WO2022208004A1 - Superalliage a base de nickel, aube monocristalline et turbomachine - Google Patents
Superalliage a base de nickel, aube monocristalline et turbomachine Download PDFInfo
- Publication number
- WO2022208004A1 WO2022208004A1 PCT/FR2022/050558 FR2022050558W WO2022208004A1 WO 2022208004 A1 WO2022208004 A1 WO 2022208004A1 FR 2022050558 W FR2022050558 W FR 2022050558W WO 2022208004 A1 WO2022208004 A1 WO 2022208004A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- superalloy
- rhenium
- chromium
- cobalt
- Prior art date
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 120
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 72
- 239000013078 crystal Substances 0.000 title abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 35
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 33
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 33
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 31
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 23
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 22
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 21
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010937 tungsten Substances 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 230000004888 barrier function Effects 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000011253 protective coating Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 59
- 239000000956 alloy Substances 0.000 abstract description 59
- 239000002244 precipitate Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 230000007547 defect Effects 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000005496 eutectics Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 101100439208 Caenorhabditis elegans cex-1 gene Proteins 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 101100439211 Caenorhabditis elegans cex-2 gene Proteins 0.000 description 5
- 208000003351 Melanosis Diseases 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 206010014970 Ephelides Diseases 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003071 parasitic effect Effects 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- 229910001011 CMSX-4 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001687 destabilization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 229910000907 nickel aluminide Chemical group 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012720 thermal barrier coating Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000027311 M phase Effects 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005495 investment casting Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2300/00—Materials; Properties thereof
- F05D2300/10—Metals, alloys or intermetallic compounds
- F05D2300/17—Alloys
- F05D2300/175—Superalloys
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
- F05D2300/00—Materials; Properties thereof
- F05D2300/60—Properties or characteristics given to material by treatment or manufacturing
- F05D2300/607—Monocrystallinity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Definitions
- This presentation relates to nickel-based superalloys for gas turbines, in particular for stationary blades, also called distributors or rectifiers, or mobiles of a gas turbine, for example in the field of aeronautics.
- nickel-based superalloys for single-crystal blades have undergone significant changes in chemical composition, with the particular aim of improving their creep properties at high temperature while maintaining resistance to the environment. very aggressive in which these superalloys are used.
- metal coatings adapted to these alloys have been developed in order to increase their resistance to the aggressive environment in which these alloys are used, in particular the resistance to oxidation and the resistance to corrosion.
- a ceramic coating of low thermal conductivity, performing a thermal barrier function can be added to reduce the temperature at the surface of the metal.
- a complete protection system comprises at least two layers.
- the first layer also called sub-layer or bonding layer
- the first layer is directly deposited on the part to be protected in nickel-based superalloy, also called substrate, for example a blade.
- the deposit step is followed by a step of diffusion of the underlayer in the superalloy.
- the deposition and the diffusion can also be carried out during a single step.
- M Ni (nickel) or Co (cobalt)
- Cr chromium
- NiAlyPtz nickel aluminide type alloys
- the second layer is a ceramic coating comprising for example yttria zirconia, also called “YSZ” in accordance with the acronym English for “Yttria Stabilized Zirconia” or “YPSZ” in accordance with the English acronym for “Yttria Partially Stabilized Zirconia” and having a porous structure.
- yttria zirconia also called “YSZ” in accordance with the acronym English for “Yttria Stabilized Zirconia” or “YPSZ” in accordance with the English acronym for “Yttria Partially Stabilized Zirconia” and having a porous structure.
- This layer can be deposited by various processes, such as evaporation under an electron beam (“EB-PVD” in accordance with the English acronym for “Electron Beam Physical Vapor Deposition”), thermal spraying (“APS” in accordance with the English acronym for “Atmospheric Plasma Spraying” or “SPS” in accordance with the English acronym for “Suspension Plasma Spraying”), or any other process making it possible to obtain a porous ceramic coating with low thermal conductivity.
- EB-PVD electron beam
- APS in accordance with the English acronym for “Atmospheric Plasma Spraying” or “SPS” in accordance with the English acronym for “Suspension Plasma Spraying”
- any other process making it possible to obtain a porous ceramic coating with low thermal conductivity.
- inter-diffusion phenomena occur on a microscopic scale between the nickel-based superalloy of the substrate and the metal alloy of the underlayer.
- These phenomena of inter-diffusion, associated with the oxidation of the underlayer modify in particular the chemical composition, the microstructure and consequently the mechanical properties of the underlayer from the manufacture of the coating, then during the use of dawn in the turbine.
- These inter-diffusion phenomena also modify the chemical composition, the microstructure and consequently the mechanical properties of the superalloy of the substrate under the coating.
- a secondary reaction zone can thus form in the superalloy under the sub-layer to a depth of several tens, or even hundreds, of micrometers.
- the mechanical characteristics of this ZRS are clearly inferior to those of the superalloy of the substrate.
- the formation of ZRS is undesirable because it leads to a significant reduction in the mechanical strength of the superalloy.
- foundry defects are likely to form in the parts, such as blades, during their manufacture by directional solidification. These defects are generally parasitic grains of the "Freckle" type, the presence of which can cause premature failure of the part in service. The presence of these defects, related to the chemical composition of the superalloy, generally leads to the rejection of the part, which leads to an increase in the cost of production.
- the present presentation aims to propose compositions of nickel-based superalloys for the manufacture of single-crystal components, presenting increased performance in terms of service life and mechanical strength and making it possible to reduce the production costs of the part ( decrease in scrap rate) compared to existing alloys.
- These superalloys exhibit higher high temperature creep resistance than existing alloys while demonstrating good microstructural stability within the bulk of the superalloy (low susceptibility to PTC formation), good microstructural stability under the coating underlayer of the thermal barrier (low sensitivity to the formation of ZRS), good resistance to oxidation and corrosion while avoiding the formation of parasitic grains of the "Freckle" type.
- the present presentation relates to a nickel-based superalloy comprising, in mass percentages, 5.5 to 7.5% aluminum, 1.0 to 4.0% tantalum, 0.50 to 3.0% Titanium, 3.0-7.0% Cobalt, 8.0-12.0% Chromium, 0-2.5% Molybdenum, 0-3.0% Tungsten, 0.50 to 2.8% rhenium, 0.05 to 0.25% hafnium, 0 to 0.15% silicon, the balance consisting of nickel and inevitable impurities.
- This superalloy is intended for the manufacture of monocrystalline gas turbine components, such as fixed or moving blades.
- the creep resistance is improved compared to existing superalloys, in particular at temperatures which can go up to 1100° C. and the adhesion of the thermal barrier is reinforced compared to that observed on existing superalloys.
- This alloy therefore has improved creep resistance at high temperature. As the service life of this alloy is thus long, this alloy also has improved resistance to corrosion and oxidation. This alloy may also exhibit improved thermal fatigue resistance.
- These superalloys have a density less than or equal to 8.50 g/cm 3 (gram per cubic centimeter), preferably less than or equal to 8.20 g/cm 3 .
- a monocrystalline nickel-based superalloy part is obtained by a process of directed solidification under a thermal gradient in a lost-wax casting.
- the single-crystal nickel-based superalloy comprises an austenitic matrix of face-centered cubic structure, nickel-based solid solution, known as the gamma (“y”) phase.
- This matrix contains gamma prime (“y'") hardening phase precipitates of structure ordered cubic L1 2 of type Ni 3 AI.
- the whole (matrix and precipitates) is therefore described as a g/g′ superalloy.
- this composition of the nickel-based superalloy allows the implementation of a heat treatment which redissolves the phase precipitates g′ and the eutectic phases g/g′ which form during the solidification of the superalloy. It is thus possible to obtain a monocrystalline nickel-based superalloy containing precipitates g' of controlled size, preferably between 300 and 500 nanometers (nm), and containing a low proportion of eutectic phases g/g'.
- the heat treatment also makes it possible to control the volume fraction of the g′ phase precipitates present in the single-crystal nickel-based superalloy.
- the percentage by volume of the precipitates of phase g′ may be greater than or equal to 50%, preferably greater than or equal to 60%, even more preferably equal to 70%.
- the major addition elements are cobalt (Co), chromium (Cr), molybdenum (Mo), rhenium (Re), tungsten (W), aluminum (Al), titanium ( Ti) and tantalum (Ta).
- the minor addition elements are hafnium (Hf) and silicon (Si), for which the maximum mass content is less than 1% by mass.
- Hf hafnium
- Si silicon
- Unavoidable impurities mention may be made, for example, of sulfur (S), carbon (C), boron (B), yttrium (Y), lanthanum (La) and cerium (Ce ).
- Unavoidable impurities are defined as those elements which are not intentionally added to the composition and which are added with other elements.
- the superalloy may comprise 0.005% by mass of carbon.
- the addition of tungsten, chromium, cobalt, rhenium or molybdenum mainly makes it possible to reinforce the austenitic matrix y of face-centered cubic (cfc) crystal structure by hardening in solid solution.
- Rhenium makes it possible to slow down the diffusion of the chemical species within the superalloy and to limit the coalescence of the phase precipitates y′ during service at high temperature, a phenomenon which leads to a reduction in the mechanical strength. Rhenium thus makes it possible to improve the creep resistance at high temperature of the nickel-based superalloy.
- too high a concentration of rhenium can lead to the precipitation of PTC intermetallic phases, for example o-phase, P-phase or m-phase, which have a negative effect on the mechanical properties of the superalloy. Too high a rhenium concentration can also cause the formation of a secondary reaction zone in the superalloy under the underlayer, which has a negative effect on the mechanical properties of the superalloy.
- the simultaneous addition of silicon and hafnium makes it possible to improve the resistance to hot oxidation of nickel-based superalloys by increasing the adhesion of the layer of alumina (Al 2 O 3 ) which forms on the surface of the superalloy at high temperature.
- This layer of alumina forms a passivation layer on the surface of the nickel-based superalloy and a barrier to the diffusion of oxygen coming from the exterior towards the interior of the nickel-based superalloy.
- hafnium without also adding silicon or conversely add silicon without also adding hafnium and still improve the resistance to hot oxidation of the superalloy.
- chromium or aluminum makes it possible to improve the resistance to oxidation and to corrosion at high temperature of the superalloy.
- chromium is essential for increasing the hot corrosion resistance of nickel-based superalloys.
- too high a chromium content tends to reduce the solvus temperature of the y' phase of the nickel-based superalloy, i.e. the temperature above which the y' phase is completely dissolved in the y matrix, which is undesirable.
- the chromium concentration is between 8.0 to 12.0% in bulk in order to maintain a high solvus temperature of the y' phase of the nickel-based superalloy, for example greater than or equal to 1200° C. but also to avoid the formation of topologically compact phases in the matrix g highly saturated with d elements alloys such as rhenium, molybdenum or tungsten.
- cobalt which is an element close to nickel and which partially replaces nickel, forms a solid solution with the nickel in the y matrix.
- Cobalt makes it possible to strengthen the matrix y, to reduce the sensitivity to the precipitation of PTC and to the formation of ZRS in the superalloy under the protective coating.
- too high a cobalt content tends to reduce the solvus temperature of the y' phase of the nickel base superalloy, which is undesirable.
- refractory elements such as molybdenum, tungsten, rhenium or tantalum makes it possible to slow down the mechanisms controlling the creep of nickel-based superalloys and which depend on the diffusion of chemical elements in the superalloy .
- a very low sulfur content in a nickel-based superalloy makes it possible to increase the resistance to oxidation and to hot corrosion as well as the spalling resistance of the thermal barrier.
- a low sulfur content less than 2 ppm by mass (part per million by mass), or even ideally less than 0.5 ppm by mass, makes it possible to optimize these properties.
- Such a mass content of sulfur can be obtained by producing a low-sulphur mother casting or by a desulfurization process carried out after casting. In particular, it is possible to maintain a low sulfur content by adapting the process for producing the superalloy.
- nickel-based superalloys means superalloys in which the mass percentage of nickel is predominant. It is understood that nickel is therefore the element whose mass percentage in the alloy is the highest. [0036]
- the superalloy may comprise, in mass percentages, 5.5 to
- the superalloy may comprise, in mass percentages, 6.5 to
- the superalloy may comprise, in mass percentages, 6.0 to 7.0% aluminum, 1.0 to 4.0% tantalum, 0.50 to 2.5% titanium, 3.0 to 7.0% Cobalt, 8.0-10.0% Chromium, 1.5-2.5 Molybdenum, 0-2.5% Tungsten, 1.5-2.5% Rhenium, 0, 05 to 0.25% hafnium, 0 to 0.15% silicon, the remainder consisting of nickel and inevitable impurities.
- the superalloy may comprise, in mass percentages, 6.0% aluminum, 2.0% tantalum, 1.0% titanium, 5.0% cobalt, 11.0% chromium, 1, 0% tungsten, 1.0% rhenium, 0.10% hafnium, 0.10% silicon, balance being nickel and unavoidable impurities.
- the superalloy may comprise, in mass percentages, 7.0% aluminum, 2.0% tantalum, 1.0% titanium, 5.0% cobalt, 11.0% chromium, 1, 0% tungsten, 1.0% rhenium, 0.10% hafnium, 0.10% silicon, balance being nickel and unavoidable impurities.
- the superalloy may comprise, in mass percentages, 6.5% aluminum, 3.0% tantalum, 1.0% titanium, 5.0% cobalt, 9.0% chromium, 1, 5% molybdenum, 2.0% tungsten, 2.0% rhenium, 0.10% hafnium, 0.10% silicon, balance being nickel and unavoidable impurities.
- the superalloy may comprise, in mass percentages, 6.5% aluminum, 2.0% tantalum, 2.0% titanium, 5.0% cobalt, 9.0% chromium, 2, 0% molybdenum, 2.0% rhenium, 0.10% hafnium, 0.10% silicon, balance being nickel and unavoidable impurities.
- This presentation also relates to a single-crystal blade for a turbomachine comprising a superalloy as defined above.
- This blade therefore has improved creep resistance at high temperature. This blade therefore has improved resistance to oxidation and corrosion.
- the blade may comprise a protective coating comprising a metal underlayer deposited on the superalloy and a ceramic thermal barrier deposited on the metal underlayer.
- the composition of the nickel-based superalloy Thanks to the composition of the nickel-based superalloy, the formation of a secondary reaction zone in the superalloy resulting from inter-diffusion phenomena between the superalloy and the underlayer is avoided or limited.
- the metal underlayer can be an alloy of the MCrAlY type or an alloy of the nickel aluminide type.
- the ceramic thermal barrier can be a material based on yttria-zirconia or any other ceramic coating (based on zirconia) with low thermal conductivity.
- the blade may have a structure oriented along a ⁇ 001> crystallographic direction.
- This presentation also relates to a turbine engine comprising a blade as defined previously.
- Figure 1 is a schematic view in longitudinal section of a turbine engine.
- Nickel-based superalloys are intended for the manufacture of single-crystal blades by a directed solidification process in a thermal gradient.
- the use of a monocrystalline seed or of a grain selector at the start of solidification makes it possible to obtain this monocrystalline structure.
- the structure is oriented for example along a crystallographic direction ⁇ 001> which is the orientation which generally confers the optimum mechanical properties on superalloys.
- Single-crystal superalloys based on nickel as they solidified have a dendritic structure and consist of precipitates g′ Ni 3 (Al, Ti, Ta) dispersed in a matrix g of face-centered cubic structure, solid solution based on nickel. These g' phase precipitates are distributed heterogeneously in the volume of the single crystal due to chemical segregations resulting from the solidification process. Furthermore, g/g' eutectic phases are present in the inter-dendritic regions and constitute preferential crack initiation sites. These g/g' eutectic phases are formed at the end of solidification.
- the g/g' eutectic phases are formed to the detriment of the fine precipitates (size less than a micrometer) of the hardening phase g'. These g' phase precipitates constitute the main source of hardening of nickel-based superalloys. Also, the presence of residual g/g' eutectic phases does not make it possible to optimize the hot creep resistance of the nickel-based superalloy.
- the as-solidified nickel-based superalloys are therefore heat-treated to obtain the desired distribution of the different phases.
- the first heat treatment is a treatment for homogenizing the microstructure, the purpose of which is to dissolve the g′ phase precipitates and to eliminate the g/g′ eutectic phases or to significantly reduce their volume fraction. This treatment is carried out at a temperature above the solvus temperature of the g' phase and below the starting melting temperature of the superalloy (T SO iidus) A quenching is then carried out at the end of this first heat treatment to obtain a fine and homogeneous dispersion of the precipitates g'. Tempering heat treatments are then carried out in two stages, at temperatures below the solvus temperature of phase g′. During a first step, to enlarge the precipitates g' and obtain the desired size, then during a second step, to make increase the volume fraction of this phase to about 70% at room temperature.
- FIG. 1 shows, in section along a vertical plane passing through its main axis A, a turbofan engine 10.
- the turbofan engine 10 comprises, from upstream to downstream according to the circulation of the air flow, a fan 12, a low pressure compressor 14, a high pressure compressor 16, a combustion chamber 18, a high pressure turbine 20, and a low pressure turbine 22.
- the high pressure turbine 20 comprises a plurality of blades 20A rotating with the rotor and 20B rectifiers (fixed blades) mounted on the stator.
- the stator of the turbine 20 comprises a plurality of stator rings 24 arranged opposite the moving blades 20A of the turbine 20.
- a turbomachine can in particular be a turbojet engine such as a turbofan engine 10.
- the turbomachine can also be a single-flow turbojet engine, a turboprop engine or a turboshaft engine.
- the density at ambient temperature of each superalloy was estimated using a modified version of the Hull formula (FC Hull, Metal Progress, November 1969, ppl39-140).
- This empirical equation was proposed by Hull.
- the empirical equation is based on a law of mixtures and includes corrective terms deduced from an analysis by linear regression of experimental data (chemical compositions and measured densities) concerning 235 nickel-based, cobalt-based and iron-based superalloys.
- This Hull formula has been modified, in particular to take into account elements such as rhenium and this, from 272 nickel-based, cobalt-based and iron-based superalloys.
- the modified Hull formula is: where D x are the densities of the elements Cr, Ni, ..., X and D is the density of the superalloy, the densities being expressed in g/cm 3 , where A x is a coefficient expressed in g/cm 3 elements Cr, Ni, ..., X and are the 0.0156. where %X are the contents, expressed in mass percentages, of the superalloy elements Cr, Ni, ..., X.
- the densities calculated for the alloys of the invention are less than 8.20 g/cm 3 (see Table 2).
- Density is of prime importance for applications of rotating components such as turbine blades. Indeed, an increase in the density of the alloy of the blades imposes a reinforcement of the disc carrying them, and therefore another additional cost in weight.
- CEx 3 and CEx 4 alloys do not meet current superalloy development standards for vanes.
- the composition of the CEx 3 and CEx 4 alloys comes from developments for conventional foundry and not for foundry by directional solidification.
- This equation (2) was obtained by analysis by multiple linear regression from observations made after aging for 400 hours at 1093° C. (degree centigrade) of samples of various nickel-based superalloys, close to the René N6® composition, under a NiPtAl coating.
- NFP [%Ta + 1.5%Hf + 0.5%Mo - 0.5%%Ti)]/[%W + 1.2%Re)] where %Cr, %Ni, .. .%X are the contents, expressed in mass percentages, of the superalloy elements Cr, Ni, ..., X.
- the NFP parameter makes it possible to quantify the sensitivity to the formation of parasitic grains of the “Freckles” type during the directed solidification of the part (document US Pat. No. 5,888,451). To avoid the formation of “Freckles” type faults, the NFP parameter must be greater than or equal to 0.7. A low sensitivity to this type of defect is an important parameter because it implies a low scrap rate linked to this defect during the manufacture of parts.
- the Ex 1 to Ex 4 superalloys all have an NFP parameter greater than or equal to 0.7.
- Commercial alloys containing rhenium such as CEx 6 or CEx 7 have higher sensitivities to the formation of this type of defect as indicated in Table 2.
- a low sensitivity to this type of defect is an important parameter because it implies a low rate. of scrap linked to this defect during the manufacture of parts.
- the cost per kilogram of Ex 1 to Ex 4 superalloys is calculated based on the composition of the superalloy and the costs of each compound (updated April 2020). This cost is given as an indication.
- the estimated cost of the Ex 1 to Ex 4 superalloys is approximately $80-100/kg. This cost is higher than alloys not containing rhenium such as CEx 5 or CEx 1 but lower than alloys containing rhenium such as CEx 6 or CEx 7.
- the alloys of the invention are competitive given their position vis-à-vis screws of the reference alloys.
- Table 2 presents different parameters for Ex 1 to Ex 4 and CEx 1 to CEx 7 superalloys.
- Thermo-Cale software (TCNI9.1 database, Thermo-Cale Software AB, Sweden) based on the CALPHAD method was used to calculate the solvus temperature of the g' phase at equilibrium.
- the superalloys Ex 1 to Ex 4 have a solvus temperature g′ greater than 1200° C.
- TTH Heat Treatment Interval
- Thermo-Cale software (TCNI9.1 database) based on the CALPHAD method was used to calculate the heat treatment interval of the superalloys.
- the manufacturability of the alloys of the invention was also estimated on the basis of the possibility of re-dissolving the g′ phase precipitates industrially in order to optimize the mechanical properties of the alloys.
- the heat treatment range was estimated from the calculation of the solidus temperature and the solvus temperature of the g' phase precipitates of the alloys.
- Ex 1 to Ex 4 alloys all have high heat treatment windows, above 50°C, which is compatible with industrial furnaces. It is noted that the reference alloys CEx 7 or CEx 5 have much more restricted heat treatment intervals and are therefore less easily heat treatable without risk of burning the alloy.
- Thermo-Cale software (TCNI9.1 database) based on the CALPHAD method was used to calculate the volume fraction (in percentage by volume) of phase g' at equilibrium in the superalloys Ex 1 to Ex 4 and CEx 1 to CEx 7 at 750°C and 1100°C.
- superalloys Ex 1 to Ex 4 contain volume fractions of phase y′ greater than or comparable to the volume fractions of phase g′ of commercial superalloys CEx 1 to CEx 7.
- the combination of a high solvus temperature g' and high phase volume fractions g' for superalloys Ex 1 to Ex 4 is favorable to good creep resistance at high temperature and very high temperature, for example at 1100 °C.
- volume fraction of o-type PTC [0094] Thermo-Cale software (TCNI9.1 database) based on the CALPHAD method was used to calculate the volume fraction (in volume percentage) of o phase at the equilibrium in Ex 1 to Ex 4 and CEx 1 to CEx 7 superalloys at 750°C (see table 3).
- the calculated volume fractions of phase o are relatively low, which reflects a low sensitivity to the precipitation of PTC.
- the Ex 2 and Ex 4 alloys have solvus temperatures that are significantly higher than the solvus temperature of CEx 3 (+44°C and +59°C respectively) and higher y' phase precipitate fractions than this same alloy at 750°C and 1100°C (Table 2).
- Ex 2 and Ex 4 have respectively similar solvus.
- the fractions of phase g' precipitates of Ex 2 and Ex 4 alloys are higher than those of CEx 4 (+10%).
- Ex 2 has a fraction of g' phase precipitates slightly lower than CEx 4 (-6%) while Ex 4 has a fraction of g' phase precipitates similar to CEx 4.
- Ex 3 has a similar solvus temperature to CEx 2 with a similar g' phase precipitate fraction at 750°C and slightly lower at 1100°C. Nevertheless, Ex 3 has a lower density of 0.1 g/cm 3 compared to CEx 2. Since the density variation range of nickel base superalloys is generally between 8 and 9 g/cm 3 , this 10% difference is significant.
- the Ex 2 and Ex 4 alloys have TCP volume fractions of 0 and 3% respectively at 750°C, which is similar or lower than the TCP fractions of the reference alloys CEx 1 (5.9%), CEx 3 ( 4%) and CEx 4 (3.3%). Ex 3 has a slightly lower TCP content at 750°C than CEx 2.
- the Ex 2 and Ex 4 alloys have a chemical composition and a microstructure which makes it possible to envisage a mechanical strength superior to that of the reference alloys CEx 3 and CEx 4.
- Ex 3 should have similar mechanical strength to CEx 2 with a lower density.
- the alloys of the invention have been designed so as to maintain resistance to corrosion ( ⁇ 900° C.) and oxidation ( ⁇ 1100° C.) high at high temperature.
- the flow that circulates through the turbines of turbojet engines is loaded with products that are generally a result of the fuel combustion reaction, but which also include water, sands, and salts contained in the incoming air ingested by the turbomachine.
- the fuel also contains impurities and sulfur products (always present regardless of the cleanliness of the fuel).
- the alloys oxidize under the operating conditions imposed by the engines (temperature, pressure) by reactions with the various gases contained (Ü2(g), CO x , NO x , H 2 0, etc. .) in the engine environment.
- the alloys of the invention have chromium contents similar to those of the CEx 3 and CEx 4 alloys and higher than those of the other reference alloys.
- the aluminum contents of the alloys of the invention are greater than or equal to those of the reference alloys.
- the oxidation and corrosion resistance of these alloys is assumed to be similar or superior to that of the CEx 3 and CEx 4 reference alloys and superior to that of the other reference alloys.
- the example alloys of the invention thus have strong potential for high-temperature applications, in particular for the manufacture of turbine blades, combining an adequate compromise combining low density, high mechanical strength, low sensitivity to the formation of defects (PTC, ZRS, foundry defects), while maintaining high resistance to oxidation and corrosion.
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CN202280027071.3A CN117280058A (zh) | 2021-04-02 | 2022-03-25 | 镍基超合金、单晶叶片和涡轮机 |
EP22717860.5A EP4314370A1 (fr) | 2021-04-02 | 2022-03-25 | Superalliage a base de nickel, aube monocristalline et turbomachine |
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FR2103436A FR3121453B1 (fr) | 2021-04-02 | 2021-04-02 | Superalliage a base de nickel, aube monocristalline et turbomachine |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0155827A2 (fr) * | 1984-03-19 | 1985-09-25 | Cannon-Muskegon Corporation | Alliage pour la technologie des monocristaux |
US5270123A (en) | 1992-03-05 | 1993-12-14 | General Electric Company | Nickel-base superalloy and article with high temperature strength and improved stability |
US5888451A (en) | 1996-06-17 | 1999-03-30 | Abb Research Ltd. | Nickel-base superalloy |
EP2402473A2 (fr) * | 2010-06-30 | 2012-01-04 | Alstom Technology Ltd | Procédé de fabrication d'un composant monocristallin constitué d'un superalliage à base de nickel |
EP2781613A1 (fr) * | 2013-03-21 | 2014-09-24 | Siemens Aktiengesellschaft | Alliage de nickel optimisé et aube de turbine fabriquée à partir de celui-ci |
-
2021
- 2021-04-02 FR FR2103436A patent/FR3121453B1/fr active Active
-
2022
- 2022-03-25 EP EP22717860.5A patent/EP4314370A1/fr active Pending
- 2022-03-25 WO PCT/FR2022/050558 patent/WO2022208004A1/fr active Application Filing
- 2022-03-25 CN CN202280027071.3A patent/CN117280058A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0155827A2 (fr) * | 1984-03-19 | 1985-09-25 | Cannon-Muskegon Corporation | Alliage pour la technologie des monocristaux |
US5270123A (en) | 1992-03-05 | 1993-12-14 | General Electric Company | Nickel-base superalloy and article with high temperature strength and improved stability |
US5888451A (en) | 1996-06-17 | 1999-03-30 | Abb Research Ltd. | Nickel-base superalloy |
EP2402473A2 (fr) * | 2010-06-30 | 2012-01-04 | Alstom Technology Ltd | Procédé de fabrication d'un composant monocristallin constitué d'un superalliage à base de nickel |
EP2781613A1 (fr) * | 2013-03-21 | 2014-09-24 | Siemens Aktiengesellschaft | Alliage de nickel optimisé et aube de turbine fabriquée à partir de celui-ci |
Non-Patent Citations (1)
Title |
---|
F.C. HULL, METAL PROGRESS, November 1969 (1969-11-01), pages l39 - 140 |
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CN117280058A (zh) | 2023-12-22 |
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