CN113667854B - MAX phase reinforced tungsten/molybdenum fine grain alloy and preparation method thereof - Google Patents
MAX phase reinforced tungsten/molybdenum fine grain alloy and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 60
- 239000000956 alloy Substances 0.000 title claims abstract description 60
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010937 tungsten Substances 0.000 title claims abstract description 38
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 32
- 239000011733 molybdenum Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 239000011858 nanopowder Substances 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000003870 refractory metal Substances 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
- 238000001513 hot isostatic pressing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 5
- 229910009852 Ti4AlC3 Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 21
- 239000012535 impurity Substances 0.000 abstract description 21
- 239000001301 oxygen Substances 0.000 abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 abstract description 21
- 229910001182 Mo alloy Inorganic materials 0.000 abstract description 17
- 229910001080 W alloy Inorganic materials 0.000 abstract description 14
- 239000010936 titanium Substances 0.000 description 38
- 238000011065 in-situ storage Methods 0.000 description 20
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 20
- 150000001247 metal acetylides Chemical class 0.000 description 17
- 238000000354 decomposition reaction Methods 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 229910016909 AlxOy Inorganic materials 0.000 description 6
- -1 TixCy Chemical class 0.000 description 6
- 230000001427 coherent effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005510 radiation hardening Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
The invention provides a MAX phase reinforced tungsten/molybdenum fine grain alloy and a preparation method thereof, step S1, putting MAX phase powder and tungsten and molybdenum refractory metal powder mixed in any proportion into a ball mill for ball milling to obtain superfine W/Mo-MAX composite nano powder; step S2, reducing the ball-milled composite nano powder in a furnace by using hydrogen at 450-550 ℃ for 30-120min to remove oxygen impurities; and S3, performing high-temperature sintering on the W/Mo-MAX composite nano powder obtained in the step S2 at the temperature of 1600-. The invention adds MAX phase ceramics by a traditional mechanical ball milling method, and prepares superfine MAX phase reinforced fine grain tungsten/molybdenum alloy after high-temperature sintering.
Description
Technical Field
The invention belongs to the technical field of metal material preparation, and particularly relates to a MAX phase reinforced tungsten/molybdenum fine grain alloy and a preparation method thereof.
Background
Tungsten (molybdenum) and its alloy have many excellent properties, high melting point, high thermal conductivity, high density, low thermal expansion coefficient, excellent corrosion resistance, etc., and are widely used in the fields of aerospace, electronics, chemical industry, etc. In the field of fusion nuclear energy, tungsten (molybdenum) can be applied to extreme service environments such as high temperature, strong current ion irradiation and steady-state heat flow, and is considered as the most promising first wall protective material facing to plasma. However, the characteristics of tungsten (molybdenum) such as low temperature brittleness, small interface bonding force, low recrystallization temperature, radiation hardening and embrittlement always limit the application of tungsten (molybdenum) in the fieldsThe difficulty of popularization. Currently available methods are second phase (oxide or carbide) dispersion strengthening and fine grain strengthening. In one aspect, Y2O3The tungsten (molybdenum) crystal particles are obviously refined, the smaller the tungsten (molybdenum) crystal particles are, the more uniformly the second phase oxide particles are distributed in the tungsten crystal, and the more excellent the performance of the tungsten (molybdenum) alloy is, so that the more rigorous service requirements in various application fields can be met. However, the grain size of the tungsten (molybdenum) alloy reinforced by oxide is still large, and how to prepare the tungsten (molybdenum) alloy with the size being more and more fine is important.
Compared with various chemical methods with complicated experimental processes, the mechanical ball milling method has simple experimental process, is suitable for mass production and has more engineering significance, and the main preparation process of the composite oxide-tungsten (molybdenum) alloy powder in the industry at present is the mechanical ball milling method. How to prepare the tungsten (molybdenum) alloy with finer grains and more excellent mechanical properties by using the traditional mechanical ball milling method is very important.
MAX phase ceramics are a generic name of ternary layered ceramics, M is a transition element, A is some elements in the main group III or IV, and X is C or N. The atomic bonding mode of all MAX phase ceramic compounds has covalent bonds, ionic bonds and metallic bonds, thereby having the properties of metal and ceramic, such as heat conduction, electric conductivity, thermal shock resistance and processability similar to metal, and oxidation resistance, wear resistance, self-lubricating property, corrosion resistance and high temperature resistance similar to ceramic, and therefore having important application value. MAX phase ceramics have been doped with copper alloy (CN 108913932B), nickel alloy (CN 109666815A), and titanium alloy (CN 111139376A) in the direction of metal composite materials, but have not been applied in the field of refractory metals such as molybdenum alloy and tungsten alloy. Ti with common MAX phase ceramicsn+1AlCnFor example, Ti, Al and copper alloy, nickel alloy and titanium alloy produce TiCxAnd various in-situ Cu-Al, Ni-Al and Ti-Al transition layer adding front matrixes. However, Ti and Al do not react with W or Mo, so that Ti is not reacted with W or Mo at the high-temperature sintering stagen+1AlCnMay decompose and the decomposed Al may adsorb oxygen impurities nearby to form alumina, purify and strengthen the tungsten (molybdenum) matrix. MAX phase ceramics are expected to beFurther refines the tungsten (molybdenum) alloy crystal grains, simultaneously has finer second phase and further reduces oxygen impurities.
Disclosure of Invention
In order to solve the technical problem, the embodiment of the invention provides the MAX phase reinforced tungsten/molybdenum fine grain alloy and the preparation method thereof.
In order to achieve the above purpose, the embodiment of the present invention adopts the following technical solutions:
the embodiment of the invention provides a preparation method of MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, putting MAX phase powder and tungsten and molybdenum refractory metal powder mixed in any proportion into a ball mill for ball milling, fully refining and mixing the powder to obtain superfine W/Mo-MAX composite nano powder;
s2, reducing the ball-milled W/Mo-MAX composite nano powder in a furnace by using hydrogen at 450-;
and S3, performing high-temperature sintering on the W/Mo-MAX composite nano powder obtained in the step S2 at the temperature of 1600-.
Further, in the step S1, the mass fraction of the MAX phase powder is 0.01-10% of the W/Mo-MAX composite nano powder.
Further, the MAX phase is any one of or a combination of at least two of 312 phase MAX phase ceramics, 211 phase MAX phase ceramics, and 413 phase MAX phase ceramics.
Further, the 312-phase MAX-phase ceramic is Ti3AlC2Or Zr3AlC2Or Hf3AlC2The 211-phase MAX-phase ceramic is Ti2AlC or Zr2AlC or Hf2AlC; the 413-phase MAX-phase ceramic is Ti4AlC3Or Zr4AlC3Or Hf4AlC3。
Further, in step S1, ball milling is performed in argon or nitrogen atmosphere, the ball milling rotation speed is 200-.
Further, the high-temperature sintering in step S3 is atmospheric pressure sintering or spark plasma sintering or hot isostatic pressing sintering in a hydrogen or argon atmosphere.
Further, the residence time of the highest temperature of the high-temperature sintering in the step 3, which is normal-pressure sintering, is 3-10h, the residence time of the highest temperature of the high-temperature sintering, which is spark plasma sintering, is 2-10min, and the residence time of the highest temperature of the high-temperature sintering, which is hot isostatic pressing sintering, is 2-8 h.
The invention also provides the MAX phase reinforced tungsten/molybdenum fine grain alloy prepared by the preparation method of the MAX phase reinforced tungsten/molybdenum fine grain alloy.
The invention has the following beneficial effects:
the MAX phase reinforced tungsten/molybdenum fine grain alloy and the preparation method thereof provided by the invention have the advantages that MAX phase ceramics are added through a traditional mechanical ball milling method, and then the superfine MAX phase reinforced fine grain tungsten/molybdenum alloy is prepared after high-temperature sintering.
1. The MAX phase undergoes self-decomposition during the high temperature sintering phase and adsorbs oxygen impurities in the alloy to form smaller size in situ oxides/carbides, which are smaller than the size of the oxides directly added in conventional ball-milled alloys.
2. Compared with the traditional single rare earth oxide or carbide, the oxide/carbide ceramic phase obtained by MAX decomposition is finer, and the movement of W/Mo crystal grains can be more effectively pinned, so that the effect of refining tungsten (molybdenum) crystal grains is better; compared with the traditional rare earth oxide or carbide, the oxide/carbide ceramic obtained by MAX in-situ decomposition can form a coherent interface with a W/Mo matrix more easily, the W/Mo matrix is strengthened by coherent strengthening, and the coherent interface can block the movement of a phase boundary and limit the growth of the sizes of the W/Mo matrix and the W/Mo matrix.
The in-situ oxides/carbides generated by the MAX phase during the high-temperature sintering stage are more located inside the matrix grains (as shown in fig. 1), while the second phase is more located inside the grains to improve the mechanical properties, compared with the rare earth oxides directly added (as shown in fig. 2), so that the MAX-doped tungsten/molybdenum alloy has more excellent mechanical properties.
4. Different from other alloy systems with the added MAX phase, the MAX added into the tungsten/molybdenum alloy does not form a transition layer with the substrate after decomposition, but adsorbs nearby oxygen impurities to generate a ceramic oxide strengthening phase, so that the substrate is further strengthened.
5. Compared with the traditional chemical methods such as a sol-gel method, a hydrothermal synthesis method, a wet chemical method and the like, the method adopts mechanical ball milling, has simpler experimental process and is more suitable for mass production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is apparent that the drawings in the following description are only some embodiments of the present invention.
FIG. 1 shows Mo-Ti provided in example 1 of the present invention2SEM pictures of AlC alloys;
FIG. 2 shows Mo-Y of comparative example 1 in inventive example 12O3SEM pictures of the alloys;
FIG. 3 is an SEM photograph of pure Mo of comparative example 2 in inventive example 1;
FIG. 4 shows W-Ti provided in example 2 of the present invention2SEM pictures of AlC alloys;
FIG. 5 shows W-Y of a comparative sample in inventive example 22O3SEM pictures of the alloys.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
and step S1, putting MAX phase powder and tungsten and molybdenum refractory metal powder mixed in any proportion into a ball mill, carrying out ball milling in an argon or nitrogen atmosphere at the ball milling rotation speed of 200-400r/min for 6-24h, and fully refining and mixing the powder to obtain the superfine W/Mo-MAX composite nano powder.
The mass fraction of the MAX phase powder is 0.01-10% of that of the W/Mo-MAX composite nano powder. The MAX phase is any one of or a combination of at least two of 312 phase MAX phase ceramics, 211 phase MAX phase ceramics, and 413 phase MAX phase ceramics. The 312-phase MAX-phase ceramic is Ti3AlC2Or Zr3AlC2Or Hf3AlC2The 211-phase MAX-phase ceramic is Ti2AlC or Zr2AlC or Hf2AlC; the 413-phase MAX-phase ceramic is Ti4AlC3Or Zr4AlC3Or Hf4AlC3。
And step S2, reducing the ball-milled W/Mo-MAX composite nano powder in a furnace by using hydrogen at 450 ℃ and 550 ℃ for 30-120min to remove oxygen impurities.
And S3, performing normal pressure sintering or spark plasma sintering or hot isostatic pressing sintering on the W/Mo-MAX composite nano powder obtained in the step S2 in a hydrogen or argon atmosphere at the temperature of 1600-2000 ℃, wherein the MAX phase powder is subjected to self-decomposition during high-temperature sintering and adsorbs oxygen impurities in the alloy to generate in-situ oxides/carbides with smaller size and more distributed in alloy crystals, and finally obtaining the tungsten alloy or molybdenum alloy or tungsten-molybdenum alloy with finer grain size. Wherein the residence time of the high-temperature sintering is 3-10h at the highest temperature of normal-pressure sintering, 2-10min at the highest temperature of spark plasma sintering and 2-8h at the highest temperature of hot isostatic pressing sintering.
The invention also provides the MAX phase reinforced tungsten/molybdenum fine grain alloy prepared by the preparation method of the MAX phase reinforced tungsten/molybdenum fine grain alloy.
Example 1
The embodiment provides a preparation method of a MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, mixing 1gTi2And putting AlC powder and 99g of pure molybdenum powder into a ball milling tank, vacuumizing, filling argon gas, repeating for 3 times, and then performing ball milling for 12 hours at the rotating speed of 400 r/min.
Step S2, reducing the ball-milled composite powder in a furnace by hydrogen at 550 ℃ for 40min to remove oxygen impurities to obtain superfine Mo-Ti2AlC composite nanopowder.
Step S3, and then Mo-Ti obtained in step S22Performing AlC composite nano powder under the pressure of 20MPa, and then sintering the powder for 6 hours under normal pressure in a pure hydrogen atmosphere at the temperature of 1600 ℃ to finally obtain MAX phase reinforced Mo-Ti2An AlC alloy.
Mo-Ti prepared by the method of this example2The average grain size of the AlC alloy grains is about 1.2 μm, and the scanning picture is shown in FIG. 1.
At the same time, two comparative samples were also prepared, with comparative sample 1 having a composition of Mo-1 wt% Y2O3And the composition of comparative example 2 was pure Mo. Mo-1 wt% Y2O3The surface morphology of (A) is shown in FIG. 2, the average grain size of the alloy grains is 1.6 μm, the surface morphology of pure Mo is shown in FIG. 3, and the average grain size of the alloy grains is > 10 μm. This demonstrates that MAX doping significantly refines the molybdenum alloy grain, Mo-Ti, compared to the conventional doped rare earth oxides2AlC alloys have significant advantages in grain size. And, Ti2The AlC undergoes self-decomposition in the high-temperature sintering stage and adsorbs a large amount of oxygen impurities in the molybdenum substrate to generate in-situ oxides/carbides, such as TixCy、AlxOy、TixOyAnd TixAlyOzThese in situ oxides/carbides are much finer and more intragranular than the conventional directly added rare earth oxides (as shown in fig. 1 and 2). It is well known that finer and more localized second phases within the grains are more favorable for improving the mechanical properties, and thus the properties of MAX-doped molybdenum alloys are more excellent.
Example 2
The embodiment provides a preparation method of a MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, mixing 1gTi2And putting the AlC powder and 99g of pure tungsten powder into a ball milling tank, vacuumizing, filling argon gas, repeating for 3 times, and then performing ball milling for 24 hours at the rotating speed of 300 r/min.
Step S2, reducing the ball-milled composite powder in a furnace by using hydrogen at 450 ℃ for 120min to remove oxygen impurities to obtain superfine W-Ti2AlC composite nanopowder.
Step S3, and then the W-Ti obtained in the step S22Performing AlC composite nano powder under the pressure of 20MPa, and then sintering the powder for 5 hours under normal pressure in a pure hydrogen atmosphere at the temperature of 1600 ℃ to finally obtain MAX phase reinforced W-Ti2An AlC alloy.
W-Ti prepared by the method of this example2The average grain size of the AlC alloy grains is 4.5 μm, and the scanning picture is shown in FIG. 4.
At the same time, we also prepared 1 comparative sample with composition W-1 wt% Y2O3。W-1wt％Y2O3The surface morphology of (2) is shown in FIG. 5, and the average grain size of the alloy grains is 8.1. mu.m. This indicates that MAX doping significantly refines the grain size of the W alloy, W-Ti, compared to conventional doped rare earth oxides2AlC alloys have significant advantages in grain size. And, Ti2The AlC undergoes self-decomposition in the high-temperature sintering stage and adsorbs a large amount of oxygen impurities in the tungsten matrix to generate in-situ oxides/carbides, such as TixCy、AlxOy、TixOyAnd TixAlyOzThese in situ oxides/carbides are much finer and more intragranular than the conventional direct addition rare earth oxides. It is well known that finer and more localized second phases within the grains are more beneficial for improving the mechanical properties, and thus the properties of MAX-doped tungsten alloys are more excellent.
Example 3
The embodiment provides a preparation method of a MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, adding 2g of Ti3AlC2Putting the powder, 49g of pure tungsten powder and 49g of pure molybdenum powder into a ball milling tank, vacuumizing, filling argon gas, repeating for 3 times, and then ball milling for 6 hours at the rotating speed of 400 r/min.
Step S2, reducing the ball-milled composite powder in a furnace by hydrogen at 500 ℃ for 60min to remove oxygen impurities to obtain the super-fineFine W/Mo-Ti3AlC2And (3) compounding the nano powder.
Step S3, and then the W/Mo-Ti obtained in step S23AlC2Performing the composite nano powder under the pressure of 20MPa, and then sintering the composite nano powder for 10 hours under normal pressure in a pure argon atmosphere at the temperature of 1800 ℃ to finally obtain MAX phase reinforced W/Mo-Ti3AlC2And (3) alloying.
The average grain size of the W/Mo-Ti3AlC2 alloy grains prepared by the method of the embodiment is 16.0 μm. This indicates that MAX doping can significantly refine the grain size of the tungsten-molybdenum alloy, W/Mo-Ti3AlC2The alloy has significant advantages in grain size. And, Ti3AlC2Self-decomposition occurs in the high-temperature sintering stage and a large amount of oxygen impurities in the tungsten-molybdenum matrix are absorbed to generate in-situ oxides/carbides, such as TixCy、AlxOy、TixOyAnd TixAlyOzThese in situ oxides/carbides are much finer and more intragranular than the conventional direct addition rare earth oxides. It is known that the smaller and more inside of the crystal grains of the second phase is more beneficial to improving the mechanical property, so that the MAX doped tungsten-molybdenum alloy has more excellent performance.
Example 4
The embodiment provides a preparation method of a MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, adding 5gZr3AlC2Putting the powder and 95g of pure molybdenum powder into a ball milling tank, vacuumizing, filling nitrogen and repeating for 3 times, and then ball milling for 20 hours at the rotating speed of 350 r/min.
Step S2, reducing the ball-milled composite powder in a furnace by using hydrogen at 480 ℃ for 90min to remove oxygen impurities to obtain superfine Mo-Zr3AlC2And (3) compounding the nano powder.
Step S3, and then adding the Mo-Zr obtained in the step S23AlC2Performing the composite nano powder under the pressure of 20MPa, and then sintering the composite nano powder for 3 hours under normal pressure in a pure hydrogen atmosphere at the temperature of 2000 ℃ to finally obtain MAX phase reinforced Mo-Zr3AlC2And (3) alloying.
Mo-Zr prepared by the method of this example3AlC2The average grain size of the alloy grains was 28.1. mu.m. This indicates that MAX doping can significantly refine the grain size of the molybdenum alloy, Mo-Zr3AlC2The alloy has significant advantages in grain size. And, Zr3AlC2Self-decomposition occurs in the high-temperature sintering stage and a large amount of oxygen impurities in the molybdenum matrix are absorbed to generate in-situ oxides/carbides, such as ZrxCy、AlxOy、ZrxOyAnd ZrxAlyOzThese in situ oxides/carbides are much finer and more intragranular than the conventional direct addition rare earth oxides. It is well known that finer and more localized second phases within the grains are more favorable for improving the mechanical properties, and thus the properties of MAX-doped molybdenum alloys are more excellent.
Example 5
The embodiment provides a preparation method of a MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, mixing 10gTi2And placing AlC powder, 30g of pure tungsten powder and 60g of pure molybdenum powder into a ball milling tank, vacuumizing, filling argon gas, repeating for 3 times, and then performing ball milling for 15 hours at the rotating speed of 360 r/min.
Step S2, reducing the ball-milled composite powder in a furnace by using hydrogen at 520 ℃ for 80min to remove oxygen impurities to obtain superfine Mo/W-Ti2AlC composite nanopowder.
Step S3, performing Mo/W-Ti2AlC composite nano powder obtained in the step S2 under the pressure of 20MPa, performing hot isostatic pressing sintering at 1600 ℃, and performing high-temperature sintering for 4 hours to finally obtain MAX phase reinforced Mo/W-Ti2The A1C alloy.
Mo/W-Ti prepared by the method of this example2The average grain diameter of AlC alloy grains is 2.6 mu m. This indicates that MAX doping can significantly refine the grains of the Mo-W alloy, Mo/W-Ti2AlC alloys have significant advantages in grain size. And, Ti2The AlC is subject to self-decomposition in the high-temperature sintering stage and adsorbs a large amount of oxygen impurities in the tungsten-molybdenum substrate to generate in-situ oxides/carbides, such as TixCy、AlxOy、TixOyAnd TixAlyOzThese in situ oxides/carbides are much finer and more intragranular than the conventional direct addition rare earth oxides. It is known that the smaller and more inside of the crystal grains of the second phase is more beneficial to improving the mechanical property, so that the MAX doped tungsten-molybdenum alloy has more excellent performance.
Example 6
The embodiment provides a preparation method of a MAX phase reinforced tungsten/molybdenum fine grain alloy, which comprises the following steps:
step S1, adding 0.1gZr4AlC3Putting the powder and 99.9g of pure tungsten powder into a ball milling tank, vacuumizing, filling argon gas and repeating for 3 times, and then ball milling for 10 hours at the rotating speed of 400 r/min.
Step S2, reducing the ball-milled composite powder in a furnace by hydrogen at 550 ℃ for 30min to remove oxygen impurities to obtain superfine W-Zr4AlC3And (3) compounding the nano powder.
Step S3, and then the W-Zr obtained in the step S24AlC3The composite nano powder is directly subjected to spark plasma sintering at 1700 ℃ for 5min to finally obtain MAX phase reinforced W-Zr4AlC3And (3) alloying.
W-Zr prepared by the method of this example4AlC3The average grain size of the alloy grains was 8.9. mu.m. This indicates that MAX doping can significantly refine the grain size of the tungsten alloy, W-Zr4AlC3The alloy has significant advantages in grain size. And, Zr4AlC3Self-decomposition occurs in the high-temperature sintering stage and a large amount of oxygen impurities in the tungsten matrix are absorbed to generate in-situ oxides/carbides, such as ZrxCy、AlxOy、ZrxOyAnd ZrxAlyOzThese in situ oxides/carbides are much finer and more intragranular than the conventional direct addition rare earth oxides. It is well known that finer and more localized second phases within the grains are more beneficial for improving the mechanical properties, and thus the properties of MAX-doped tungsten alloys are more excellent.
According to the technical scheme, the MAX phase reinforced tungsten/molybdenum fine-grained alloy and the preparation method thereof provided by the embodiment are characterized in that MAX phase ceramics are added through a traditional mechanical ball milling method, and then the superfine MAX phase reinforced fine-grained tungsten/molybdenum alloy is prepared through high-temperature sintering. The MAX phase undergoes self-decomposition during the high temperature sintering phase and adsorbs oxygen impurities in the alloy to form smaller size in situ oxides/carbides, which are smaller than the size of the oxides directly added in conventional ball-milled alloys. Compared with the traditional single rare earth oxide or carbide, the oxide/carbide ceramic phase obtained by MAX decomposition is finer, and the movement of W/Mo crystal grains can be more effectively pinned, so that the effect of refining tungsten (molybdenum) crystal grains is better; compared with the traditional rare earth oxide or carbide, the oxide/carbide ceramic obtained by MAX in-situ decomposition can form a coherent interface with a W/Mo matrix more easily, the W/Mo matrix is strengthened by coherent strengthening, and the coherent interface can block the movement of a phase boundary and limit the growth of the sizes of the W/Mo matrix and the W/Mo matrix.
The in-situ oxides/carbides generated by the MAX phase in the high-temperature sintering stage are more located in the matrix grains (as shown in fig. 1), while the second phase is more located in the grains to improve the mechanical properties, compared with the rare earth oxides directly added (as shown in fig. 2), so that the MAX-doped tungsten/molybdenum alloy has more excellent mechanical properties. Different from other alloy systems with the added MAX phase, the MAX added into the tungsten/molybdenum alloy does not form a transition layer with the substrate after decomposition, but adsorbs nearby oxygen impurities to generate a ceramic oxide strengthening phase, so that the substrate is further strengthened. Compared with the traditional chemical methods such as a sol-gel method, a hydrothermal synthesis method, a wet chemical method and the like, the method adopts mechanical ball milling, has simpler experimental process and is more suitable for mass production.
The embodiments of the present invention have been described in detail through the embodiments, but the description is only exemplary of the embodiments of the present invention and should not be construed as limiting the scope of the embodiments of the present invention. The scope of protection of the embodiments of the invention is defined by the claims. In the present invention, the technical solutions described in the embodiments of the present invention or those skilled in the art, based on the teachings of the embodiments of the present invention, design similar technical solutions to achieve the above technical effects within the spirit and the protection scope of the embodiments of the present invention, or equivalent changes and modifications made to the application scope, etc., should still fall within the protection scope covered by the patent of the embodiments of the present invention.
Claims (4)
1. A method for preparing a MAX phase strengthened tungsten/molybdenum fine grain alloy, characterized by comprising the steps of:
step S1, putting MAX phase powder and tungsten and molybdenum refractory metal powder mixed in any proportion into a ball mill for ball milling, fully refining and mixing the powder to obtain superfine W/Mo-MAX composite nano powder; the MAX phase is any one or a combination of at least two of 312-phase MAX-phase ceramics, 211-phase MAX-phase ceramics and 413-phase MAX-phase ceramics; the 312-phase MAX-phase ceramic is Ti3AlC2Or Zr3AlC2Or Hf3AlC2The 211-phase MAX-phase ceramic is Ti2AlC or Zr2AlC or Hf2AlC; the 413-phase MAX-phase ceramic is Ti4AlC3Or Zr4AlC3Or Hf4AlC3(ii) a The mass fraction of the MAX phase powder is 0.01-10% of that of the W/Mo-MAX composite nano powder;
s2, reducing the ball-milled W/Mo-MAX composite nano powder in a furnace by using hydrogen at 450-;
s3, performing high-temperature sintering on the W/Mo-MAX composite nano powder obtained in the step S2 at the temperature of 1600-; the residence time of the high temperature sintering is 3-10h at the highest temperature of normal pressure sintering, 2-10min at the highest temperature of spark plasma sintering, or 2-8h at the highest temperature of hot isostatic pressing sintering.
2. The method for preparing MAX phase reinforced tungsten/molybdenum fine crystal alloy as claimed in claim 1, wherein step S1 is ball milling in argon or nitrogen atmosphere, the ball milling speed is 200-.
3. The method of producing a MAX phase strengthened tungsten/molybdenum fine crystalline alloy according to claim 1 wherein the high temperature sintering in step S3 is atmospheric sintering or spark plasma sintering or hot isostatic sintering in a hydrogen or argon atmosphere.
4. A MAX phase strengthened tungsten/molybdenum fine grain alloy, characterized by being prepared by the method of any one of claims 1 to 3.
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