperature of the superalloy, thus facilitating the implementation of a step of redissolving the precipitates g 'during the manufacture of the part.
- such a superalloy composition makes it possible to improve the manufacture by reducing the risk of formation of defects during the manufacture of the part, and in particular the formation of parasitic grains of the "Freckle" type during the directed solidification.
- the superalloy composition makes it possible to reduce the part's sensitivity to the formation of parasitic “Freckles” grains.
- the part's sensitivity to the formation of "Freckles” parasitic grains is evaluated using Konter's criterion, denoted NFP, which is given by the following equation (1):
- Ta corresponds to the tantalum content in the superalloy, in percentage by mass
- Hf corresponds to the hafnium content in the superalloy, in percentage by mass
- Mo corresponds to the molybdenum content in the superalloy, in percentage by mass
- Ti corresponds to the content of titanium in the superalloy, in percentage by mass
- W corresponds to the content of tungsten in the superalloy, in percentage by mass
- % Re corresponds to the content of rhenium in the superalloy, in percentage by mass.
- the superalloy composition makes it possible to obtain an NFP parameter greater than or equal to 0.7, a value from which the formation of parasitic “Freckles” grains is greatly reduced. Moreover, such a superalloy composition makes it possible to obtain a reduced density, in particular a density of less than 8.9 g / cm 3 .
- Table 1 below gives the composition, in percentages by weight, of four examples of superalloys according to the invention, Examples 1 to 4, as well as commercial or reference superalloys, Examples 5 to 9.
- Example 5 corresponds to the René®N5 superalloy
- example 6 corresponds to the CMSX-4® superalloy
- example 7 corresponds to the CMSX-4 Plus® Mod C superalloy
- example 8 corresponds to the René®N6 superalloy
- example 9 corresponds with CMSX-10 K® superalloy.
- Table 2 gives estimated characteristics of the superalloys cited in Table 1.
- the characteristics given in Table 2 are density (density), Konter's criterion (NFP), as well as the ultimate stress at 950 ° C for 110Oh, the breaking stress at 1050 ° C for 550h, and the breaking stress at 1200 ° C for 51 Oh, the breaking stresses are named CRF in Table 2, for creep criterion. [Table 2]
- the superalloys according to the invention make it possible to maintain the density below 8.9 g. cm 3 , thus making the superalloys according to the invention compatible with rotating applications, such as, for example, turbine blades.
- the microstructure of the superalloys according to the invention makes it possible to improve the mechanical properties at high temperature of said superalloys according to the invention.
- Such a microstructure is obtained by promoting the hardening of the matrix g at high temperature rather than promoting hardening by precipitation g ', the promotion of the hardening of the matrix g being obtained by the enrichment in hardening elements such as rhenium, tungsten, molybdenum, chromium and cobalt.
- the alloys according to the invention exhibit a breaking stress at 950 ° C. for 110Oh greater than 290 MPa, or even greater than or equal to 300 MPa for examples 1, 3 and 4, while at most the alloy according to Example 9 exhibits a breaking stress at 950 ° C. for 110 hours of 285 MPa.
- the alloys according to the invention exhibit a breaking stress at 1050 ° C for 550 hours greater than 180 IVPa, while at most the alloy according to Example 9 exhibits a breaking stress at 1050 ° C. for 550 hours of 160 MPa.
- the alloys according to the invention exhibit a breaking stress at 1200 ° C for 51 Ohm greater than 75 MF3 ⁇ 4, or even greater than or equal to 80 MPa for Examples 1, 2 and 4, while at most the alloy according to The example 5 exhibits a breaking stress at 1200 ° C hanging 51 Oh of 73 MPa.
- the alloys according to the invention have an overall breaking stress 10% to 30% greater than the breaking stress of the alloys of Examples 5 to 9.
- Table 3 gives the estimated characteristics of the superalloys mentioned in Table 1.
- the characteristics given in Table 3 are the different transformation temperatures (the solvus, the solidus and the liquidus), the molar fraction of the phase g 'at 900 ° C, at 1050 ° C and at 1200 ° C, the molar fraction of the topologically compact phases (PTC) at 900 ° C and at 1050 ° C.
- the mole fraction of topologically compact phases, which are embrittling phases, for the superalloys of Examples 1 to 4 is low at 900 ° C ( ⁇ 3%) and zero at 1050 ° C, reflecting also great stability of the microstructure, which is beneficial for the mechanical characteristics at high temperature.
- Table 4 gives estimated characteristics of the superalloys cited in Table 1.
- the characteristics given in Table 4 are the activity of chromium in phase g at 900 ° C, and the activity of aluminum in phase g at 1100 ° C.
- the activities of chromium and aluminum in matrix g are an indication of the resistance to corrosion and oxidation, the higher the activity of chromium and the activity of aluminum in the matrix, the higher the resistance to corrosion and oxidation.
- the superalloys according to the invention exhibit a chromium activity at 900 ° C of the same order of magnitude as the superalloys of Examples 5 and 6 which are superalloys recognized for having high corrosion resistance.
- the superalloys according to the invention exhibit an aluminum activity at 1100 ° C greater than the superalloy according to Example 9, thus ensuring satisfactory resistance to oxidation.
- the nickel-based superalloy part can be produced by casting.
- Casting of the part is accomplished by melting the superalloy, with the liquid superalloy being poured into a mold to cool and solidify.
- the manufacture by foundry of the part can for example be carried out with the lost wax technique, in particular to manufacture a blade.
- the part manufacturing process may include a step of depositing a thermal protective coating on the part made of superalloy. nickel.
- the thermal protective coating is deposited according to the following steps:
- the function of the tie layer is to form an alumina layer which provides protection against oxidation of the underlying superalloy.
- the tie layer can have a thickness between 50 ⁇ m and 100 ⁇ m.
- the bonding layer can be obtained by depositing a layer of platinum on the superalloy, for example by electrodeposition or by chemical vapor deposition, aluminization at a temperature above 1000 ° C then being carried out in order on the one hand to deposit aluminum on the platinum layer, and on the other hand to ensure a supply of nickel from the superalloy in the bonding layer by diffusion.
- the bonding layer may also be formed by depositing a plurality of elementary layers of platinum, nickel and aluminum, for example by physical vapor deposition, a heat treatment then being carried out in order to ensure a reaction between the metals of the layers. filed.
- the thermal barrier layer can be a ceramic, such as, for example, yttriated zirconia, which offers the advantage of having very low thermal conductivity and a high coefficient of expansion.
- the thermal barrier layer can be deposited by plasma spraying, or even by physical vapor deposition.
- the tie layer can have a thickness between 100 ⁇ m and 200 ⁇ m.
- the thermal protective coating makes it possible, on the one hand, to limit the temperature to which the superalloy is exposed, and on the other hand to protect the superalloy from the oxygen of the environment in which the part is located.
- the protective coating is advantageous for turbine blades which are parts exposed to combustion gases.
- the method can comprise a directed solidification step. Directed solidification is carried out by controlling the thermal gradient and the rate of solidification of the superalloy, and by introducing a monocrystalline seed, in order to avoid the appearance of new seeds in front of the solidification front.
- Directed solidification can in particular allow the manufacture of a monocrystalline part whose crystalline structure is oriented in a crystallographic direction ⁇ 001>, such an orientation offering better mechanical properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Ceramic Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1900390A FR3091709B1 (fr) | 2019-01-16 | 2019-01-16 | Superalliage à base de nickel à tenue mécanique élevée à haute température |
| PCT/FR2020/050049 WO2020148504A1 (fr) | 2019-01-16 | 2020-01-14 | Superalliage a base de nickel a tenue mecanique elevee a haute temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3911774A1 true EP3911774A1 (fr) | 2021-11-24 |
| EP3911774B1 EP3911774B1 (fr) | 2023-03-01 |
Family
ID=67875496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20706569.9A Active EP3911774B1 (fr) | 2019-01-16 | 2020-01-14 | Superalliage a base de nickel a tenue mecanique elevee a haute temperature |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US12312658B2 (fr) |
| EP (1) | EP3911774B1 (fr) |
| CN (1) | CN113544303A (fr) |
| FR (1) | FR3091709B1 (fr) |
| WO (1) | WO2020148504A1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230357897A1 (en) * | 2022-05-05 | 2023-11-09 | General Electric Company | Nickel-based superalloys and articles |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119458A (en) | 1977-11-14 | 1978-10-10 | General Electric Company | Method of forming a superalloy |
| US4801513A (en) | 1981-09-14 | 1989-01-31 | United Technologies Corporation | Minor element additions to single crystals for improved oxidation resistance |
| US6015630A (en) * | 1997-04-10 | 2000-01-18 | The University Of Connecticut | Ceramic materials for thermal barrier coatings |
| FR2780982B1 (fr) * | 1998-07-07 | 2000-09-08 | Onera (Off Nat Aerospatiale) | Superalliage monocristallin a base de nickel a haut solvus |
| AU2001243302A1 (en) * | 2000-02-29 | 2001-09-12 | General Electric Company | Nickel base superalloys and turbine components fabricated therefrom |
| US20030041930A1 (en) * | 2001-08-30 | 2003-03-06 | Deluca Daniel P. | Modified advanced high strength single crystal superalloy composition |
| DE50112339D1 (de) * | 2001-12-13 | 2007-05-24 | Siemens Ag | Hochtemperaturbeständiges Bauteil aus einkristalliner oder polykristalliner Nickel-Basis-Superlegierung |
| US8241560B2 (en) * | 2003-04-28 | 2012-08-14 | Howmet Corporation | Nickel base superalloy and single crystal castings |
| CN101652487B (zh) * | 2006-09-13 | 2012-02-08 | 独立行政法人物质.材料研究机构 | Ni基单结晶超合金 |
| US7704332B2 (en) * | 2006-12-13 | 2010-04-27 | United Technologies Corporation | Moderate density, low density, and extremely low density single crystal alloys for high AN2 applications |
| CA2680650C (fr) * | 2007-03-12 | 2012-07-03 | Ihi Corporation | Superalliage monocristallin a base de nickel et pale de turbine comportant cet alliage |
| US9138963B2 (en) * | 2009-12-14 | 2015-09-22 | United Technologies Corporation | Low sulfur nickel base substrate alloy and overlay coating system |
| US9518311B2 (en) * | 2014-05-08 | 2016-12-13 | Cannon-Muskegon Corporation | High strength single crystal superalloy |
| FR3057880B1 (fr) * | 2016-10-25 | 2018-11-23 | Safran | Superalliage a base de nickel, aube monocristalline et turbomachine |
-
2019
- 2019-01-16 FR FR1900390A patent/FR3091709B1/fr active Active
-
2020
- 2020-01-14 WO PCT/FR2020/050049 patent/WO2020148504A1/fr not_active Ceased
- 2020-01-14 EP EP20706569.9A patent/EP3911774B1/fr active Active
- 2020-01-14 CN CN202080009476.5A patent/CN113544303A/zh active Pending
- 2020-01-14 US US17/422,044 patent/US12312658B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US12312658B2 (en) | 2025-05-27 |
| US20220098705A1 (en) | 2022-03-31 |
| FR3091709A1 (fr) | 2020-07-17 |
| WO2020148504A1 (fr) | 2020-07-23 |
| CN113544303A (zh) | 2021-10-22 |
| FR3091709B1 (fr) | 2021-01-22 |
| EP3911774B1 (fr) | 2023-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3532648B1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine. | |
| EP3710610B1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| EP3710611B1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| EP3802895B1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| EP3911774B1 (fr) | Superalliage a base de nickel a tenue mecanique elevee a haute temperature | |
| EP4367278B1 (fr) | Superalliage à base de nickel, aube monocristalline et turbomachine | |
| FR3113255A1 (fr) | Protection contre l’oxydation ou la corrosion d’une pièce creuse en superalliage | |
| EP3911773B1 (fr) | Superalliage a base de nickel a faible densite et avec une tenue mecanique et environnementale elevee a haute temperature | |
| EP4314370A1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| EP3918101B1 (fr) | Superalliage a base de nickel a tenue mecanique et environnementale elevee a haute temperature et a faible densite | |
| EP4359580B1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| FR3124195A1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| FR3139347A1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
| FR3147571A1 (fr) | Superalliage a base de nickel, aube monocristalline | |
| WO2022029388A1 (fr) | Protection contre l'oxydation ou la corrosion d'une piece creuse en superalliage |
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: 20210811 |
|
| 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 |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| 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: 20220907 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1551023 Country of ref document: AT Kind code of ref document: T Effective date: 20230315 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602020008490 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: 20230301 |
|
| 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: 20230301 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: 20230601 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: 20230301 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: 20230301 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: 20230301 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: 20230301 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1551023 Country of ref document: AT Kind code of ref document: T Effective date: 20230301 |
|
| 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: 20230301 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: 20230301 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: 20230301 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: 20230602 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: 20230301 |
|
| 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: 20230301 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: 20230301 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: 20230703 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: 20230301 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: 20230301 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: 20230301 |
|
| 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: 20230301 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: 20230701 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602020008490 Country of ref document: DE |
|
| 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: 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: 20230301 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: 20230301 |
|
| 26N | No opposition filed |
Effective date: 20231204 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230301 |
|
| 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: 20230301 |
|
| 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: 20230301 |
|
| 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: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240114 |
|
| 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: 20240114 |
|
| 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: 20240131 |
|
| 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: 20240131 |
|
| 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: 20240131 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240131 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20240131 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20230301 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20230301 |
|
| 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: 20240114 |
|
| 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: 20240114 |
|
| 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; INVALID AB INITIO Effective date: 20200114 |
|
| 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: 20200114 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20230301 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20260122 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20260120 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20260121 Year of fee payment: 7 |