EP3256279B1 - Cermet materials and method for making such materials - Google Patents
Cermet materials and method for making such materials Download PDFInfo
- Publication number
- EP3256279B1 EP3256279B1 EP16707872.4A EP16707872A EP3256279B1 EP 3256279 B1 EP3256279 B1 EP 3256279B1 EP 16707872 A EP16707872 A EP 16707872A EP 3256279 B1 EP3256279 B1 EP 3256279B1
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- phase
- alc
- tial
- max
- powder
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- 239000000463 material Substances 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 21
- 239000011195 cermet Substances 0.000 title claims description 11
- 239000010936 titanium Substances 0.000 claims description 146
- 238000005245 sintering Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 238000007731 hot pressing Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052729 chemical element Inorganic materials 0.000 claims description 5
- 238000001513 hot isostatic pressing Methods 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 149
- 229910010038 TiAl Inorganic materials 0.000 description 70
- 239000002131 composite material Substances 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- 238000000280 densification Methods 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000007545 Vickers hardness test Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 229910010039 TiAl3 Inorganic materials 0.000 description 2
- 229910008484 TiSi Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000001995 intermetallic alloy Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002970 Calcium lactobionate Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- -1 TiC Substances 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
-
- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- 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
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
Definitions
- the invention relates to the field of composite materials comprising a MAX phase and an intermetallic alloy phase.
- MAX composite materials have good mechanical properties and corrosion resistance. This makes them excellent candidates for the manufacture of high performance structural parts, particularly in the aeronautical field and for the manufacture of blades, abradables and protective coatings.
- Materials in MAX solid form can be obtained by two types of known syntheses.
- the first type of synthesis involves a reactive pressing during which the microstructure of the raw materials is modified. A solid material is then formed in which appears the desired MAX phase and one or more secondary phases.
- the MAX phase is created in situ (during sintering).
- the second type of synthesis implements a first operation making it possible to obtain the desired MAX phase compound in pulverulent form, for example by self-propagating synthesis at high temperature.
- the MAX phase is created upstream.
- a subsequent sintering operation makes it possible to obtain a solid composite material comprising the MAX phase combined with at least one secondary phase.
- the following documents describe such syntheses: WO97 / 18162 , WO97 / 27965 , WO2006 / 057618 and CN1250039 .
- the secondary phases are unintentionally obtained.
- the very term "secondary" highlights the low interest of the secondary phases in the mechanical behavior of the solid materials obtained. Very often, the volume quantity of the secondary phases is nevertheless greater than that of the MAX phase. Their natures and relative amounts in the products obtained are not very detailed but generally depend on the precursors used.
- TiC is the most common phase for MAX phases such as Ti 3 AlC 2 or Ti 3 SiC 2 .
- Gold TiC is a phase recognized as harmful for the mechanical properties and corrosion resistance.
- CN1789463 a method comprising plasma-assisted sintering (or SPS for Spark Plasma Sintering ) is proposed.
- the majority phase is TiAl intermetallic.
- the goal would be to improve the mechanical properties of this majority phase by adding TiC. This has the consequence of promoting the formation of Ti 2 AlC precipitates which pin the grain boundaries and limit the growth of TiAl grains during sintering. Only the mechanical properties of the intermetallic are improved. There is no question of the properties of the MAX phase, minority: Ti 2 AlC.
- the friction behavior of MAX phase materials has been further studied, for example in the following documents: US7572313 , US2010 / 0055492 and WO98 / 22244 .
- Syntheses of solid material with MAX phase are described therein.
- a metal is added to a previously produced MAX phase powder or foam.
- the volume proportion of the metal can reach about 70%.
- a heat treatment makes it possible to obtain a thermodynamically stable composite.
- the products obtained include, again, undesirable secondary phases.
- the solid material obtained can only be used at temperatures below the melting temperature of the metal used. Neither the limitations in the conditions of use, the duration of production nor the manufacturing costs are satisfactory.
- WO98 / 22244 is described a method to increase the density of the material obtained to improve the friction behavior by removing, or almost, the intermetallic phase in favor of the MAX phase.
- This method involves sintering a MAX phase powder with an intermetallic powder in thermodynamic equilibrium and soluble in the MAX phase. The sintering is carried out at a temperature above the melting temperature of the intermetallic phase but below the melting temperature of the MAX phase. In the examples, the minimum temperature is about 1475 ° C, the melting temperature of the TiSi 2 intermetallic, and the maximum temperature is about 3000 ° C, the decomposition temperature of the MAX phase. Ti 3 SiC 2 .
- the intermetallic phase previously synthesized then goes into liquid form and is dissolved in the phase MAX.
- the amount of intermetallic phase in the final product is less than 5% by weight.
- the invention improves the situation.
- the volume proportion of TiC alloy is less than 5% to the thermodynamic equilibrium.
- the powder is atomized or granulated prior to the sintering step c).
- the sintering step c) is carried out under vacuum or in the presence of a neutral gas.
- the sintering may comprise the implementation of at least one of reactive hot pressing, reactive hot isostatic pressing and reactive natural sintering.
- the powder is placed in a pressing matrix during sintering.
- the powder may further be encapsulated in a metal sheath.
- the MAX phases have a particular crystalline structure, consisting of layers at the atomic scale.
- this crystalline structure is described as alternating sheets of carbide octahedra, for example titanium carbide (TiC), respectively a titanium nitride. (TiN), and a metal such as aluminum (Al) constituting the planes A.
- TiC titanium carbide
- TiN titanium nitride
- Al aluminum
- the MAX phases have excellent resistance to mechanical and thermal shock, high electrical and thermal conductivity and good machinability thanks to a self-lubricating effect.
- MAX phases have low densities, high Young's moduli, high mechanical strengths, low thermal expansion coefficients, and high melting temperatures.
- the MAX phases Compared with the usual ceramics, the MAX phases have a better tolerance to damage and a high capacity for deformation. These properties are operative especially at room temperature for low rates of deformation.
- the MAX phases exhibit a reversible nonlinear mechanical behavior. They also have a low sensitivity to surface defects and increased toughness compared to conventional ceramics.
- the porosity is generally harmful for the properties of the materials, in particular in mechanical strength and resistance to oxidation. In this context, reducing the porosity is considered equivalent to increasing the density in the envisaged range.
- the Applicant has successfully tried to reduce the intergranular porosity of the final composite while obtaining a significant proportion of intermetallic phase.
- the MAX phases were generally performed by hot pressing, uniaxial or isostatic. Residual unwanted secondary phases appeared in an uncontrolled manner.
- the secondary phases are, for example, made of TiC or TiSi 2 .
- the growth of the MAX phases is plane by plane with a growth rate in the hexagonal base plane much faster than its orthogonal, the mesh parameter c.
- This mode of growth leads to the formation of ellipsoid-shaped platelets slender of any orientation.
- the pads can not fill the entire space.
- areas of little or no activity are created, remote from the growth stages, resulting in slow diffusion and the formation of pores or unreacted phases.
- elaboration by conventional methods leads to the formation of randomly oriented platelets, which creates intergranular porosities.
- the secondary phases may also be due, for example, to a non-reactivity of the starting elements or to the volatilization of certain elements such as metal.
- porosity promotes oxidation by diffusion of oxygen (O).
- O oxygen
- the Applicant has tried to reduce it as well as the proportion of some only secondary or unreacted phases, in particular TiC.
- the Applicant has developed composites of thermodynamically stable materials based on a MAX phase of general formula Ti n + 1 AlC n , and an intermetallic phase of general formula Ti x Al y , where n is 1 or 2, x is between 1 and 3, y is between 1 and 3, and x + y ⁇ 4.
- the intermetallic phase is lower than the MAX phase.
- the volume proportion of the intermetallic phase relative to the MAX phase is between 5% and 30%.
- the MAX phases take, for example, the form of Ti 2 AlC or Ti 3 AlC 2 .
- the intermetallics take, for example, the form of TiAl, Ti 3 Al or TiAl 3 .
- the Ti 2 AlC / Ti x Al y or Ti 3 AlC 2 / Ti x Al y composites are prepared here by hot-pressing.
- the powders are intimately mixed by grinding.
- a jar crushing and in the presence of tungsten carbide balls (WC) is implemented.
- the grinding is carried out in ethanol. The grinding lasts 2 hours.
- the mixture thus obtained is dried.
- the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
- the powder obtained is hot pressed.
- hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1200 ° C., for 2 hours, under a uniaxial stress of 30 MPa, under an argon (Ar) atmosphere. 1 bar.
- soft graphite covers the inner walls of the mold.
- leaves sold under the trade name Papyex are used.
- the material obtained is removed from the mold and has a plate shape of 36 mm ⁇ 36 mm and a thickness of 3 mm.
- X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate.
- Ti 2 AlC and TiAl are detected and represent in volume respectively 76% and 19%.
- residues of TiAl 3 and TiC are detected which represent in volume respectively 2.5% and 2.4%. The sum of TiAl 3 and TiC residues is less than 5% by volume.
- the open porosity rate is measured by buoyancy. A rate of 1% is measured. This confirms the good densification of the material.
- the Young modulus measured by dynamic resonance is 225 GPa (standard ASTM Standard “E1876-07”).
- the three-point bending stress at room temperature is 253 MPa ⁇ 20 MPa.
- the toughness measured by notched bending is 5.1 MPa.m 1/2 ⁇ 0.1 MPa.m 1/2 (standard "E399 -83")
- the hardness measured by Vickers indentation (50 g load) is 4.7 GPa ⁇ 0.5 GPa.
- the tests are carried out under the same conditions and with the same standards.
- the powders are intimately mixed by grinding.
- a jar crushing and in the presence of tungsten carbide balls (WC) is implemented.
- the grinding is carried out in ethanol. The grinding lasts 2 hours.
- the mixture thus obtained is dried.
- the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
- the powder obtained is hot pressed.
- the hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1430 ° C, for 2 hours, under a uniaxial stress of 30 MPa, under an argon (Ar) atmosphere. 1 bar.
- soft graphite covers the inner walls of the mold.
- leaves sold under the trade name Papyex are used.
- the material obtained is removed from the mold and has a plate shape of 36 mm ⁇ 36 mm and a thickness of 3 mm.
- X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate.
- Ti 3 AlC 2 and TiAl 3 are detected and represent in volume respectively 88.5% and 7%.
- Residues of Al 2 O 3 and TiC are also detected, which represent in volume respectively 1.5% and 3%.
- the sum of Al 2 O 3 and TiC residues is less than 5% by volume.
- the figure 2 is a snapshot from microscopic observations made on a sample of the obtained material. On this shot, the light parts correspond to Ti 3 AlC 2 while the dark phases correspond to TiAl 3 .
- the open porosity rate is measured by buoyancy. A rate of 0.8% is measured. This confirms the good densification of the material.
- the Young modulus measured by dynamic resonance is 297 GPa.
- the three-point bending stress at room temperature is 367 MPa ⁇ 31 MPa.
- the toughness measured by notch bending is 7.3 MPa.m 1/2 ⁇ 0.4 MPa.m 1/2 .
- the hardness measured by Vickers indentation is 5.2 GPa ⁇ 0.6 GPa.
- the powders are intimately mixed by grinding.
- a jar crushing and in the presence of tungsten carbide balls (WC) is implemented.
- the grinding is carried out in ethanol. The grinding lasts 2 hours.
- the mixture thus obtained is dried.
- the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
- the powder obtained is hot pressed.
- the hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1300 ° C, for 1 hour and 30 minutes, under a uniaxial stress of 30 MPa, under an argon atmosphere ( Ar) at 1 bar.
- soft graphite covers the inner walls of the mold.
- leaves sold under the trade name Papyex are used.
- the material obtained is removed from the mold and has a plate shape of 36 mm ⁇ 36 mm and a thickness of 3 mm.
- X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate.
- Ti 2 AlC and TiAl 3 are detected and represent in volume respectively 80.5% and 15%.
- TiAl and TiC residues which represent 1.5% and 3% by volume respectively, are also detected. The sum of TiAl and TiC residues is less than 5% by volume.
- the open porosity rate is measured by buoyancy. A rate of 1% is measured. This confirms the good densification of the material.
- the Young's modulus measured by dynamic resonance is 220 GPa.
- the three-point bending stress at room temperature is 350 MPa ⁇ 55 MPa.
- the toughness measured by notch bending is 8.7 MPa.m 1/2 ⁇ 0.2 MPa.m 1/2 .
- the hardness measured by Vickers indentation is 4.5 GPa ⁇ 0.1 GPa.
- Example 4 Preparation of a Ti material 2 Single-phase AlC and comparison of the oxidation behavior with the Ti composite 2 AlC / TiAl of Example 1
- the powders are intimately mixed by grinding.
- a jar crushing and in the presence of tungsten carbide balls (WC) is implemented.
- the grinding is carried out in ethanol. The grinding lasts 2 hours.
- the mixture thus obtained is dried.
- the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
- the powder obtained is hot pressed.
- hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1430 ° C, for 1 hour, under a uniaxial stress of 40 MPa, under an argon (Ar) atmosphere. 1 bar.
- soft graphite covers the inner walls of the mold.
- leaves sold under the trade name Papyex are used.
- the material obtained is removed from the mold and has a plate shape of 36 mm ⁇ 36 mm and a thickness of 3 mm.
- X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate. Ti 2 AlC is detected in a volume proportion of greater than 98%. The material obtained can therefore be considered as single phase.
- the complementary phase comprises Ti 3 Al.
- the open porosity rate is measured by buoyancy. A rate of 1% is measured. This confirms the good densification of the material.
- FIGS. 3 and 4 are snapshots from these observations under the microscope.
- the figure 3 shows a microstructure of a Ti 2 AlC fracture from microscopic observations.
- the figure 4 shows a microstructure of a polished section of Ti 2 AlC from microscopic observations.
- closed porosities are visible in black.
- a Ti 2 AlC / TiAl composite is prepared in the same manner as was done in Example 1.
- the two samples are placed together in an oven at 1100 ° C.
- the samples are taken out of the oven, cooled by a fan and weighed. Depending on the initial dimensions and the initial mass of each sample, it is deduced a weight gain area. This weight gain is representative of the evolution of the oxidation of the samples.
- the Ti 2 AlC / TiAl samples are again placed in the oven at 1100 ° C. After an additional one hour, the samples are again taken out of the oven and cooled by a fan. Once cooled, the samples are returned to the oven at 1100 ° C for a new cycle of one hour. These operations are repeated many times. During certain phases outside the oven, the sample is weighed so as to follow the weighting of the surface over time.
- the results are shown in the comparative graph of the figure 5 .
- the abscissa axis represents the duration of the oxidation at 1100 ° C expressed in number of cycles of 1 hour.
- the ordinate axis represents the cumulative mass density expressed in mg.cm -2 .
- Example 1 2 3 4 (single phase) Powder mixture (in molar equivals) 83% Ti 2 AlC + 17% TiAl 83% Ti 2 AlC + 17% TiAl 91.5% Ti 2 AlC + 8.5% TiAl 100% Ti 2 AlC Sintering pressure (in MPa) uniaxial - 30 MPa uniaxial - 30 MPa uniaxial - 30 MPa uniaxial - 40 MPa Sintering temperature (in ° C) 1200 1430 1300 1430 Sintering time (in hours) 2.0 2.0 1.5 1.0 phase (s) obtained (in% by volume) 76% Ti 2 AlC + 19% TiAl + ⁇ 5% (TiAl 3 + TiC) 88.5% Ti 3 AlC 2 + 7.5% TiAl 3 + ⁇ 5% (TiC + Al 2 O 3 ) 80.5% Ti 2 AlC + 15% TiAl 3 + ⁇ 5% (TiAl + TiC) 98% Ti 2 AlC + 2% Ti 3 Al Corresponding figure (s) 2 3,
- the Applicant has developed a manufacturing method for obtaining MAX cermet materials with improved properties.
- the proportion of the intermetallic phase relative to the MAX phase in the product obtained may vary from 5% to 30% by volume.
- the mixing is carried out by methods known per se, for example by means of a planetary mill, or by attrition. Grinding balls may be used, for example tungsten carbide (WC) as in the previous examples, zirconia dioxide (ZrO 2 ) or alumina (Al 2 O 3 ). Non-oxide balls such as those made of tungsten carbide (WC) have demonstrated better efficiency and can limit pollution by oxides.
- tungsten carbide WC
- ZrO 2 zirconia dioxide
- Al 2 O 3 alumina
- Non-oxide balls such as those made of tungsten carbide (WC) have demonstrated better efficiency and can limit pollution by oxides.
- the mixture can be carried out in an organic medium such as ethanol as described in the preceding examples.
- the medium may be aqueous.
- Organic solvents may be added to improve the homogeneity of the mixture.
- a dispersant such as a phosphoric ester known under the trade name "Beycostat C 213" or ammonium polymethacrylate known under the trade designation "Darvan C”.
- the suspension is dried, in particular in a rotary evaporator.
- the powder thus obtained can be worked to obtain a powder which is easier to cast and easier to handle in the subsequent steps of press forming.
- the resulting powder may be atomized or granulated by techniques known per se such as atomization or sieving.
- the powder is then sintered.
- the sintering is carried out by known techniques as such, for example, by hot-pressing reagent, hot isostatic pressing reactive, or by a natural sintering reactive.
- hot-pressing reagent for example, by hot-pressing reagent, hot isostatic pressing reactive, or by a natural sintering reactive.
- Reactive hot pressing providing a degree of containment of the material and easier to implement, is preferred.
- the previously obtained powder is placed in a pressing die of the desired simple shape, for example square or cylindrical, or complex.
- the composition of the pressing matrix is adapted to the temperatures used, for example graphite or metal.
- an applied stress greater than 15 MPa made it possible to obtain good results.
- a range of between 20 MPa and 40 MPa is suitable.
- the powder may be encapsulated in a metal sheath. This avoids the volatilization of chemical species. Hot isostatic pressing also makes it possible to increase the density.
- the powder is first subjected to natural sintering, that is to say without applying pressure. Then, in a second step, hot isostatic sintering is carried out.
- natural sintering that is to say without applying pressure.
- hot isostatic sintering is carried out.
- the sintering is carried out under vacuum or in a neutral atmosphere such as under argon (Ar), dinitrogen (N 2 ) or helium (He). Argon is preferred.
- the applied gas pressure can vary between 0 and 1 bar.
- the materials obtained are two-phase, which does not exclude the presence of third-party residues, but in proportions of less than 3% by mass (detection limit of XRDs).
- obtaining the Ti 2 AlC / Ti x Al y or Ti 3 AlC 2 / Ti x Al y composite can be selected by varying the temperature during sintering.
- the Ti 2 AlC phase is formed between 1000 ° C. and 1200 ° C. It becomes lacunary in Al at about 1300 ° C. At higher temperatures, the cumulative volume of the gaps increases so that at 1400 ° C, Al tends to exit Ti 2 AlC. Indeed, the aluminum atoms located in the planes A crystallographic structures of these materials are weakly related. The gap-forming energy of Al is by far the weakest relative to that of Ti or C. The creation of gaps in the planes A generates a further weakening of this connection. This results in an increase in the vibration entropy.
- the intermetallic TiAl phase is formed at low temperature, below 800 ° C, and enriches in Al, in particular released by the MAX phase. When the enrichment is sufficient, the TiAl 3 intermetallic phase is formed.
- a single-phase material would be deteriorated even though a part made from two-phase materials according to the invention can withstand, at least temporarily, the same temperature without being degraded. This makes it possible to use parts based on two-phase materials under more difficult operating conditions.
- Equation 6 represents the temperature limit of the materials thus created for which Al is nevertheless expelled.
- the Ti 3 AlC 2 phase can be converted at least partly into TiC, which is detrimental to the desired properties of the material.
- the composites are preferably prepared at temperatures higher than 1200 ° C. but lower than that of the decomposition of Ti 3 AlCl 2 (between 1450 ° C. and 1500 ° C.).
- very high density materials are obtained.
- densification rates greater than 95% of the theoretical density are achieved. TiC formation is prevented, or very limited.
- MAX-phase intermetallic phase cermet materials makes it possible to maintain, at the time of growth of the MAX phase, an intermetallic phase which fills the porosities between the MAX phase platelets.
- MAX phase and phase intermetallic are then in thermodynamic equilibrium during transformations of microstructures. Diffusion paths are preserved between the different phases.
- FIG. 1 a view of a fracture, shows the microstructure in platelets while the figure 2 , a polished cut, makes it possible to distinguish the intergranular porosity, in black, between entangled plates without particular orientation.
- the absence or almost absence of a black zone on the Figures 1 and 2 demonstrate that the porosity rate observed is much lower than that of the single-phase MAX phase.
- the figure 2 shows, moreover, that the porosity of Ti 3 AlC 2 is filled by the intermetallic TiAl 3 phase.
- the filling of the porosity by the intermetallic phase explains the improvement of the mechanical properties.
- the density of macroscopic defects, such as pores, is significantly reduced.
- the properties of toughness and creep resistance are improved.
- Ti 2 AlC / TiAl is obtained at 1200 ° C or Ti 3 AlC 2 / TiAl 3 is obtained at 1430 ° C.
- the Applicant surprisingly found that the tested materials also exhibited significantly improved oxidation resistance.
- the results of the oxidation tests of Example 4 show the contribution of the TiAl intermetallic phase to the oxidation resistance at 1100 ° C.
- the Ti 2 AlC / TiAl composite is less oxidized than single-phase Ti 2 AlC in a single one-hour period. The Applicant then sought to identify the phenomenon at the origin of this unexpected property.
- the material developed is still in a high concentration of aluminum during its manufacture, thanks to the coexistence of Ti 2 AlC or Ti 3 AlC 2 and Ti x Al y phases, it seems that the high aluminum content allows to promote the formation of a protective alumina (Al 2 O 3 ) surface layer.
- Reactive sintering of a powder mixture includes, from the start, the chemical elements that will become MAX phase and intermetallic phase during sintering. Since all the chemical elements are arranged in the mold before the sintering operation, the heat treatment operation of the MAX phase alone used until now is rendered superfluous in the processes according to the invention. The methods used to form the cermets are simpler and less expensive.
- the formation of the different phases is controlled, in particular by the temperature applied.
- the amount of intermetallic is controlled, as is the microstructure obtained by reactive pressing.
- the terms " secondary phases" hitherto used to designate the undesirable phases are therefore no longer suitable for intermetallics.
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Description
L'invention relève du domaine des matériaux composites comprenant une phase MAX et une phase d'alliage intermétallique.The invention relates to the field of composite materials comprising a MAX phase and an intermetallic alloy phase.
Il est établi depuis plus de quarante ans que les matériaux composites à phase MAX présentent de bonnes propriétés mécaniques et de résistance à la corrosion. Ceci en fait d'excellents candidats pour entrer dans la fabrication de pièces de structures à haute performance, notamment dans le domaine aéronautique et pour la fabrication d'aubes, d'abradables et de revêtements protecteurs.It has been established for more than forty years that MAX composite materials have good mechanical properties and corrosion resistance. This makes them excellent candidates for the manufacture of high performance structural parts, particularly in the aeronautical field and for the manufacture of blades, abradables and protective coatings.
Les matériaux sous forme solide à phase MAX peuvent être obtenus par deux types de synthèses connues. Le premier type de synthèse met en oeuvre un pressage réactif durant lequel la microstructure des matières premières est modifiée. Se forme alors un matériau solide dans lequel apparaît la phase MAX souhaitée et une ou plusieurs phases secondaires. La phase MAX est créée in situ (lors du frittage). Le second type de synthèse met en oeuvre une première opération permettant l'obtention du composé de la phase MAX souhaitée sous forme pulvérulente, par exemple par synthèse auto-propagée à haute température. La phase MAX est créée en amont. Une opération ultérieure de frittage permet l'obtention d'un matériau composite solide comprenant la phase MAX combinée à au moins une phase secondaire. Les documents suivants décrivent de telles synthèses :
Dans la plupart des cas, les phases secondaires sont obtenues involontairement. Le terme même de « secondaire » met en avant le faible intérêt des phases secondaires dans le comportement mécanique des matériaux solides obtenus. Bien souvent, la quantité volumique des phases secondaires est pourtant supérieure à celle de la phase MAX. Leurs natures et leurs quantités relatives dans les produits obtenus sont peu détaillées mais dépendent généralement des précurseurs utilisés. Parmi les phases secondaires détectées dans les produits, TiC est la phase la plus commune pour les phases MAX comme Ti3AlC2 ou Ti3SiC2. Or TiC est une phase reconnue comme néfaste pour les propriétés mécaniques et de résistance à la corrosion.In most cases, the secondary phases are unintentionally obtained. The very term "secondary" highlights the low interest of the secondary phases in the mechanical behavior of the solid materials obtained. Very often, the volume quantity of the secondary phases is nevertheless greater than that of the MAX phase. Their natures and relative amounts in the products obtained are not very detailed but generally depend on the precursors used. Among the secondary phases detected in the products, TiC is the most common phase for MAX phases such as Ti 3 AlC 2 or Ti 3 SiC 2 . Gold TiC is a phase recognized as harmful for the mechanical properties and corrosion resistance.
Dans
Le comportement en friction des matériaux à phase MAX a en outre été étudié, par exemple dans les documents suivants :
Dans
Un essai de synthèse de phases MAX est décrit dans l'article de
Aucun des matériaux composites de formule générale Tin+1AlCn/TixAly, connu ne présente une proportion finale entre phase MAX et phase intermétallique contrôlée avec précision et une densité élevée (avec n égal à 1 ou 2, x compris entre 1 et 3, y compris entre 1 et 3, et x + y ≤ 4). Aucun des matériaux connus ne permet donc de bénéficier pleinement des propriétés à la fois de la phase MAX, de la phase intermétallique et de leur combinaison, notamment les propriétés mécaniques et de résistance à la corrosion.None of the composite materials of general formula Ti n + 1 AlC n / Ti x Al y , known has a final proportion between MAX phase and intermetallic phase accurately controlled and a high density (with n equal to 1 or 2, x between 1 and 3, including between 1 and 3, and x + y ≤ 4). None of the known materials therefore makes it possible to fully benefit from the properties of both the MAX phase, the intermetallic phase and their combination, in particular the mechanical properties and the corrosion resistance properties.
L'invention vient améliorer la situation.The invention improves the situation.
À cette fin, la Demanderesse propose un matériau en cermet comprenant :
- une première phase MAX de formule générale Tin+1AlCn, et
- une seconde phase intermétallique de formule générale TixAly, où
x est compris entre 1 et 3,
y est compris entre 1 et 3, et
x + y ≤ 4,
la proportion volumique de la première phase dans le matériau étant comprise entre 70 % et 95 %,
la proportion volumique de la seconde phase dans le matériau étant comprise entre 30 % et 5 %,
le taux de porosité étant inférieur à 5 %.To this end, the Applicant proposes a cermet material comprising:
- a first MAX phase of general formula Ti n + 1 AlC n , and
- a second intermetallic phase of general formula Ti x Al y , where
x is between 1 and 3,
y is between 1 and 3, and
x + y ≤ 4,
the volume proportion of the first phase in the material being between 70% and 95%,
the volume proportion of the second phase in the material being between 30% and 5%,
the porosity rate being less than 5%.
Avantageusement, la proportion volumique en alliage TiC est inférieure à 5 % à l'équilibre thermodynamique.Advantageously, the volume proportion of TiC alloy is less than 5% to the thermodynamic equilibrium.
Dans le matériau cermet, la formule générale de la seconde phase intermétallique correspond, par exemple, aux valeurs
x = 1 et y = 1, ou
x = 1 et y = 3, ou
x = 3 et y = 1.In the cermet material, the general formula of the second intermetallic phase corresponds, for example, to the values
x = 1 and y = 1, or
x = 1 and y = 3, or
x = 3 and y = 1.
Selon un second aspect de l'invention, la Demanderesse propose un procédé de fabrication d'un matériau en cermet comprenant les étapes suivantes :
- a) mélanger
- du titane (Ti),
- de l'aluminium (Al), et
- un composé titane-carbone (TiC) ;
sous forme pulvérulente dans un milieu aqueux ou organique,
la teneur de chacun des éléments chimiques correspondant sensiblement aux proportions molaires finales souhaitées pour le matériau en cermet avec un excès d'aluminium (Al) entre 8 % et 17 % molaire ;
- b) sécher le mélange jusqu'à obtention d'une poudre ;
- c) fritter la poudre sous des conditions de températures comprises entre 800 °C et 1 400 °C et de pressions comprises entre 20 MPa et 40 MPa pendant un temps compris entre 1 et 3 heures pour former, à l'équilibre thermodynamique :
- une première phase MAX de formule générale Tin+1AlCn en proportion volumique dans le mélange comprise entre 70 % et 95 %, et
- une seconde phase intermétallique de formule générale TixAly en proportion volumique dans le mélange comprise entre 30 % et 5 %, et où
n est égal à 1ou 2,
x est compris entre 1 et 3,
y est compris entre 1 et 3, et
x + y ≤ 4.
- a) mix
- titanium (Ti),
- aluminum (Al), and
- a titanium-carbon compound (TiC);
in pulverulent form in an aqueous or organic medium,
the content of each of the chemical elements substantially corresponding to the final desired molar proportions for the cermet material with an excess of aluminum (Al) between 8% and 17 mol%;
- b) drying the mixture until a powder is obtained;
- c) sintering the powder under conditions of temperatures between 800 ° C and 1400 ° C and pressures between 20 MPa and 40 MPa for a time of between 1 and 3 hours to form, at thermodynamic equilibrium:
- a first MAX phase of general formula Ti n + 1 AlC n in a proportion by volume in the mixture of between 70% and 95%, and
- a second intermetallic phase of general formula Ti x Al y in a volume proportion in the mixture of between 30% and 5%, and
n is 1 or 2,
x is between 1 and 3,
y is between 1 and 3, and
x + y ≤ 4.
Avantageusement, la poudre est atomisée ou granulée préalablement à l'étape c) de frittage.Advantageously, the powder is atomized or granulated prior to the sintering step c).
Avantageusement, l'étape c) de frittage est mise en oeuvre sous vide ou en présence d'un gaz neutre.Advantageously, the sintering step c) is carried out under vacuum or in the presence of a neutral gas.
Le frittage peut comprendre la mise en oeuvre de l'une au moins des techniques parmi le pressage à chaud réactif, le pressage isostatique à chaud réactif et le frittage naturel réactif.The sintering may comprise the implementation of at least one of reactive hot pressing, reactive hot isostatic pressing and reactive natural sintering.
Selon un mode de réalisation du procédé de l'invention, la poudre est placée dans une matrice de pressage lors du frittage.According to one embodiment of the process of the invention, the powder is placed in a pressing matrix during sintering.
La poudre peut, de plus être encapsulée dans une gaine métallique.The powder may further be encapsulated in a metal sheath.
D'autres caractéristiques, détails et avantages de l'invention apparaîtront à la lecture de la description détaillée ci-après, et des figures annexées, sur lesquelles :
- la
figure 1 montre une vue au microscope électronique à balayage (MEB) d'un composite Ti2AlC/TiAl3 selon l'invention élaboré par pressage à chaud réactif à 1 300 °C, - la
figure 2 montre une vue au MEB d'un composite Ti3AlC2/TiAl3 selon l'invention élaboré par pressage à chaud réactif à 1 430 °C, - la
figure 3 montre une vue au MEB d'un échantillon fracturé de Ti2AlC monophasé élaboré par pressage à chaud réactif à 1 430 °C, - la
figure 4 montre une vue au MEB d'une coupe polie de Ti2AlC monophasé élaboré par pressage à chaud réactif à 1 430 °C, et - la
figure 5 est un graphique comparatif représentant l'évolution de l'oxydation du Ti2AlC monophasée et du composite Ti2AlC/TiAl.
- the
figure 1 shows a scanning electron microscope (SEM) view of a Ti 2 AlC / TiAl 3 composite according to the invention prepared by reactive hot pressing at 1300 ° C, - the
figure 2 shows a SEM view of a Ti 3 AlC 2 / TiAl 3 composite according to the invention prepared by hot-pressing at 1430 ° C, - the
figure 3 shows a SEM view of a fractured single-phase Ti 2 AlC sample prepared by hot-pressing at 1430 ° C, - the
figure 4 shows a SEM view of a polished section of single-phase Ti 2 AlC made by hot-pressing at 1430 ° C, and - the
figure 5 is a comparative graph showing the evolution of oxidation of single-phase Ti 2 AlC and Ti 2 AlC / TiAl composite.
Les figures et la description ci-après contiennent, pour l'essentiel, des éléments de caractère certain. Ils pourront donc non seulement servir à mieux faire comprendre la présente invention, mais aussi contribuer à sa définition, le cas échéant. Les valeurs des grossissements « x1000 » et « x500 » indiquées sur les
On rappelle que les termes « phase MAX » désignent un composé de formule générale Mn+1AXn, où
- n est égal à 1 à 3,
- M représente l'un des métaux choisis des colonnes
- III B (groupe 3 ; Sc) ;
- IV B (groupe 4 ; Ti, Zr ou Hf) ;
- V B (groupe 5 ; V, Nb ou Ta) ;
- VI B (groupe 6 ; Cr ou Mo) ;
- A représente l'un des éléments choisis des colonnes
- III B (
groupe 12 ; Cd) ; - III A (groupe 13 ; Al, Ga, In ou Tl) ;
- IV A (
groupe 14 ; Si, Ge, Sn ou Pb) ; - V A (groupe 15 ; P ou As) ;
- VI A (
groupe 16 ; S) ;
- III B (
- X représente le carbone (C) et/ou l'azote (N).
- n is 1 to 3,
- M represents one of the chosen metals of the columns
- III B (group 3; Sc);
- IV B (group 4, Ti, Zr or Hf);
- VB (group 5; V, Nb or Ta);
- VI B (group 6, Cr or Mo);
- A represents one of the chosen elements of the columns
- III B (
group 12, Cd); - III A (group 13, Al, Ga, In or Tl);
- IV A (
group 14, Si, Ge, Sn or Pb); - VA (group 15, P or As);
- VI A (
group 16; S);
- III B (
- X represents carbon (C) and / or nitrogen (N).
On notera que les phases MAX présentent une structure cristalline particulière, constituée de feuillets à l'échelle atomique.It will be noted that the MAX phases have a particular crystalline structure, consisting of layers at the atomic scale.
Dans le cas des carbures (X = C), respectivement nitrures (X = N), cette structure cristalline se décrit comme une alternance de feuillets d'octaèdres de carbure, par exemple du carbure de titane (TiC), respectivement un nitrure de titane (TiN), et d'un métal comme l'aluminium (Al) constituant les plans A. L'empilement de ces feuillets conduit à une structure cristalline définie comme un arrangement hexagonal dont le groupe d'espace est P63/m mc.In the case of carbides (X = C), respectively nitrides (X = N), this crystalline structure is described as alternating sheets of carbide octahedra, for example titanium carbide (TiC), respectively a titanium nitride. (TiN), and a metal such as aluminum (Al) constituting the planes A. The stack of these sheets leads to a crystalline structure defined as a hexagonal arrangement whose space group is P6 3 / m mc.
Une telle alternance conduit à une nano-structuration naturelle qui confère des propriétés particulières qui se situent entre celles des métaux et celles des céramiques. Comme les métaux, les phases MAX présentent une excellente résistance aux chocs mécaniques et thermiques, une forte conductivité électrique et thermique et une bonne usinabilité grâce à un effet d'autolubrification. Comme les céramiques, les phases MAX présentent de faibles densités, des modules de Young élevés, des résistances mécaniques élevées, de faibles coefficients de dilatation thermique et des températures de fusion élevées.Such alternation leads to a natural nano-structuring which confers particular properties which lie between those of metals and those of ceramics. Like metals, the MAX phases have excellent resistance to mechanical and thermal shock, high electrical and thermal conductivity and good machinability thanks to a self-lubricating effect. Like ceramics, MAX phases have low densities, high Young's moduli, high mechanical strengths, low thermal expansion coefficients, and high melting temperatures.
Par rapport aux céramiques usuelles, les phases MAX présentent une meilleure tolérance aux dommages et une grande capacité de déformation. Ces propriétés sont opérantes notamment à température ambiante pour de faibles vitesses de déformation. Les phases MAX présentent un comportement mécanique non linéaire réversible. Ils présentent également une faible sensibilité aux défauts de surface et une ténacité accrue par rapport aux céramiques usuelles.Compared with the usual ceramics, the MAX phases have a better tolerance to damage and a high capacity for deformation. These properties are operative especially at room temperature for low rates of deformation. The MAX phases exhibit a reversible nonlinear mechanical behavior. They also have a low sensitivity to surface defects and increased toughness compared to conventional ceramics.
Il est admis que la porosité est généralement néfaste pour les propriétés des matériaux, notamment en résistance mécanique et en résistance à l'oxydation. Dans ce contexte, réduire la porosité est considéré comme équivalent à augmenter la densité dans la plage envisagée.It is accepted that the porosity is generally harmful for the properties of the materials, in particular in mechanical strength and resistance to oxidation. In this context, reducing the porosity is considered equivalent to increasing the density in the envisaged range.
Jusqu'à maintenant, la porosité intergranulaire et l'apparition de phases secondaires résiduelles non souhaitées lors de la création de cermets à phase MAX étaient considérées comme des phénomènes indissociables et néfastes. Par conséquent, la réduction de la proportion de phase intermétallique était un but en soi.Until now, intergranular porosity and the appearance of undesired residual secondary phases during the creation of MAX phase cermets were considered indissociable and harmful phenomena. Therefore, reducing the proportion of intermetallic phase was a goal in itself.
La Demanderesse a essayé, avec succès, de réduire la porosité intergranulaire du composite final tout en obtenant une proportion significative de phase intermétallique.The Applicant has successfully tried to reduce the intergranular porosity of the final composite while obtaining a significant proportion of intermetallic phase.
Jusqu'à maintenant, les phases MAX étaient généralement réalisées par pressage à chaud, uniaxial ou isostatique. Des phases secondaires résiduelles non souhaitées apparaissaient de manière non maîtrisée. Les phases secondaires sont, par exemple, constituées de TiC ou de TiSi2.Until now, the MAX phases were generally performed by hot pressing, uniaxial or isostatic. Residual unwanted secondary phases appeared in an uncontrolled manner. The secondary phases are, for example, made of TiC or TiSi 2 .
La croissance des phases MAX se fait plan par plan avec une vitesse de croissance dans le plan de base hexagonal beaucoup plus rapide que suivant son orthogonale, le paramètre de maille c. Ce mode de croissance conduit à la formation de plaquettes en forme d'ellipsoïdes élancées d'orientations quelconques. Les plaquettes ne peuvent donc pas remplir tout l'espace. Par nécessité topologique, il se crée des zones peu ou pas actives, éloignées des marches de croissance, entraînant une diffusion ralentie et la formation de pores ou de phases non réagies. Autrement dit, l'élaboration par les méthodes classiques conduit à la formation de plaquettes orientées de façon aléatoire, ce qui crée des porosités intergranulaires.The growth of the MAX phases is plane by plane with a growth rate in the hexagonal base plane much faster than its orthogonal, the mesh parameter c. This mode of growth leads to the formation of ellipsoid-shaped platelets slender of any orientation. The pads can not fill the entire space. By topological necessity, areas of little or no activity are created, remote from the growth stages, resulting in slow diffusion and the formation of pores or unreacted phases. In other words, elaboration by conventional methods leads to the formation of randomly oriented platelets, which creates intergranular porosities.
Les phases secondaires peuvent aussi être dues, par exemple, à une non-réactivité des éléments de départ ou à la volatilisation de certains éléments comme le métal.The secondary phases may also be due, for example, to a non-reactivity of the starting elements or to the volatilization of certain elements such as metal.
Généralement, la porosité favorise l'oxydation par diffusion de l'oxygène (O). La Demanderesse a essayé de la réduire ainsi que la proportion de certaines seulement des phases secondaires ou non réagies, en particulier TiC.Generally, porosity promotes oxidation by diffusion of oxygen (O). The Applicant has tried to reduce it as well as the proportion of some only secondary or unreacted phases, in particular TiC.
La Demanderesse a élaboré des composites de matériaux thermodynamiquement stables à base d'une phase MAX de formule générale Tin+1AlCn, et d'une phase intermétallique de formule générale TixAly, où
n est égal à 1 ou 2,
x est compris entre 1 et 3,
y est compris entre 1 et 3, et
x + y ≤ 4.The Applicant has developed composites of thermodynamically stable materials based on a MAX phase of general formula Ti n + 1 AlC n , and an intermetallic phase of general formula Ti x Al y , where
n is 1 or 2,
x is between 1 and 3,
y is between 1 and 3, and
x + y ≤ 4.
En proportion volumique, la phase intermétallique est inférieure à la phase MAX. Dans les exemples décrits ici, la proportion volumique de la phase intermétallique par rapport à la phase MAX est comprise entre 5 % et 30 %.In volume proportion, the intermetallic phase is lower than the MAX phase. In the examples described here, the volume proportion of the intermetallic phase relative to the MAX phase is between 5% and 30%.
Les phases MAX prennent, par exemple, la forme de Ti2AlC ou Ti3AlC2. Les intermétalliques prennent, par exemple, la forme de TiAl, Ti3Al ou TiAl3. Les composites Ti2AlC/TixAly ou Ti3AlC2/TixAly sont élaborés, ici, par pressage à chaud réactif.The MAX phases take, for example, the form of Ti 2 AlC or Ti 3 AlC 2 . The intermetallics take, for example, the form of TiAl, Ti 3 Al or TiAl 3 . The Ti 2 AlC / Ti x Al y or Ti 3 AlC 2 / Ti x Al y composites are prepared here by hot-pressing.
Le mélange suivant est réalisé :
- 6,39 g de Ti,
- 3,17 g d'Al, et
- 5,43 g de TiC
- 6.39 g of Ti,
- 3.17 g of Al, and
- 5.43 g of TiC
Sont ajoutés :
- 1,03 g de Ti, et
- 0,64 g d'Al
- 1.03 g of Ti, and
- 0.64 g of Al
Les poudres sont intimement mélangées par broyage. Dans cet exemple, un broyage en jarre et en présence de billes en carbure de tungstène (WC) est mis en oeuvre. Le broyage est réalisé dans de l'éthanol. Le broyage dure 2 heures.The powders are intimately mixed by grinding. In this example, a jar crushing and in the presence of tungsten carbide balls (WC) is implemented. The grinding is carried out in ethanol. The grinding lasts 2 hours.
Le mélange ainsi obtenu est séché. Dans cet exemple, le mélange est disposé dans un évaporateur rotatif. Il est ensuite placé dans une étuve à 100 °C pendant 12 heures.The mixture thus obtained is dried. In this example, the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
La poudre obtenue est pressée à chaud. Dans cet exemple, le pressage à chaud est réalisé dans un moule en graphite de 36 mm x 36 mm, à 1 200 °C, pendant 2 heures, sous une contrainte uniaxiale de 30 MPa, sous une atmosphère d'argon (Ar) à 1 bar. Pour faciliter le démoulage, du graphite souple recouvre les parois intérieures du moule. Ici, des feuilles vendues sous le nom commercial Papyex sont utilisées.The powder obtained is hot pressed. In this example, hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1200 ° C., for 2 hours, under a uniaxial stress of 30 MPa, under an argon (Ar) atmosphere. 1 bar. To facilitate demolding, soft graphite covers the inner walls of the mold. Here, leaves sold under the trade name Papyex are used.
Le matériau obtenu est démoulé et présente une forme de plaque de 36 mm x 36 mm et d'épaisseur de 3 mm.The material obtained is removed from the mold and has a plate shape of 36 mm × 36 mm and a thickness of 3 mm.
En vue des caractérisations mécaniques et morphologiques, des barrettes de flexion de 35 mm x 5 mm x 2 mm et des éprouvettes entaillées de 35 mm x 3,6 mm x 1,8 mm sont découpées dans la plaque.For mechanical and morphological characterization, 35 mm x 5 mm x 2 mm bending bars and 35 mm x 3.6 mm x 1.8 mm notched specimens are cut from the plate.
Des caractérisations par diffraction des rayons X (DRX) sont menées sur des échantillons tirés de la plaque. Du Ti2AlC et du TiAl sont détectés et représentent en volume respectivement 76 % et 19 %. Il est en outre détecté des résidus de TiAl3 et de TiC qui représentent en volume respectivement 2,5 % et 2,4 %. La somme des résidus de TiAl3 et de TiC est inférieure à 5 % en volume.X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate. Ti 2 AlC and TiAl are detected and represent in volume respectively 76% and 19%. In addition, residues of TiAl 3 and TiC are detected which represent in volume respectively 2.5% and 2.4%. The sum of TiAl 3 and TiC residues is less than 5% by volume.
Le taux de porosité ouverte est mesuré par poussée d'Archimède. Un taux de 1 % est mesuré. Ceci confirme la bonne densification du matériau.The open porosity rate is measured by buoyancy. A rate of 1% is measured. This confirms the good densification of the material.
Le module de Young mesuré par résonance dynamique (« GrindoSonic MK5i ») est de 225 GPa (norme ASTM Standard « E1876-07 »).The Young modulus measured by dynamic resonance ("GrindoSonic MK5i") is 225 GPa (standard ASTM Standard "E1876-07").
La contrainte à la rupture en flexion trois points à température ambiante est de 253 MPa ± 20 MPa.The three-point bending stress at room temperature is 253 MPa ± 20 MPa.
La ténacité mesurée par flexion sur éprouvette entaillée (ou SENB pour « Single-Edge Notched Bending ») est de 5,1 MPa.m1/2 ± 0,1 MPa.m1/2 (norme « E399 -83 »)The toughness measured by notched bending (or SENB for Single-Edge Notched Bending ) is 5.1 MPa.m 1/2 ± 0.1 MPa.m 1/2 (standard "E399 -83")
La dureté mesurée par indentation Vickers (charge 50 g) est de 4,7 GPa ± 0,5 GPa.The hardness measured by Vickers indentation (50 g load) is 4.7 GPa ± 0.5 GPa.
Dans les autres exemples, les essais sont réalisés dans les mêmes conditions et en respectant les mêmes normes.In the other examples, the tests are carried out under the same conditions and with the same standards.
Le mélange suivant est réalisé :
- 6,39 g de Ti,
- 3,17 g d'Al, et
- 5,43 g de TiC
- 6.39 g of Ti,
- 3.17 g of Al, and
- 5.43 g of TiC
Sont ajoutés :
- 1,03 g de Ti, et
- 0,64 g d'Al
- 1.03 g of Ti, and
- 0.64 g of Al
Les poudres sont intimement mélangées par broyage. Dans cet exemple, un broyage en jarre et en présence de billes en carbure de tungstène (WC) est mis en oeuvre. Le broyage est réalisé dans de l'éthanol. Le broyage dure 2 heures.The powders are intimately mixed by grinding. In this example, a jar crushing and in the presence of tungsten carbide balls (WC) is implemented. The grinding is carried out in ethanol. The grinding lasts 2 hours.
Le mélange ainsi obtenu est séché. Dans cet exemple, le mélange est disposé dans un évaporateur rotatif. Il est ensuite placé dans une étuve à 100 °C pendant 12 heures.The mixture thus obtained is dried. In this example, the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
La poudre obtenue est pressée à chaud. Dans cet exemple, le pressage à chaud est réalisé dans un moule en graphite de 36 mm x 36 mm, à 1 430 °C, pendant 2 heures, sous une contrainte uniaxiale de 30 MPa, sous une atmosphère d'argon (Ar) à 1 bar. Pour faciliter le démoulage, du graphite souple recouvre les parois intérieures du moule. Ici, des feuilles vendues sous le nom commercial Papyex sont utilisées.The powder obtained is hot pressed. In this example, the hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1430 ° C, for 2 hours, under a uniaxial stress of 30 MPa, under an argon (Ar) atmosphere. 1 bar. To facilitate demolding, soft graphite covers the inner walls of the mold. Here, leaves sold under the trade name Papyex are used.
Le matériau obtenu est démoulé et présente une forme de plaque de 36 mm x 36 mm et d'épaisseur de 3 mm.The material obtained is removed from the mold and has a plate shape of 36 mm × 36 mm and a thickness of 3 mm.
En vue des caractérisations mécaniques et morphologiques, des barrettes de flexion de 35 mm x 5 mm x 2 mm et des éprouvettes entaillées de 35 mm x 3,6 mm x 1,8 mm sont découpées dans la plaque.For mechanical and morphological characterization, 35 mm x 5 mm x 2 mm bending bars and 35 mm x 3.6 mm x 1.8 mm notched specimens are cut from the plate.
Des caractérisations par diffraction des rayons X (DRX) sont menées sur des échantillons tirés de la plaque. Du Ti3AlC2 et du TiAl3 sont détectés et représentent en volume respectivement 88,5 % et 7 %. Il est en outre détecté des résidus de Al2O3 et de TiC qui représentent en volume respectivement 1,5 % et 3 %. La somme des résidus de Al2O3 et de TiC représente une proportion en volume inférieure à 5 %.X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate. Ti 3 AlC 2 and TiAl 3 are detected and represent in volume respectively 88.5% and 7%. Residues of Al 2 O 3 and TiC are also detected, which represent in volume respectively 1.5% and 3%. The sum of Al 2 O 3 and TiC residues is less than 5% by volume.
La
Le taux de porosité ouverte est mesuré par poussée d'Archimède. Un taux de 0,8 % est mesuré. Ceci confirme la bonne densification du matériau.The open porosity rate is measured by buoyancy. A rate of 0.8% is measured. This confirms the good densification of the material.
Le module de Young mesuré par résonance dynamique est de 297 GPa.The Young modulus measured by dynamic resonance is 297 GPa.
La contrainte à la rupture en flexion trois points à température ambiante est de 367 MPa ± 31 MPa.The three-point bending stress at room temperature is 367 MPa ± 31 MPa.
La ténacité mesurée par flexion sur éprouvette entaillée (ou SENB pour « Single-Edge Notched Bending ») est de 7,3 MPa.m1/2 ± 0,4 MPa.m1/2.The toughness measured by notch bending (or SENB for " Single-Edge Notched Bending ") is 7.3 MPa.m 1/2 ± 0.4 MPa.m 1/2 .
La dureté mesurée par indentation Vickers est de 5,2 GPa ± 0,6 GPa.The hardness measured by Vickers indentation is 5.2 GPa ± 0.6 GPa.
Le mélange suivant est réalisé :
- 6,39 g de Ti,
- 3,17 g d'Al, et
- 5,43 g de TiC
- 6.39 g of Ti,
- 3.17 g of Al, and
- 5.43 g of TiC
Sont ajoutés :
- 0,5 g de Ti, et
- 0,32 g d'Al
- 0.5 g of Ti, and
- 0.32 g of Al
Les poudres sont intimement mélangées par broyage. Dans cet exemple, un broyage en jarre et en présence de billes en carbure de tungstène (WC) est mis en oeuvre. Le broyage est réalisé dans de l'éthanol. Le broyage dure 2 heures.The powders are intimately mixed by grinding. In this example, a jar crushing and in the presence of tungsten carbide balls (WC) is implemented. The grinding is carried out in ethanol. The grinding lasts 2 hours.
Le mélange ainsi obtenu est séché. Dans cet exemple, le mélange est disposé dans un évaporateur rotatif. Il est ensuite placé dans une étuve à 100 °C pendant 12 heures.The mixture thus obtained is dried. In this example, the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
La poudre obtenue est pressée à chaud. Dans cet exemple, le pressage à chaud est réalisé dans un moule en graphite de 36 mm x 36 mm, à 1 300 °C, pendant 1 heure et 30 minutes, sous une contrainte uniaxiale de 30 MPa, sous une atmosphère d'argon (Ar) à 1 bar. Pour faciliter le démoulage, du graphite souple recouvre les parois intérieures du moule. Ici, des feuilles vendues sous le nom commercial Papyex sont utilisées.The powder obtained is hot pressed. In this example, the hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1300 ° C, for 1 hour and 30 minutes, under a uniaxial stress of 30 MPa, under an argon atmosphere ( Ar) at 1 bar. To facilitate demolding, soft graphite covers the inner walls of the mold. Here, leaves sold under the trade name Papyex are used.
Le matériau obtenu est démoulé et présente une forme de plaque de 36 mm x 36 mm et d'épaisseur de 3 mm.The material obtained is removed from the mold and has a plate shape of 36 mm × 36 mm and a thickness of 3 mm.
En vue des caractérisations mécaniques et morphologiques, des barrettes de flexion de 35 mm x 5 mm x 2 mm et des éprouvettes entaillées de 35 mm x 3,6 mm x 1,8 mm sont découpées dans la plaque.For mechanical and morphological characterization, 35 mm x 5 mm x 2 mm bending bars and 35 mm x 3.6 mm x 1.8 mm notched specimens are cut from the plate.
Des caractérisations par diffraction des rayons X (DRX) sont menées sur des échantillons tirés de la plaque. Du Ti2AlC et du TiAl3 sont détectés et représentent en volume respectivement 80,5 % et 15 %. Il est en outre détecté des résidus de TiAl et de TiC qui représentent en volume respectivement 1,5 % et 3 %. La somme des résidus de TiAl et de TiC est inférieure à 5 % en volume.X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate. Ti 2 AlC and TiAl 3 are detected and represent in volume respectively 80.5% and 15%. TiAl and TiC residues, which represent 1.5% and 3% by volume respectively, are also detected. The sum of TiAl and TiC residues is less than 5% by volume.
Le taux de porosité ouverte est mesuré par poussée d'Archimède. Un taux de 1 % est mesuré. Ceci confirme la bonne densification du matériau.The open porosity rate is measured by buoyancy. A rate of 1% is measured. This confirms the good densification of the material.
Le module de Young mesuré par résonance dynamique est de 220 GPa.The Young's modulus measured by dynamic resonance is 220 GPa.
La contrainte à la rupture en flexion trois points à température ambiante est de 350 MPa ± 55 MPa.The three-point bending stress at room temperature is 350 MPa ± 55 MPa.
La ténacité mesurée par flexion sur éprouvette entaillée (ou SENB pour « Single-Edge Notched Bending ») est de 8,7 MPa.m1/2 ± 0,2 MPa.m1/2.The toughness measured by notch bending (or SENB for " Single-Edge Notched Bending ") is 8.7 MPa.m 1/2 ± 0.2 MPa.m 1/2 .
La dureté mesurée par indentation Vickers est de 4,5 GPa ± 0,1 GPa.The hardness measured by Vickers indentation is 4.5 GPa ± 0.1 GPa.
Le mélange suivant est réalisé :
- 6,39 g de Ti,
- 3,17 g d'Al, et
- 5,43 g de TiC
- 6.39 g of Ti,
- 3.17 g of Al, and
- 5.43 g of TiC
Les poudres sont intimement mélangées par broyage. Dans cet exemple, un broyage en jarre et en présence de billes en carbure de tungstène (WC) est mis en oeuvre. Le broyage est réalisé dans de l'éthanol. Le broyage dure 2 heures.The powders are intimately mixed by grinding. In this example, a jar crushing and in the presence of tungsten carbide balls (WC) is implemented. The grinding is carried out in ethanol. The grinding lasts 2 hours.
Le mélange ainsi obtenu est séché. Dans cet exemple, le mélange est disposé dans un évaporateur rotatif. Il est ensuite placé dans une étuve à 100 °C pendant 12 heures.The mixture thus obtained is dried. In this example, the mixture is placed in a rotary evaporator. It is then placed in an oven at 100 ° C for 12 hours.
La poudre obtenue est pressée à chaud. Dans cet exemple, le pressage à chaud est réalisé dans un moule en graphite de 36 mm x 36 mm, à 1 430 °C, pendant 1 heure, sous une contrainte uniaxiale de 40 MPa, sous une atmosphère d'argon (Ar) à 1 bar. Pour faciliter le démoulage, du graphite souple recouvre les parois intérieures du moule. Ici, des feuilles vendues sous le nom commercial Papyex sont utilisées.The powder obtained is hot pressed. In this example, hot pressing is carried out in a 36 mm x 36 mm graphite mold, at 1430 ° C, for 1 hour, under a uniaxial stress of 40 MPa, under an argon (Ar) atmosphere. 1 bar. To facilitate demolding, soft graphite covers the inner walls of the mold. Here, leaves sold under the trade name Papyex are used.
Le matériau obtenu est démoulé et présente une forme de plaque de 36 mm x 36 mm et d'épaisseur de 3 mm.The material obtained is removed from the mold and has a plate shape of 36 mm × 36 mm and a thickness of 3 mm.
Des caractérisations par diffraction des rayons X (DRX) sont menées sur des échantillons tirés de la plaque. Du Ti2AlC est détecté dans une proportion volumique supérieure à 98 %. Le matériau obtenu peut donc être considéré comme monophasé. La phase complémentaire comprend du Ti3Al.X-ray diffraction (XRD) characterizations are conducted on samples taken from the plate. Ti 2 AlC is detected in a volume proportion of greater than 98%. The material obtained can therefore be considered as single phase. The complementary phase comprises Ti 3 Al.
Le taux de porosité ouverte est mesuré par poussée d'Archimède. Un taux de 1 % est mesuré. Ceci confirme la bonne densification du matériau.The open porosity rate is measured by buoyancy. A rate of 1% is measured. This confirms the good densification of the material.
En outre, des porosités fermées sont observées par microscopie. Les
En parallèle de la préparation du Ti2AlC monophasé, un composite Ti2AlC/TiAl est préparé de manière identique à ce qui a été fait dans l'exemple 1.In parallel with the preparation of the single-phase Ti 2 AlC, a Ti 2 AlC / TiAl composite is prepared in the same manner as was done in Example 1.
En vue des essais comparatifs d'oxydation suivants, deux échantillons de 15 mm x 5 mm x 2 mm, sont découpés dans les plaques obtenues, du Ti2AlC monophasé pour l'un, du composite Ti2AlC/TiAl pour l'autre.For the following oxidation comparison tests, two 15 mm × 5 mm × 2 mm samples are cut from the resulting plates, one-phase Ti 2 AlC for one, the Ti 2 AlC / TiAl composite for the other. .
Les deux échantillons sont placés ensemble dans un four à 1 100 °C.The two samples are placed together in an oven at 1100 ° C.
Après une heure, les échantillons sont sortis du four, refroidis par un ventilateur et pesés. En fonction des dimensions initiales et de la masse initiale de chaque échantillon, il en est déduit une prise en masse surfacique. Cette prise en masse surfacique est représentative de l'évolution de l'oxydation des échantillons.After one hour, the samples are taken out of the oven, cooled by a fan and weighed. Depending on the initial dimensions and the initial mass of each sample, it is deduced a weight gain area. This weight gain is representative of the evolution of the oxidation of the samples.
Ensuite, les échantillons de Ti2AlC/TiAl sont de nouveau placés dans le four à 1 100 °C. Après une durée supplémentaire d'une heure, les échantillons sont de nouveau sortis du four et refroidis par un ventilateur. Une fois refroidis, les échantillons sont replacés dans le four à 1 100 °C pour un nouveau cycle d'une heure. Ces opérations sont répétées de nombreuses fois. Lors de certaines phases hors du four, l'échantillon est pesé de manière à suivre la prise en masse surfacique au cours du temps.Then, the Ti 2 AlC / TiAl samples are again placed in the oven at 1100 ° C. After an additional one hour, the samples are again taken out of the oven and cooled by a fan. Once cooled, the samples are returned to the oven at 1100 ° C for a new cycle of one hour. These operations are repeated many times. During certain phases outside the oven, the sample is weighed so as to follow the weighting of the surface over time.
Les résultats sont représentés dans le graphique comparatif de la
Les quatre exemples décrits ci-avant constituent une sélection parmi l'ensemble des essais réalisés par la Demanderesse.The four examples described above constitute a selection among all the tests carried out by the Applicant.
La Demanderesse a mis au point un procédé de fabrication permettant d'obtenir des matériaux en cermet à phase MAX aux propriétés améliorées.The Applicant has developed a manufacturing method for obtaining MAX cermet materials with improved properties.
Le titane (Ti), l'aluminium (Al) et le composé titane-carbone (TiC) sont mélangés dans les proportions stoechiométriques auxquelles est ajouté un excès d'aluminium compris entre 8 % et 17 % molaire. Le mélange ainsi formé présente les proportions des éléments chimiques des composés finaux, dès la forme pulvérulente, avant le frittage. On peut alors parler de former un équivalent Ti2AlC - TiAl in situ, par opposition aux procédés pour lesquels :
- i) dans un premier temps, la phase MAX est synthétisée séparément, puis
- ii) dans un second temps, le métal est ajouté et solubilisé dans une phase liquide de la phase MAX pour former l'intermétallique, puis
- iii) un traitement thermique est appliqué au mélange.
- i) first, the MAX phase is synthesized separately, then
- ii) in a second step, the metal is added and solubilized in a liquid phase of the MAX phase to form the intermetallic, then
- iii) a heat treatment is applied to the mixture.
La proportion de la phase intermétallique par rapport à la phase MAX dans le produit obtenu peut varier de 5 % à 30 % en volume.The proportion of the intermetallic phase relative to the MAX phase in the product obtained may vary from 5% to 30% by volume.
Le mélange est effectué par des méthodes connues en tant que telles, par exemple au moyen d'un broyeur planétaire, ou par attrition. Des billes de broyage peuvent être utilisées, par exemple en carbure de tungstène (WC) comme dans les exemples précédents, en dioxyde de zircone (ZrO2) ou encore en alumine (Al2O3). Les billes non oxyde telles que celles en carbure de tungstène (WC) ont démontré une meilleure efficacité et permettent de limiter la pollution par des oxydes.The mixing is carried out by methods known per se, for example by means of a planetary mill, or by attrition. Grinding balls may be used, for example tungsten carbide (WC) as in the previous examples, zirconia dioxide (ZrO 2 ) or alumina (Al 2 O 3 ). Non-oxide balls such as those made of tungsten carbide (WC) have demonstrated better efficiency and can limit pollution by oxides.
Le mélange peut être effectué dans un milieu organique tel que l'éthanol comme cela est décrit dans les exemples précédents. En variante, le milieu peut être aqueux.The mixture can be carried out in an organic medium such as ethanol as described in the preceding examples. Alternatively, the medium may be aqueous.
Des solvants organiques peuvent être ajoutés afin d'améliorer l'homogénéité du mélange. Par exemple, un dispersant tel qu'un ester phosphorique connu sous la référence commerciale « Beycostat C 213 » ou un polyméthacrylate d'ammonium connu sous la référence commerciale « Darvan C ».Organic solvents may be added to improve the homogeneity of the mixture. For example, a dispersant such as a phosphoric ester known under the trade name "Beycostat C 213" or ammonium polymethacrylate known under the trade designation "Darvan C".
La suspension est séchée, en particulier dans un évaporateur rotatif.The suspension is dried, in particular in a rotary evaporator.
La poudre ainsi obtenue peut être travaillée pour obtenir une poudre plus facile à couler et plus facile à manipuler dans les étapes ultérieures de mise en forme par pressage. Par exemple, la poudre obtenue peut être atomisée ou granulée par des techniques connues en tant que telles comme l'atomisation ou le tamisage.The powder thus obtained can be worked to obtain a powder which is easier to cast and easier to handle in the subsequent steps of press forming. For example, the resulting powder may be atomized or granulated by techniques known per se such as atomization or sieving.
La poudre est ensuite frittée. Le frittage s'effectue par des techniques connues en tant que telles, par exemple, par pressage à chaud réactif, par pressage isostatique à chaud réactif, ou encore par un frittage naturel réactif. Pour plus de détails sur lesdites techniques, le lecteur est invité à consulter, par exemple, le document « Fondamentaux en chimie » ; Référence TIB106DUO, édité par « Les techniques de l'ingénieur », volume 42106210, référence AF6620, publié le 10 juillet 2005.The powder is then sintered. The sintering is carried out by known techniques as such, for example, by hot-pressing reagent, hot isostatic pressing reactive, or by a natural sintering reactive. For more details on these techniques, the reader is invited to consult, for example, the document " Fundamentals in Chemistry "; Reference TIB106DUO, published by " The techniques of the engineer ", volume 42106210, reference AF6620, published on July 10, 2005.
Le pressage à chaud réactif, assurant un certain degré de confinement de la matière et de plus facile à mettre en oeuvre, est préféré. Dans ce cas, la poudre précédemment obtenue est placée dans une matrice de pressage de la forme désirée simple, par exemple carrée ou cylindrique, ou complexe. La composition de la matrice de pressage est adaptée aux températures mises en oeuvre, par exemple en graphite ou en métal.Reactive hot pressing, providing a degree of containment of the material and easier to implement, is preferred. In this case, the previously obtained powder is placed in a pressing die of the desired simple shape, for example square or cylindrical, or complex. The composition of the pressing matrix is adapted to the temperatures used, for example graphite or metal.
La Demanderesse a observé qu'une contrainte appliquée supérieure à 15 MPa permettait d'obtenir de bons résultats. En particulier, une plage comprise entre 20 MPa et 40 MPa est adaptée.The Applicant has observed that an applied stress greater than 15 MPa made it possible to obtain good results. In particular, a range of between 20 MPa and 40 MPa is suitable.
Dans le cas d'un pressage isostatique à chaud, la poudre peut être encapsulée dans une gaine métallique. Ceci permet d'éviter la volatilisation d'espèces chimiques. Le pressage isostatique à chaud permet, en outre, d'augmenter la densité.In the case of hot isostatic pressing, the powder may be encapsulated in a metal sheath. This avoids the volatilization of chemical species. Hot isostatic pressing also makes it possible to increase the density.
Dans des variantes, la poudre subit dans un premier temps un frittage naturel, c'est-à-dire sans appliquer de pression. Puis, dans un second temps, un frittage isostatique à chaud est mis en oeuvre. Ces variantes permettent, en particulier, de fermer la porosité lors du frittage naturel, puis de compléter la densification par le frittage isostatique à chaud. Ainsi, des produits de formes très complexes peuvent être réalisés. Cela dispense également de l'encapsulation dans une gaine.In variants, the powder is first subjected to natural sintering, that is to say without applying pressure. Then, in a second step, hot isostatic sintering is carried out. These variants make it possible, in particular, to close the porosity during natural sintering, and then to complete the densification by hot isostatic sintering. Thus, products of very complex shapes can be made. This also exempts encapsulation in a sheath.
Le frittage s'effectue sous vide ou sous atmosphère neutre tel que sous argon (Ar), diazote (N2) ou hélium (He). L'argon est préféré. La pression de gaz appliquée peut varier entre 0 et 1 bar.The sintering is carried out under vacuum or in a neutral atmosphere such as under argon (Ar), dinitrogen (N 2 ) or helium (He). Argon is preferred. The applied gas pressure can vary between 0 and 1 bar.
La formation du composite s'effectue in situ par réaction au cours du frittage.Composite formation occurs in situ by reaction during sintering.
Les matériaux obtenus sont biphasés, ce qui n'exclut pas la présence de résidus tiers, mais dans des proportions inférieures à 3% en masse (limite de détection des DRX).The materials obtained are two-phase, which does not exclude the presence of third-party residues, but in proportions of less than 3% by mass (detection limit of XRDs).
Comme le montrent notamment les exemples 1 et 2 précédents, obtenir le composite Ti2AlC/TixAly ou Ti3AlC2/TixAly peut être sélectionné en jouant sur la température lors du frittage.As shown in particular in Examples 1 and 2 above, obtaining the Ti 2 AlC / Ti x Al y or Ti 3 AlC 2 / Ti x Al y composite can be selected by varying the temperature during sintering.
Les chemins réactionnels pour la synthèse des composites selon l'invention ont été identifiés et sont décrits par les équations suivantes :
De 600 °C à 800 °C :- À 900 °C :
Diminution de Ti au profit de TiAl - De 1 000 °C à 1 200 °C :
- À 1 300 °C :
- À 1 400 °C :
- Pour une température supérieure à 1 450 °C ou 1 500 °C : par exemple,
- From 600 ° C to 800 ° C:
- At 900 ° C:
Decrease of Ti in favor of TiAl - From 1000 ° C to 1200 ° C:
- At 1300 ° C:
- At 1400 ° C:
- For a temperature above 1450 ° C or 1500 ° C: for example,
La phase Ti2AlC se forme entre 1 000 °C et 1 200 °C. Elle devient lacunaire en Al à environ 1 300 °C. À plus haute température, le volume cumulé des lacunes augmente de telle façon qu'à 1 400 °C, l'Al a tendance à sortir de Ti2AlC. En effet, les atomes d'aluminium situés dans les plans A des structures cristallographiques de ces matériaux sont faiblement liés. L'énergie de formation des lacunes d'Al est de loin la plus faible par rapport à celle de Ti ou C. La création de lacunes dans les plans A génère un affaiblissement supplémentaire de cette liaison. Il en résulte une augmentation de l'entropie de vibration. Ainsi, lorsque la température augmente jusqu'à 1 430 °C, les lacunes d'Al augmentent dans la phase MAX Ti2AlC jusqu'à la formation de la phase MAX Ti3AlC2 (cf. équations 3 et 5). Ceci explique notamment pourquoi les spécialistes des phases MAX considèrent généralement Ti2AlC comme une phase intermédiaire lors de la synthèse de Ti3AlC2. Ces phénomènes ont lieu dans le cas de l'exemple 2. Ti3AlC2 devient la phase majoritaire.The Ti 2 AlC phase is formed between 1000 ° C. and 1200 ° C. It becomes lacunary in Al at about 1300 ° C. At higher temperatures, the cumulative volume of the gaps increases so that at 1400 ° C, Al tends to exit Ti 2 AlC. Indeed, the aluminum atoms located in the planes A crystallographic structures of these materials are weakly related. The gap-forming energy of Al is by far the weakest relative to that of Ti or C. The creation of gaps in the planes A generates a further weakening of this connection. This results in an increase in the vibration entropy. Thus, when the temperature rises to 1430 ° C, the Al gaps increase in the MAX Ti 2 AlC phase until the formation of the MAX Ti 3 AlC 2 phase (see Equations 3 and 5). This explains why the MAX phase specialists generally consider Ti 2 AlC as an intermediate phase during the synthesis of Ti 3 AlC 2 . These phenomena take place in the case of Example 2. Ti 3 AlC 2 becomes the majority phase.
En parallèle, la phase intermétallique TiAl se forme à basse température, inférieure à 800 °C, et s'enrichit en Al, notamment libéré par la phase MAX. Lorsque l'enrichissement est suffisant, la phase intermétallique TiAl3 se forme.In parallel, the intermetallic TiAl phase is formed at low temperature, below 800 ° C, and enriches in Al, in particular released by the MAX phase. When the enrichment is sufficient, the TiAl 3 intermetallic phase is formed.
Ici, on permet volontairement un transfert d'Al de la phase MAX à la phase intermétallique TiAl, celle-ci pouvant admettre une sur-stoechiométrie en Al. Les liaisons interatomiques dans TiAl présentant une forte composante covalente. L'Al n'est pas enclin à se vaporiser ou à se dissocier de l'alliage. Il est donc possible de maintenir un équilibre thermodynamique entre TiAl et la phase MAX sur une large gamme de température. En toute hypothèse, les changements cristallographiques sont réversibles. Grâce à ces phénomènes contrôlés lors de la mise en oeuvre des procédés de fabrication décrits ci-avant, l'intégrité de la phase MAX est préservée.Here, a transfer of Al from the MAX phase to the TiAl intermetallic phase is deliberately allowed, the latter being able to admit an over-stoichiometry in Al. The interatomic bonds in TiAl having a strong covalent component. Al is not prone to vaporize or dissociate from the alloy. It is therefore possible to maintain a thermodynamic equilibrium between TiAl and the MAX phase over a wide temperature range. In any case, the crystallographic changes are reversible. Thanks to these phenomena controlled during the implementation of the manufacturing processes described above, the integrity of the MAX phase is preserved.
En particulier, et pour un domaine de température donné, un matériau monophasé serait détérioré alors même qu'une pièce réalisée à base des matériaux biphasés selon l'invention peut supporter, au moins de manière transitoire, la même température sans être dégradée. Ceci permet d'utiliser les pièces à base de matériaux biphasés dans des conditions de fonctionnement plus difficiles.In particular, and for a given temperature range, a single-phase material would be deteriorated even though a part made from two-phase materials according to the invention can withstand, at least temporarily, the same temperature without being degraded. This makes it possible to use parts based on two-phase materials under more difficult operating conditions.
L'équation 6 représente la limite en température des matériaux ainsi créés pour laquelle de l'Al est néanmoins expulsé. Dans ce cas, la phase Ti3AlC2 peut se transformer au moins en partie en TiC, ce qui est néfaste pour les propriétés recherchées du matériau.Equation 6 represents the temperature limit of the materials thus created for which Al is nevertheless expelled. In this case, the Ti 3 AlC 2 phase can be converted at least partly into TiC, which is detrimental to the desired properties of the material.
Les composites sont préférentiellement élaborés à des températures supérieures à 1 200 °C mais inférieures à celle de la décomposition de Ti3AlC2 (entre 1 450 °C et 1 500 °C). Ainsi, des matériaux à très haute densité sont obtenus. Par exemple, des taux de densification supérieurs à 95 % de la densité théorique sont atteints. La formation de TiC est empêchée, ou très limitée.The composites are preferably prepared at temperatures higher than 1200 ° C. but lower than that of the decomposition of Ti 3 AlCl 2 (between 1450 ° C. and 1500 ° C.). Thus, very high density materials are obtained. For example, densification rates greater than 95% of the theoretical density are achieved. TiC formation is prevented, or very limited.
La fabrication de tels matériaux cermets phase MAX-phase intermétallique permet de conserver, au moment de la croissance de la phase MAX, une phase intermétallique qui remplit les porosités entre les plaquettes de phase MAX. La phase MAX et la phase intermétallique sont alors en équilibre thermodynamique au cours des transformations de microstructures. Des chemins de diffusion sont préservés entre les différentes phases.The manufacture of such MAX-phase intermetallic phase cermet materials makes it possible to maintain, at the time of growth of the MAX phase, an intermetallic phase which fills the porosities between the MAX phase platelets. MAX phase and phase intermetallic are then in thermodynamic equilibrium during transformations of microstructures. Diffusion paths are preserved between the different phases.
Des comparaisons entre la microstructure du composé monophasé, ou monolithique, de phase MAX Ti2AlC de l'exemple 4 (
Le comblement de la porosité par la phase intermétallique explique l'amélioration des propriétés mécaniques. La densité de défauts macroscopiques, tels que les pores, est significativement réduite. En particulier, les propriétés de ténacité et de tenue au fluage sont améliorées.The filling of the porosity by the intermetallic phase explains the improvement of the mechanical properties. The density of macroscopic defects, such as pores, is significantly reduced. In particular, the properties of toughness and creep resistance are improved.
Les deux phases étant maintenues en équilibre thermodynamique, des traitements thermiques ultérieurs permettent de modifier les microstructures. Par exemple, Ti2AlC/TiAl est obtenu à 1 200 °C ou Ti3AlC2/TiAl3 est obtenu à 1 430 °C.The two phases being maintained in thermodynamic equilibrium, subsequent heat treatments make it possible to modify the microstructures. For example, Ti 2 AlC / TiAl is obtained at 1200 ° C or Ti 3 AlC 2 / TiAl 3 is obtained at 1430 ° C.
Au cours de ses recherches, la Demanderesse a constaté avec surprise que les matériaux testés présentaient, en outre, une résistance à l'oxydation significativement améliorée. Ainsi, les résultats des essais sur l'oxydation de l'exemple 4 montrent l'apport de la phase intermétallique TiAl sur la tenue à l'oxydation à 1 100 °C. En 1 000 périodes d'une heure, le composite Ti2AlC/TiAl est moins oxydé que Ti2AlC monophasé en une seule période d'une heure. La Demanderesse a alors cherché à identifier le phénomène à l'origine de cette propriété inattendue.In the course of its research, the Applicant surprisingly found that the tested materials also exhibited significantly improved oxidation resistance. Thus, the results of the oxidation tests of Example 4 show the contribution of the TiAl intermetallic phase to the oxidation resistance at 1100 ° C. In 1000 periods of one hour, the Ti 2 AlC / TiAl composite is less oxidized than single-phase Ti 2 AlC in a single one-hour period. The Applicant then sought to identify the phenomenon at the origin of this unexpected property.
Le matériau élaboré étant toujours dans un domaine de forte concentration en aluminium lors de sa fabrication, grâce à la coexistence des phases Ti2AlC ou Ti3AlC2 et TixAly, il semblerait que la forte teneur en aluminium permette de favoriser la formation d'une couche superficielle protectrice d'alumine (Al2O3).The material developed is still in a high concentration of aluminum during its manufacture, thanks to the coexistence of Ti 2 AlC or Ti 3 AlC 2 and Ti x Al y phases, it seems that the high aluminum content allows to promote the formation of a protective alumina (Al 2 O 3 ) surface layer.
En résumé, l'élaboration de tels composites céramique/intermétallique permet d'améliorer les propriétés mécaniques et d'oxydation par rapport à une phase MAX, notamment par les mécanismes suivants :
- une meilleure densification et la diminution de la porosité intergranulaire,
- l'élimination de phases secondaires indésirables comme TiC,
- la présence d'une réserve d'aluminium (TixAly),
- un enrichissement en aluminium permettant de développer une couche d'alumine en surface.
- better densification and reduction of intergranular porosity,
- elimination of unwanted secondary phases such as TiC,
- the presence of an aluminum reserve (Ti x Al y ),
- an enrichment of aluminum to develop a layer of alumina on the surface.
En outre, la formation des composites est réalisée in-situ. Le frittage réactif d'un mélange de poudre inclut, dès le début, les éléments chimiques qui deviendront phase MAX et phase intermétallique lors du frittage. L'ensemble des éléments chimiques étant disposés dans le moule avant l'opération de frittage, l'opération de traitement thermique de la phase MAX seule utilisée jusqu'à maintenant est rendue superflue dans les procédés selon l'invention. Les procédés mis en oeuvre pour former les cermets sont plus simples et moins coûteux. La formation des différentes phases est contrôlée, notamment par la température appliquée. La quantité d'intermétallique est maîtrisée, tout comme la microstructure obtenue par le pressage réactif. Les termes de « phases secondaires » employées jusqu'à maintenant pour désigner les phases indésirables ne sont donc plus appropriés pour désigner les intermétalliques.In addition, the formation of the composites is carried out in situ. Reactive sintering of a powder mixture includes, from the start, the chemical elements that will become MAX phase and intermetallic phase during sintering. Since all the chemical elements are arranged in the mold before the sintering operation, the heat treatment operation of the MAX phase alone used until now is rendered superfluous in the processes according to the invention. The methods used to form the cermets are simpler and less expensive. The formation of the different phases is controlled, in particular by the temperature applied. The amount of intermetallic is controlled, as is the microstructure obtained by reactive pressing. The terms " secondary phases " hitherto used to designate the undesirable phases are therefore no longer suitable for intermetallics.
L'invention ne se limite pas aux exemples de matériaux et de procédés de fabrication décrits ci-avant, seulement à titre d'exemple, mais elle englobe toutes les variantes que pourra envisager l'homme de l'art dans le cadre des revendications ci-après.The invention is not limited to the examples of materials and methods of manufacture described above, only by way of example, but it encompasses all the variants that may be considered by those skilled in the art within the scope of the present claims. -after.
Claims (8)
- A cermet material consisting of:- a first MAX phase of formula Ti2AlC or Ti3AlC2, and- a second intermetallic phase of general formula TixAly, where- residues comprising TiC, wherein
x is between 1 and 3,
y is between 1 and 3, and
x + y ≤ 4,
the volume proportion of the first phase in the material being between 70% and 95%, the volume proportion of the second phase in the material being between 30% and 5%, the volume proportion of residues is less than 5%
the porosity fraction being less than 5%. - The material as claimed in claim 1, wherein
x = 1 and y = 1, or
x = 1 and y = 3, or
x = 3 and y = 1. - A process for manufacturing a cermet material comprising the following steps:a) mixing- titanium (Ti),- aluminum (Al), and- a titanium-carbon compound (TiC);in pulverulent form in an aqueous or organic medium,
the content of each of the chemical elements corresponding substantially to the final molar proportions desired for the cermet material with an excess of aluminum (Al) of between 8 mol% and 17 mol%;b) drying the mixture until a powder is obtained;c) sintering the powder under temperature conditions between 800°C and 1400°C and pressure conditions between 20 MPa and 40 MPa for a time of between 1 and 3 hours in order to form, at thermodynamic equilibrium:- a first MAX phase of general formula Tin+1AlCn in a volume proportion in the mixture of between 70% and 95%, and- a second intermetallic phase of general formula TixAly in a volume proportion in the mixture of between 30% and 5%, and wheren is equal to 1 or 2,
x is between 1 and 3,
y is between 1 and 3, and
x + y ≤ 4. - The process as claimed in claim 3, wherein, prior to the sintering step c), the powder is atomized or granulated.
- The process as claimed in either of claims 3 and 4, wherein the sintering step c) is carried out under vacuum or in the presence of an inert gas.
- The process as claimed in one of claims 3 to 5, wherein the sintering step c) comprises the use of at least one of the techniques from among reactive hot pressing, reactive hot isostatic pressing and reactive natural sintering.
- The process as claimed in one of claims 3 to 6, wherein the sintering step c) comprises the placement of the powder in a pressing die.
- The process as claimed in one of claims 3 to 7, wherein, during the sintering step c), the powder is encapsulated in a metal casing.
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CN112694333A (en) * | 2021-01-15 | 2021-04-23 | 安徽工业大学 | TixAlCy/TiCz/TiaAlb multi-component complex-phase ceramic powder and low-temperature rapid preparation method thereof |
CN115594181A (en) * | 2021-07-08 | 2023-01-13 | 苏州北科纳米科技有限公司(Cn) | Aluminum-excess MAX phase ceramic and preparation method thereof |
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