EP3007844A1 - Procédé de fabrication d'une pièce en alliage en titane-aluminium - Google Patents
Procédé de fabrication d'une pièce en alliage en titane-aluminiumInfo
- Publication number
- EP3007844A1 EP3007844A1 EP14734884.1A EP14734884A EP3007844A1 EP 3007844 A1 EP3007844 A1 EP 3007844A1 EP 14734884 A EP14734884 A EP 14734884A EP 3007844 A1 EP3007844 A1 EP 3007844A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- temperature
- titanium
- manufacture
- tungsten
- mpa
- 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
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 229910000838 Al alloy Inorganic materials 0.000 title description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 239000010937 tungsten Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000010955 niobium Substances 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 31
- 238000005245 sintering Methods 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims 1
- 238000002490 spark plasma sintering Methods 0.000 abstract description 16
- 239000000843 powder Substances 0.000 abstract description 8
- 239000004411 aluminium Substances 0.000 abstract 2
- 229910045601 alloy Inorganic materials 0.000 description 50
- 239000000956 alloy Substances 0.000 description 50
- 239000000126 substance Substances 0.000 description 10
- 238000007711 solidification Methods 0.000 description 9
- 238000004663 powder metallurgy Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 230000002093 peripheral effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910000927 Ge alloy Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021324 titanium aluminide Inorganic materials 0.000 description 2
- 238000006677 Appel reaction Methods 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012011 method of payment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/008—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of engine cylinder parts or of piston parts other than piston rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/009—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of turbine components other than turbine blades
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/04—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of turbine blades
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
- C22C1/0458—Alloys based on titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L2303/00—Manufacturing of components used in valve arrangements
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2201/00—Metals
- F05C2201/02—Light metals
- F05C2201/021—Aluminium
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2201/00—Metals
- F05C2201/02—Light metals
- F05C2201/025—Boron
Definitions
- the present invention relates to the manufacture of a titanium-aluminum alloy (TiAl) for use as a structural material for the production of a part, for example in the aeronautical sector for the manufacture of turbine blades for aircraft or helicopter engines, or in the automobile field for the manufacture of valves.
- TiAl titanium-aluminum alloy
- a problem that arises in this type of industry is related to the quality of materials used in particular for the manufacture of parts exposed to very high temperature and pressure constraints.
- TiAI alloys have been the subject of intensive research since the 1980s with the aim of replacing nickel-base monocrystalline superalloys used for over fifty years for turbine blades.
- TiAl alloys have the advantage of having a density half that of superalloys. Their use improves engine performance, reduces structural load, reduces noise, saves fuel and reduces greenhouse gas emissions.
- Today most engine manufacturers have integrated TiAl alloy turbine blades in their latest aircraft engines. Until now, all these blades have a chemical composition called GE type (46 to 48% aluminum, 2% niobium and 2% chromium, titanium balancing) and are developed by the foundry pathway, followed heat treatments.
- the casting channel on GE alloys allows the manufacture of blades for low pressure stages of an aircraft engine.
- a GE type alloy is creep efficient due to the presence of a predominantly or totally lamellar microstructure.
- the incorporation into stages of more constrained and warmer engines through the manufacture of blades made of more efficient materials, especially more resistant to oxidation where the introduction in larger quantities of elements such as niobium and / or refractory elements such as tungsten. Since these alloys doped with refractory elements are characterized in the foundry by a poor ductility resulting from a high resistance, it is not currently possible to use such blades at other stages of an aircraft engine.
- the microstructures of these TiAI alloys Due to a relatively complex equilibrium diagram, the microstructures of these TiAI alloys, which are decisive for the properties, are strongly dependent on the heat history experienced by the alloy and the process of preparation used.
- biphasic ( ⁇ + 2 ), duplex ( ⁇ + lamellar) and lamellar microstructures are obtained.
- the ⁇ phase is quadratic with structure L1 0 , the phase a being hexagonal disordered and the phase with 2 hexagonal ordered structure DO 19 .
- the lamellar structure is obtained during the cooling of grains a.
- Solidification processes such as foundry or directed solidification allow the formation of columnar structures formed of elongate and lamellar grains with interfaces perpendicular to the longitudinal axis of the grains.
- Research shows that the most efficient microstructures are microstructures whose crystallographic grains have a size of a few tens of microns and are formed either exclusively or in a large proportion of lamellar grains. It has also been demonstrated that a small-grain lamellar microstructure obtained by a succession of heat treatments has a good mechanical strength and a ductility of the order of 5%, which is quite exceptional.
- Table 1 compares the mechanical properties of the alloys cited in this review.
- the numerical data characterize resistance and ductility at room temperature.
- the creep resistance is qualified for a temperature range of 700 to 750 ° C.
- column YS indicates the elastic limit (in MPa) at 0.2% of strain
- RM the stress at break (in MPa)
- A is the elongation at break of the material under consideration.
- Alloys containing niobium (called TNB: Ti-45AI- (5-10) Nb) were then developed, more particularly in connection with the forging process or for the manufacture of thin sheets.
- TNB Ti-45AI- (5-10) Nb
- the best creep results were obtained for extruded alloys containing carbon.
- the creep rate is 6.10 "9 s " 1 at 500 MPa at 700 ° C but the ductility of these alloys is on average 0.69%, with samples breaking at 0.34% deformation (Strength properties of hardened high-niobium precipitates containing titanium aluminum alloy, PAUL J, OEHRING M, HOPPE R, CALL F, Gamma Titanium Aluminides 2003, 403, TMS, 2003).
- ABB-type alloys US Pat. Nos. 5,286,443 and US 5,207,982
- G4 alloys FR-2,732,038
- ABB type alloys contain 2% by weight of tungsten and less than 0.5% of silicon and boron.
- One of the alloys of the ABB family of composition Ti-47AI-2W-0.5Si has been studied in detail. It has a fine microstructure formed of lamellar grains, feather structures and ⁇ zones and excellent resistance to creep but a very limited ductility.
- G4-type alloys contain 1% by weight of tungsten, 1% by weight of rhenium and 0.2% of silicon. These alloys exhibit excellent creep performance, as well as a reasonable ductility of 1.2% at 20 ° C.
- the strong interest of these alloys G4 comes from the fact that their mechanical properties are optimal in a simple structural state without homogenization treatment at very high temperature, unlike ABB type alloys.
- Line 7 of Table 1 gives the properties of alloys obtained by directed solidification: their microstructure is formed of elongated lamellar grains in the direction of solidification and with the interface planes parallel to this same direction.
- the alloy of composition ⁇ -46 ⁇ -1 Mo-0.5Si has an elongation at break of more than 25% at room temperature and a creep resistance of 3.5.10 "10 s " 1 at 750 ° C and 240 MPa .
- a process called ARCAM consists of the melting of powders by an electron beam, a technique that allows like the SPS (acronym for Spark Plasma Sintering, called in French flash sintering) to give a complex shape to the part.
- SPS synchrom for Spark Plasma Sintering
- Tensile test results show a ductility of the order of 1, 2% and a yield strength of the order of 350 MPa, for GE-type alloys densified by this process.
- a disadvantage related to this route lies in a loss of aluminum (typically 2 at% AI) during melting while the aluminum concentration is very critical for the properties.
- the implementation of this process also requires a vacuum chamber, which results in a high industrial cost.
- the present invention aims to overcome the disadvantages of the prior art. Its purpose is in particular to provide the means for producing a part exhibiting advantageous mechanical properties making it possible in particular to meet the needs of engine manufacturers for aeronautics by having a yield point of about 400 MPa at 0.2% ambient temperature at 0.2%. and an elongation at break of the order of 1, 5%, and creep at 700 ° C - 300 MPa and at 750 ° C - 200 MPa, a time before rupture of at least 400 hours.
- the present invention aims to provide a part with excellent properties including the point of view of the ductility at room temperature and the hot resistance.
- the term "piece” here means any product obtained by the present invention and intended to be used subsequently as a blank for a mechanical part, as a mechanical part (turbine blade, valve, etc.) or part of mechanical part (valve head, ...) or several mechanical parts (realization of several blades or valves or any set of mechanical parts, including complex mechanical parts).
- a pellet, a block, a bar or any other basic element that can be used for machining a mechanical component are here also considered to be one piece.
- the method according to the invention is also intended to obtain a part having a high homogeneity of microstructures and therefore excellent reproducibility of mechanical properties.
- the present invention will provide a method characterized by a low cost and robustness of the means for its implementation.
- the method according to the invention will advantageously also offer a high speed of elaboration and will allow the manufacture of the part without subsequent heat treatment, thus offering the possibility of directly manufacturing blade preforms and thus limiting the machining.
- the present invention proposes a flash sinter fabrication method of a metal alloy part (PF), comprising the simultaneous application of a uniaxial pressure and of an electric current to a tooling containing a constituent powder material to the following atomic percentage composition:
- chromium optionally 0 to 5% of one or more elements selected from chromium, niobium, molybdenum, silicon and carbon,
- titanium balancing and all the elements except aluminum and titanium being between 0.25 and 12%.
- the present invention therefore proposes to combine in a completely novel manner a titanium-aluminum alloy, having a particular chemical composition, with a flash sintering (or SPS) manufacturing process.
- a flash sintering (or SPS) manufacturing process is a process that makes it possible to obtain parts with mechanical characteristics that largely meet the requirements of the engine manufacturers in the aeronautical industry.
- the chemical composition of the material used in the process according to the invention is based on elements which are relatively inexpensive such as tungsten.
- the TiAl alloys conventionally manufactured by the foundry process are much less efficient in terms of the ductility / creep resistance compromise and the reproducibility of the microstructures than the alloys obtained by a process according to the present invention.
- this path (foundry) requires to apply to the alloys heat treatments and material machining more important than for the SPS channel.
- the use of the powder metallurgy (PW) pathway associated with that of flash sintering makes it possible here to refine and homogenize the microstructures for the alloys selected by the present invention and allows them to be used at the highest temperatures in the field. 'use.
- the electric current can pass directly into the powder material and / or into the tooling and thus causes an increase in the temperature of the material.
- the metal alloy part (PF) obtained at the end of the process according to the invention contains heavy elements in an amount of less than 5 atomic% and boron in a very small amount (0.05 to 1.5 atomic%), which makes it possible to obtain a lamellar microstructure with small grains resistant to creep.
- Another advantage of the present invention lies in the fact that it is not it is not necessary to systematically obtain low-aluminum grades to, for example, promote ⁇ -solidification, since the alloy obtained at the end of the process contains boron in order to obtain a fine microstructure with equiaxed grains. An originality compared to existing alloys is thus to be able to offer a rich aluminum grade which also has an interest in ductility and resistance to oxidation.
- the chemical composition-densification coupling by Spark Plasma Sintering makes it possible to obtain an alloy having a particular microstructure with exceptional mechanical properties. It is formed of small lamellar grains, surrounded by peripheral ⁇ zones. It is the combination of this method with the claimed chemical composition that makes it possible to obtain a piece with qualities far superior to those of the alloy parts of the prior art. In fact, a part with the same chemical composition as the one claimed but which would be produced by powder metallurgy (PW) in combination with the conventional hot isostatic compaction (DUC) process would not have exceptional properties. which confirms the original character obtained thanks to the method according to the invention.
- PW powder metallurgy
- DUC hot isostatic compaction
- the method thus defined according to the present invention makes it possible to limit the magnification of the grains, to obtain a thin lamellar microstructure, to have a ⁇ phase intrinsically resistant to heat and at ambient temperature, to have good reproducibility of the mechanical properties as well as a very good compromise between ductility at room temperature and resistance to creep at high temperature.
- the material used in the process according to the invention comprises at least one of the following elements in the proportions defined below:
- the material used in the context of the process according to the invention has the following composition in atomic percentage: 49.92% of titanium, 48.00% of aluminum, 2.00% of tungsten, 0.08% boron.
- the method according to the present invention comprises the following steps:
- a pressure of between 80 and 120 MPa is applied during step b).
- the pressure increases gradually during step b) over a period of less than 5 minutes.
- the temperature increases from 80 to 120 ° C / min.
- step c the temperature is maintained at the plateau for two minutes.
- the method according to the present invention is particularly advantageously used for the manufacture of a turbine blade preform and / or a turbocharger turbine wheel and / or a valve (or at least one valve head) and / or a piston pin.
- Figure 1 illustrates a change in pressure and temperature measured as a function of time during an SPS cycle implemented according to the invention
- FIG. 2 illustrates images obtained by SEM (acronym for Scanning Electron Microscopy) of a microstructure of a part resulting from the process according to the invention at different magnitudes
- FIG. 3 illustrates a large area of a microstructure of a part resulting from the process according to the invention studied in SEM and MET (acronym for Electron Microscopy in Transmission),
- FIG. 4 illustrates a peripheral ⁇ zone containing phase B2 precipitates between lamellar grains observed by TEM of the microstructure of a part resulting from the process according to the invention
- FIG. 5 illustrates local chemical analyzes by EDS-MEB (for energy dispersive X-ray spectroscopy - Scanning Electron Microscopy) of a part resulting from the process according to the invention
- FIG. 6 illustrates room temperature tensile curves obtained in two samples of the alloy obtained by the process according to the invention.
- FIG. 7 illustrates creep curves obtained at 700 ° C. under 300 MPa in two samples of the alloy obtained by the process according to the invention.
- one or more elements selected from chromium, niobium, molybdenum, silicon and carbon, titanium balancing and all the elements excluding aluminum and titanium being between 0.25 and 12%.
- This material contains heavy elements in a smaller amount at 5 atomic% and boron in very small quantity (0.05 to 1.5%).
- it comprises, in addition to titanium, aluminum and boron, at least one of the following elements in the proportions defined below:
- Alloys of small-grain lamellar structure are thus obtained by a simple SPS cycle according to the present invention.
- the SPS cycle used in the context of the invention is based on the process described in international application WO 2012/131625 in which a uniaxial pressure is applied, directly or via force transmission parts, by means of at least two pistons (P1, P2) sliding towards one another inside a matrix, said pistons and / or said force transmission parts having bearing surfaces in contact with the constituent and cooperating material between them to define the shape of the part to be manufactured.
- P1, P2 pistons sliding towards one another inside a matrix
- said pistons and / or said force transmission parts having bearing surfaces in contact with the constituent and cooperating material between them to define the shape of the part to be manufactured.
- FIGS. 3, 4 and 6 of this document Figure 1 of this prior international application illustrates a part obtainable with the device described.
- the device has the advantage of allowing the manufacture of complex shaped metal parts. However, it is possible to envisage using a different device allowing the implementation of an SPS method for the implementation of the present invention.
- the rise in temperature can be obtained by direct passage of the current in the powder material or by passing the current in the matrix which exchanges the heat with the powder material. After about 2 minutes of maintaining the bearing temperature (1355 ° C), the pressure and the heating are cut off. In less than 30 minutes, the densification test is complete and the sample available. It should be noted that Figure 1 illustrates in particular measured temperatures which are lower than the core temperature of the material but the temperature difference between the measured temperature and the temperature in the material is known because it can be calibrated.
- the alloy constituting the part obtained has a microstructure illustrated in FIG. 2 which presents images in scanning electron microscopy at different magnifications. It is formed of lamellar grains surrounded by ⁇ -phase peripheral zones containing phase B2 precipitates, with a strong white contrast. The lamellar grains have an average size of 30 ⁇ . The peripheral ⁇ zones are elongated (a few microns). In the lamellar zones, low-contrast ribbons (denoted BO in FIG. 2d) are observed which are borides.
- Figure 3 shows the same area observed under the microscope at scanning and transmission electron microscope.
- the lamellar zones generally have a classic appearance: they are formed of lamellae of average width 0.15 ⁇ and separated by very rectilinear interfaces. The proportion of phase a 2 in these lamellar zones is about 10%.
- Figure 4 shows in detail a peripheral zone, where we observe the extension of the phase y in the joints between lamellar grains.
- Figure 5 shows local analyzes of chemical composition by EDS-MEB. It is measured that the tungsten is distributed fairly homogeneously in all phases, which is quite unexpected because the phases B2 and a 2 are supposed to accept larger proportions.
- Figures 6 and 7 illustrate the exceptional mechanical properties of this alloy by showing tensile curves at room temperature and creep curves at 700 ° C at 300 MPa.
- two curves obtained for samples extracted from different SPS pellets were represented.
- the second test was stopped at 1.5% in order to study the microstructure of deformation by electron microscopy and to try to explain the good creep behavior.
- the superposition of the curves illustrates the high reproducibility of the mechanical properties of the samples obtained by the SPS process.
- the tensile curve at room temperature gives: an elongation at break of 1, 6%, a yield strength of 496 MPa and a breaking strength of 646 MPa. In creep at 700 ° C.
- the secondary velocity is 3.7 ⁇ 10 -9 s -1 and the time to rupture is 4076 hours, which is exceptional.
- the creep rate at 750 ° C. was measured. It is 2.3 ⁇ 10 -9 sec -1 at 120 MPa and 5.8 ⁇ 10 -9 sec -1 at 200 MPa, values which confirm the excellent creep resistance of the parts obtained according to the present invention.
- the ductility obtained could be explained by: i) the presence of peripheral ⁇ zones that accept a fairly large amount of deformation, ii) the characteristics of the lamellar zones (fairly large lamella size) which are also deformable and iii) the small size lamellar grains which limit the formation of internally constraining stacks causing rupture.
- the exceptional resistance to creep could be explained by the resistance of the lamellar structure and the good dispersion of tungsten in the matrix y that is deformed. It seems that the characteristic dimensions of the microstructure obtained at the end of the process according to the invention, namely the size of the grains and the width of the lamellae, are close to the ideal so that at the same time the dislocations do not move. not too easily by involving diffusion and that there are enough interfaces and grain boundaries to hinder the movement of dislocations.
- a metal alloy part could be manufactured.
- This part had characteristics going beyond the characteristics corresponding to the aforementioned requirements for turbine blades of an aircraft engine (elastic limit of about 400 MPa at 0.2% at room temperature and an elongation at break of the order of 1, 5%, and creep at 700 ° C - 300 MPa and at 750 ° C - 200 MPa, a time before break of at least 400 hours) and even filled the whole required specifications.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL14734884T PL3007844T3 (pl) | 2013-06-11 | 2014-06-11 | Sposób wytwarzania części ze stopu tytanu i glinu |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1355393A FR3006696B1 (fr) | 2013-06-11 | 2013-06-11 | Procede de fabrication d'une piece en alliage en titane-aluminium |
PCT/FR2014/051419 WO2014199082A1 (fr) | 2013-06-11 | 2014-06-11 | Procédé de fabrication d'une pièce en alliage en titane-aluminium |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3007844A1 true EP3007844A1 (fr) | 2016-04-20 |
EP3007844B1 EP3007844B1 (fr) | 2017-08-16 |
Family
ID=49620026
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14734884.1A Not-in-force EP3007844B1 (fr) | 2013-06-11 | 2014-06-11 | Procédé de fabrication d'une pièce en alliage en titane-aluminium |
Country Status (9)
Country | Link |
---|---|
US (1) | US10183331B2 (fr) |
EP (1) | EP3007844B1 (fr) |
JP (1) | JP6445542B2 (fr) |
KR (1) | KR20160033096A (fr) |
CN (1) | CN105451915B (fr) |
FR (1) | FR3006696B1 (fr) |
MX (1) | MX2015017070A (fr) |
PL (1) | PL3007844T3 (fr) |
WO (1) | WO2014199082A1 (fr) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104550956A (zh) * | 2015-01-20 | 2015-04-29 | 哈尔滨工业大学 | beta-gamma TiAl预合金粉放电等离子烧结制备构件的方法 |
KR20180112071A (ko) * | 2016-04-20 | 2018-10-11 | 아르코닉 인코포레이티드 | 알루미늄, 티타늄, 및 지르코늄으로 이루어진 hcp 재료, 및 이로 제조된 제품 |
CN107058799B (zh) * | 2017-01-22 | 2019-09-20 | 康硕电气集团有限公司 | 一种含铼3d打印用钛基合金材料及其制备方法 |
EP3391982B1 (fr) | 2017-04-21 | 2023-08-16 | Raytheon Technologies Corporation | Systèmes, dispositifs et procédés de frittage par plasma à étincelles |
CN108856708B (zh) * | 2017-05-09 | 2020-08-04 | 中国航空制造技术研究院 | 一种具有梯度组织的TiAl系材料及其制造方法 |
KR102010306B1 (ko) * | 2017-11-03 | 2019-08-13 | (주)차세대소재연구소 | 알루미늄-티타늄 이종 경사기능복합재료 및 이의 제조방법 |
EP3575016A1 (fr) * | 2018-06-01 | 2019-12-04 | Siemens Aktiengesellschaft | Améliorations relatives à la fabrication de composants en superalliage |
WO2020189215A1 (fr) * | 2019-03-18 | 2020-09-24 | 株式会社Ihi | Matériau d'alliage d'aluminure de titane pour forgeage à chaud, procédé de forgeage pour matériau d'alliage d'aluminure de titane, et corps forgé |
FR3105048B1 (fr) * | 2019-12-20 | 2022-08-05 | Safran | Solution de fabrication d'un disque aubage monobloc |
CN112756624A (zh) * | 2020-12-11 | 2021-05-07 | 丹阳层现三维科技有限公司 | 一种减少选区激光熔化打印钛铝合金中裂纹的方法 |
CN116607048A (zh) * | 2022-02-09 | 2023-08-18 | 中国科学院金属研究所 | 一种用于精密铸造的γ-TiAl合金及其制备方法 |
PL440911A1 (pl) | 2022-04-11 | 2023-10-16 | Kghm Polska Miedź Spółka Akcyjna | Trójskładnikowy stop tytanu, sposób jego wytwarzania i zastosowanie |
CN115404381B (zh) * | 2022-09-14 | 2023-06-30 | 西北工业大学 | 一种TiAl合金薄板及其低成本轧制方法 |
CN115466867B (zh) * | 2022-09-14 | 2023-05-05 | 西北工业大学 | 一种能够改善其均匀变形能力的TiAl合金及其制备方法 |
CN115627386B (zh) * | 2022-11-07 | 2023-10-24 | 西北工业大学 | 一种适用于轧制变形的TiAlRe合金及其轧制方法 |
CN115976367B (zh) * | 2023-02-17 | 2024-08-09 | 浙江工业大学 | 一种铼合金化钛铝合金及其制备方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE59106459D1 (de) | 1990-05-04 | 1995-10-19 | Asea Brown Boveri | Hochtemperaturlegierung für Maschinenbauteile auf der Basis von dotiertem Titanaluminid. |
JP2743720B2 (ja) * | 1992-07-03 | 1998-04-22 | トヨタ自動車株式会社 | TiB2 分散TiAl基複合材料の製造方法 |
JPH0892602A (ja) * | 1994-09-28 | 1996-04-09 | Toyo Alum Kk | TiAl金属間化合物粉末およびその焼結体 |
FR2732038B1 (fr) | 1995-03-24 | 1997-06-06 | Onera (Off Nat Aerospatiale) | Alliage intermetallique a base d'aluminiure de titane pour la fonderie |
CN100425722C (zh) * | 2005-11-30 | 2008-10-15 | 济南大学 | 改善TiAl金属间化合物基复合材料性能的方法 |
CN100496815C (zh) * | 2007-01-31 | 2009-06-10 | 哈尔滨工业大学 | 三维网状结构Ti2AlC增强的TiAl基复合材料及其制备方法 |
FR2973265B1 (fr) | 2011-03-31 | 2014-03-28 | Centre Nat Rech Scient | Procede de fabrication par frittage flash d'une piece de forme complexe et dispositif pour la mise en œuvre d'un tel procede. |
CN102492871A (zh) * | 2011-12-19 | 2012-06-13 | 武汉理工大学 | 一种TiAl金属间化合物基固体自润滑复合材料及其制备方法 |
CN102888549A (zh) * | 2012-10-19 | 2013-01-23 | 武汉理工大学 | TiAl-C-Ag-Ti2AlC-TiC自润滑复合材料及其制备方法 |
-
2013
- 2013-06-11 FR FR1355393A patent/FR3006696B1/fr not_active Expired - Fee Related
-
2014
- 2014-06-11 US US14/897,877 patent/US10183331B2/en active Active
- 2014-06-11 EP EP14734884.1A patent/EP3007844B1/fr not_active Not-in-force
- 2014-06-11 MX MX2015017070A patent/MX2015017070A/es unknown
- 2014-06-11 WO PCT/FR2014/051419 patent/WO2014199082A1/fr active Application Filing
- 2014-06-11 JP JP2016518568A patent/JP6445542B2/ja not_active Expired - Fee Related
- 2014-06-11 PL PL14734884T patent/PL3007844T3/pl unknown
- 2014-06-11 CN CN201480044701.3A patent/CN105451915B/zh not_active Expired - Fee Related
- 2014-06-11 KR KR1020167000492A patent/KR20160033096A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
FR3006696A1 (fr) | 2014-12-12 |
JP2016526602A (ja) | 2016-09-05 |
CN105451915B (zh) | 2018-01-02 |
FR3006696B1 (fr) | 2015-06-26 |
EP3007844B1 (fr) | 2017-08-16 |
US20160121400A1 (en) | 2016-05-05 |
PL3007844T3 (pl) | 2018-02-28 |
CN105451915A (zh) | 2016-03-30 |
US10183331B2 (en) | 2019-01-22 |
JP6445542B2 (ja) | 2018-12-26 |
MX2015017070A (es) | 2016-08-03 |
KR20160033096A (ko) | 2016-03-25 |
WO2014199082A1 (fr) | 2014-12-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3007844B1 (fr) | Procédé de fabrication d'une pièce en alliage en titane-aluminium | |
EP1840232B1 (fr) | Alliage à base de nickel | |
EP3850118B1 (fr) | Superalliages a base de nickel | |
JP2001316743A (ja) | TiAl基合金及びその製造方法並びにそれを用いた動翼 | |
JP6792837B2 (ja) | チタン‐アルミニウム合金 | |
EP0863219B1 (fr) | Aluminiure de titane utilisable à température élevée | |
EP2321440A2 (fr) | Procédé de préparation d'une pièce en superalliage base nickel et pièce ainsi obtenue | |
WO2000008222A1 (fr) | Procede de fabrication d'un alliage intermetallique fer-aluminium renforce par des dispersoides de ceramique et alliage ainsi obtenu | |
FR2633942A1 (fr) | Superalliage a base de nickel resistant aux pendillements par fatigue et son procede de fabrication | |
WO2019097162A1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
EP3710611B1 (fr) | Superalliage a base de nickel, aube monocristalline et turbomachine | |
JP5645054B2 (ja) | アニーリングツインを含有するニッケル基耐熱超合金と耐熱超合金部材 | |
EP3684530B1 (fr) | Piece de turbine en alliage comprenant une phase max | |
EP4073283A1 (fr) | Superalliage a base de nickel | |
FR2928661A1 (fr) | Alliage a base de ni pour rotor de turbine a vapeur et rotor de turbine a vapeur | |
CN114737084A (zh) | 高强抗蠕变高温合金及其制备方法 | |
KR101923477B1 (ko) | 질화 타이타늄 또는 질화 타이타늄 알루미나이드를 포함하는 합금의 제조방법 | |
WO2023157438A1 (fr) | PRODUIT EN ALLIAGE À BASE DE Fe-Ni-Cr | |
FR3027922A1 (fr) | Procedes pour transformer des alliages ferritiques nanostructures, et articles fabriques de cette facon | |
FR3132913A1 (fr) | Poudre d’alliage, procédé de fabrication d’une pièce à base de cet alliage et pièce ainsi obtenue. | |
WO2023161576A1 (fr) | Poudre d'alliage, procédé de fabrication d'une pièce à base de cet alliage et pièce ainsi obtenue | |
JP2012107269A (ja) | ニッケル基耐熱超合金と耐熱超合金部材 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20151221 |
|
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 |
|
DAX | Request for extension of the european patent (deleted) | ||
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: THOMAS, MARC Inventor name: MONCHOUX, JEAN-PHILIPPE Inventor name: COURET, ALAIN Inventor name: VOISIN, THOMAS |
|
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: 20170301 |
|
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: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 918580 Country of ref document: AT Kind code of ref document: T Effective date: 20170915 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602014013227 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20170816 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 918580 Country of ref document: AT Kind code of ref document: T Effective date: 20170816 |
|
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: 20170816 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: 20170816 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: 20171116 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: 20170816 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: 20170816 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: 20170816 |
|
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: 20170816 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: 20170816 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: 20171117 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: 20171216 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: 20170816 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170816 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: 20170816 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602014013227 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20170816 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: 20170816 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: 20170816 |
|
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: 20180517 |
|
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: 20170816 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170816 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180630 |
|
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: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180611 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: 20170816 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180611 |
|
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: 20180630 |
|
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: 20170816 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20170816 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170816 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: 20170816 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170816 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: 20140611 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170816 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: RO Payment date: 20200609 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20200622 Year of fee payment: 7 Ref country code: BG Payment date: 20200618 Year of fee payment: 7 Ref country code: PL Payment date: 20200605 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210611 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20211231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210611 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20220616 Year of fee payment: 9 Ref country code: FR Payment date: 20220517 Year of fee payment: 9 Ref country code: DE Payment date: 20220607 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210611 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602014013227 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20230611 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20240103 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230611 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230630 |