CN117802385A - Refractory high-entropy alloy, in-situ preparation method and application - Google Patents
Refractory high-entropy alloy, in-situ preparation method and application Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 104
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000011065 in-situ storage Methods 0.000 title abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 10
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 73
- 239000002994 raw material Substances 0.000 claims description 31
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 11
- 238000007906 compression Methods 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000010955 niobium Substances 0.000 description 36
- 230000008018 melting Effects 0.000 description 21
- 238000002844 melting Methods 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 229910000905 alloy phase Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a refractory high-entropy alloy, an in-situ preparation method and application thereof, wherein the chemical formula of the refractory high-entropy alloy is Nb a Mo b Ta c W d Zr e C f Wherein a is more than 0 and less than or equal to 35at%, b is more than 0 and less than or equal to 35at%, c is more than 0 and less than or equal to 35at%, d is more than or equal to 0 and less than or equal to 35at%, e is more than or equal to 5 and less than or equal to 35at%, f is more than or equal to 5 and less than or equal to 35at%, and a+b+c+d+e+f=100, and the refractory high-entropy alloy consists of a high-entropy alloy matrix with a body-centered cubic structure and reinforcing phases with a face-centered cubic structure which are uniformly dispersed and distributed, and the refractory high-entropy alloy is prepared by a vacuum arc furnace smelting method. The obtained refractory high-entropy alloy has compressive strength of more than 2000MPa and plastic strain of nearly 10% at room temperature, and simultaneously has strength of more than 600MPa at 1600 ℃, excellent ultrahigh temperature performance and room temperature processability, and has great application prospect in the field of ultrahigh temperature structural materials.
Description
Technical Field
The invention belongs to the field of high-entropy alloy and high-temperature-resistant alloy, and particularly relates to a refractory high-entropy alloy, an in-situ preparation method and application.
Technical Field
The continuous development in the fields of aerospace technology, nuclear power technology and the like puts higher and higher requirements on ultra-high temperature resistant structural materials, for example, when a hypersonic aircraft flies across the atmosphere or reenters, ultra-high temperatures exceeding 1600 ℃ are generated by nose cone positions of the hypersonic aircraft due to obvious pneumatic heating effects. The nickel-based superalloy serving in the high-temperature environment is limited by the melting point, the use temperature is not higher than 1200 ℃, the inherent intrinsic brittleness of the ultra-high temperature ceramic material severely limits the further application of the nickel-based superalloy, and the development of a novel high-performance ultra-high temperature resistant structural material becomes an important bottleneck for limiting the development of the high-temperature material industry.
The refractory high-entropy alloy consists of four or more high-melting-point metal elements with equal atomic ratio or near-equal atomic ratio, and has excellent strength and hardness and good high-temperature creep resistance under the actions of high mixed entropy, serious lattice distortion, delayed diffusion and cocktail effect, and is an ultra-high temperature structural material with great potential. Among the refractory high-entropy alloy systems developed at present, the NbMoTaW-based high-entropy alloy is a refractory high-entropy alloy system which only maintains a certain strength at 1600 ℃, for example, the compressive yield strength of the equal atomic ratio NbMoTaW and VNbMoTaW high-entropy alloy at 1600 ℃ is 405MPa and 477MPa respectively, but the grain coarsening phenomenon exists at the ultrahigh temperature, the ultrahigh temperature strength is still to be further improved, and the serious room temperature brittleness problem exists (the room temperature compressive plastic strain of NbMoTaW is only 2.1%). At present, the research on refractory high-entropy alloy is insufficient in China, and the requirement on high-performance ultrahigh-temperature structural materials cannot be met. Therefore, on the basis of the existing refractory high-entropy alloy system, the novel refractory high-entropy alloy with high strength and high plasticity is developed, and has great significance for improving the engineering application and theoretical research of ultra-high temperature structural materials in China.
Disclosure of Invention
The invention discloses a refractory high-entropy alloy, and an in-situ preparation method and application thereof, which are used for solving any one of the above and other potential problems in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is as follows: refractory high-entropy alloy with a chemical formula of Nb a Mo b Ta c W d Zr e C f Wherein 0 < a.ltoreq.35at%, 0 < b.ltoreq.35at%, 0 < c.ltoreq.35at%, 0 < d.ltoreq.35at%, 5.ltoreq.e.ltoreq.35at%, 5.ltoreq.f.ltoreq.35at%, and a+b+c+d+e+f=100.
Further, the refractory high-entropy alloy consists of a high-entropy alloy matrix with a body-centered cubic structure and reinforcing phases with a face-centered cubic structure which are uniformly dispersed and distributed.
Further, when a=27, b=9, c=27, d=27, e=5, f=5, the refractory high-entropy alloy has the chemical formula Nb 27 Mo 9 Ta 27 W 27 Zr 5 C 5 The room temperature compressive strength is more than 2000MPa, and the room temperature compressive plastic strain is more than 15%.
Further, when a=24, b= 8,c =24, d=24, e=10, f=10, the refractory high-entropy alloy has the chemical formula Nb 24 Mo 8 Ta 24 W 24 Zr 10 C 10 The compression strength at room temperature is more than 2400MPa, and the compressive plastic strain is more than 8%.
Further, when a=22.5, b=7.5, c=22.5, d=22.5, e=12.5, f=12.5, the refractory high-entropy alloy has the chemical formula Nb 22.5 Mo 7.5 Ta 22.5 W 22.5 Zr 12.5 C 12.5 The compression strength at room temperature is more than 2400MPa, and the compression plastic strain at room temperature is more than 9%.
Further, when a=19.5, b=6.5, c=19.5, d=19.5, e=17.5, f=17.5, the refractory high-entropy alloy has the chemical formula Nb 19.5 Mo 6.5 Ta 19.5 W 19.5 Zr 17.5 C 17.5 It is at room temperatureThe compressive strength is more than 2400MPa, and the room temperature compressive plastic strain is 8%.
Another object of the present invention is to provide a method for preparing the refractory high-entropy alloy described above, comprising in particular the steps of:
s1): accurately weighing Nb, mo, ta, W, zr and C raw materials with required weight according to a designed proportion, putting the raw materials into a copper crucible in a vacuum arc melting furnace, and putting a Ti ingot prepared in advance into the vacuum arc melting furnace;
s2): closing the furnace door, and vacuumizing the sample chamber to 5×10 -3 And after Pa, charging high-purity argon with the purity of 99.999 percent to-0.05 to-0.03 MPa, after arcing, firstly smelting a Ti ingot for 1min, then smelting an alloy raw material, wherein the smelting current is 350-450A, smelting for 5-8 times, keeping the arc for at least 2min in each smelting process, turning and tilting the ingot for 40-60 degrees before each smelting, and finally obtaining the refractory high-entropy alloy with uniform components.
Further, nb, mo, ta, W and Zr in S1) are both simple substance particles with purity more than 99.9%; the raw material C is high-purity graphite.
Further, the compressive strength of the refractory high-entropy alloy is not less than 2000MPa at room temperature, and the compressive plastic strain is not less than 8%; the compressive strength at 1600 ℃ is not less than 600MPa.
The refractory high-entropy alloy is applied to the field of ultrahigh-temperature structural materials.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. on the basis of the refractory high-entropy alloy of Nb-Mo-Ta-W, zr is added to further carry out solid solution strengthening and a second phase with high strength and high melting point is introduced to carry out strengthening, so that an ultrahigh-temperature refractory high-entropy alloy system with excellent performance is successfully developed, and the high-entropy alloy and high-temperature alloy material system is enriched;
2. compared with the traditional mechanical alloying preparation method, the preparation method has the advantages that the process is simple, the operation is easy, the preparation period can be greatly shortened, simple substance particles of each element are directly adopted as raw materials, and compared with the method that powder of each element is adopted as raw materials through ball milling, powder mixing and compression molding, the operation is simpler and easier, the raw material utilization rate is high, and the preparation method is suitable for further industrial popularization;
3. the Nb-Mo-Ta-W-Zr-C refractory high-entropy alloy system designed by the invention can adjust the phase proportion and the phase distribution condition in the alloy by changing the content of C, thereby realizing the adjustment of performances such as strength, plasticity and the like, wherein Nb 24 Mo 8 Ta 24 W 24 Zr 10 C 10 The compressive strength of the refractory high-entropy alloy is up to 678MPa at 1600 ℃, which is obviously superior to the existing NbMoTaW refractory high-entropy alloy, has the room-temperature compressive strength of 2396MPa and the plastic strain of 8 percent, can be processed at room temperature, and has outstanding application potential in the field of ultra-high-temperature structural materials.
Drawings
In order to more clearly illustrate the technical solution of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a flow chart of an in situ method for preparing a refractory high-entropy alloy according to the present invention.
FIG. 2 is an XRD pattern for a refractory high-entropy alloy of Nb-Mo-Ta-W-Zr-C system according to the invention;
FIG. 3 is a schematic drawing showing SEM observations of the microstructure of refractory high-entropy alloys prepared in examples 1-4.
(a) Microscopic structure SEM observation results of the refractory high-entropy alloy with Nb27Mo9Ta27W27Zr5C5 component prepared in example 1;
(b) Microscopic structure SEM observation results of refractory high-entropy alloy of Nb24Mo8Ta24W24Zr10C10 component, which is prepared in example 2;
(c) SEM observation results of the microstructure of the refractory high-entropy alloy with the composition nb22.5mo7.5ta22.5w22.5zr12.5c12.5 prepared in example 3;
(d) SEM observation results of microstructure of the refractory high-entropy alloy with the component Nb19.5Mo6.5Ta19.5W19.5Zr17.5C17.5 prepared in example 4;
FIG. 4 is a graph of room temperature compressive stress strain for a refractory high-entropy alloy of Nb-Mo-Ta-W-Zr-C system according to the invention;
FIG. 5 is a sample of Nb obtained in example 2 24 Mo 8 Ta 24 W 24 Zr 10 C 10 1600 ℃ high temperature compressive stress strain curve graph of the component refractory high entropy alloy.
Detailed description of the preferred embodiments
The technical scheme of the invention is further described below with reference to specific embodiments and drawings.
The refractory high-entropy alloy reinforced by the second phases distributed in a dispersing way comprises a high-entropy alloy phase with a body-centered cubic structure and a reinforced phase with a face-centered cubic structure, and the microstructure of the refractory high-entropy alloy shows different characteristics of hypoeutectic, eutectic and hypereutectic along with the change of carbon content, has excellent room temperature strong plasticity and ultrahigh temperature strength, has compressive strength at 1600 ℃ of more than 600MPa, and can be used in the fields of aerospace, national defense and military industry and the like.
The invention provides an in-situ preparation method of the refractory high-entropy alloy, which takes high-purity simple substance particles of each element as raw materials, and adopts a vacuum arc melting method to prepare the refractory high-entropy alloy, the operation is simple and easy, the second phase generated in situ in the prepared alloy through the solidification process is uniformly dispersed and distributed, and the phase interface has excellent bonding strength.
The Nb, mo, ta, W, zr raw material is simple substance particles with the purity of each element exceeding 99.9%, and the C raw material is high-purity graphite.
Removing oxide layers and impurities on the surfaces of Nb simple substance particles, mo simple substance particles, ta simple substance particles, W simple substance particles and Zr simple substance particles before smelting, putting into ethanol or acetone for ultrasonic cleaning, and shearing high-purity graphite into fine particles.
When the content of C is higher, nb and Ta elements can be selected as raw materials, and graphite particles are wrapped by the niobium foil and the tantalum foil and then placed at the bottom of the water-cooled copper crucible.
The proportion of the strengthening phase in the alloy can be regulated and controlled by changing the content of the element C, so that the strength of the alloy is regulated and controlled. When the added C content was 5at%, the volume fraction of the carbide reinforcing phase was 8.9%, the room temperature compressive strength was 2010MPa, and when the C content was increased to 12.5at%, the proportion of the reinforcing phase was increased to 34.2%, and the room temperature compressive strength was increased to 2550MPa.
The density of the refractory high-entropy alloy is regulated and controlled by changing the content of Nb and Zr elements.
Example 1:
preparation of Nb 27 Mo 9 Ta 27 W 27 Zr 5 C 5 A compositionally refractory high entropy alloy. The method comprises the following specific steps:
(1) Raw material preparation: the alloy smelting raw materials adopted by the invention are high-purity (more than or equal to 99.9%) Nb, mo, ta, W and Zr element simple substance particles, oxide skin on the surface of the raw materials is removed by means of a grinding wheel and the like, the raw materials are cleaned by ultrasonic oscillation in alcohol, high-purity graphite is prepared into smaller particles by a mechanical crushing mode, and C particles with the size of about 1mm are screened out by metal. 5.475g of Nb particles, 1.884g of Mo particles, 10.662g of Ta particles, 10.833g of W particles, 0.995g of Zr particles and 0.131g of C particles (atomic percent of Nb/Mo/Ta/W/Zr/C: 27:9:27:5:5) were weighed.
(2) Vacuum arc melting: c particles are placed at the bottom of a water-cooled crucible of a vacuum arc melting furnace, and then Nb particles, mo particles, ta particles, W particles and Zr particles are placed in the crucible in sequence from low melting point to high melting point. Vacuum is applied to the sample chamber when the vacuum degree is higher than 5 multiplied by 10 -3 After Pa, high-purity argon with the purity of 99.999% is filled as a protective gas and an arcing medium, the smelting current is 350-450A to ensure that all raw materials can be completely melted, the smelting is carried out for 5 times, the electric arc is kept for 3min in each smelting process, the ingot is turned and inclined for 40 degrees before each smelting, and finally the ingot is rapidly cooled to room temperature, so that refractory high-entropy alloy ingots with uniform components are obtained.
FIG. 2 is a graph (a) showing Nb obtained in example 1 27 Mo 9 Ta 27 W 27 Zr 5 C 5 XRD patterns of the refractory high-entropy alloy components show that the prepared refractory high-entropy alloy mainly comprises a refractory high-entropy alloy phase with a BCC structure and a second phase with an FCC structure; as observed by SEM, fig. 3 (a) shows that the microstructure is mainly a dendrite-shaped refractory high-entropy alloy phase, and a strengthening phase is distributed among dendrites; by passing throughAs can be seen from the curve (a) in FIG. 4, the alloy has high room temperature plasticity, the plastic strain is more than 15%, and the room temperature compressive strength is more than 2000MPa.
Example 2:
preparation of Nb 24 Mo 8 Ta 24 W 24 Zr 10 C 10 A compositionally refractory high entropy alloy. The method comprises the following specific steps:
(1) Raw material preparation: the alloy smelting raw materials adopted by the invention are high-purity (more than or equal to 99.9%) Nb, mo, ta, W and Zr element simple substance particles, the raw materials are removed of surface oxide skin by means of grinding wheels and the like, the raw materials are cleaned in alcohol by ultrasonic oscillation, high-purity graphite is prepared into smaller particles by a mechanical crushing mode, and carbon particles with the size of about 1mm are screened out by metal. 5.229g of Nb particles, 1.800g of Mo particles, 10.184g of Ta particles, 10.347g of W particles, 2.139g of Zr particles and 0.282g of C particles (atomic percent of Nb/Mo/Ta/W/Zr/C: 24:8:24:24:10) were weighed out.
(2) Vacuum arc melting: c particles are placed at the bottom of a water-cooled crucible of a vacuum arc melting furnace, and then Nb particles, mo particles, ta particles, W particles and Zr particles are placed in the crucible in sequence from low melting point to high melting point. Vacuum is applied to the sample chamber when the vacuum degree is higher than 5 multiplied by 10 -3 After Pa, high-purity argon with the purity of 99.999% is filled as a protective gas and an arcing medium, the smelting current is 350-450A to ensure that all raw materials can be completely melted, smelting is carried out for 8 times, the electric arc is kept for 2min in each smelting process, the ingot is turned and inclined for 40 degrees before each smelting, and finally the ingot is rapidly cooled to room temperature, so that refractory high-entropy alloy ingot with uniform components is obtained.
FIG. 2 curve (b) is Nb obtained in example 2 24 Mo 8 Ta 24 W 24 Zr 10 C 10 XRD patterns of the refractory high-entropy alloy components show that the prepared refractory high-entropy alloy mainly comprises a refractory high-entropy alloy phase with a BCC structure and a strengthening phase with an FCC structure; the microstructure is composed of a primary refractory high-entropy alloy phase and a reinforcing phase which is formed by mesh interweaving and distribution among the primary phases, as shown in fig. 3 (b); the compressive strength of the component alloy at room temperature is close to 2400MPa, and the component alloy has 8 percent of plasticSex, as shown in fig. 4 (c); fig. 5 shows the engineering stress strain curve of the alloy subjected to ultra-high temperature compression at 1600 ℃, and the alloy is known to have compressive strength exceeding 600MPa at 1600 ℃.
Example 3:
preparation of Nb 22.5 Mo 7.5 Ta 22.5 W 22.5 Zr 12.5 C 12.5 A compositionally refractory high entropy alloy. The method comprises the following specific steps:
(1) Raw material preparation: the alloy smelting raw materials adopted by the invention are high-purity (more than or equal to 99.9%) Nb foil and Mo, ta, W, zr element simple substance particles, the Nb foil is sheared into small blocks with the size of 4mm multiplied by 4mm by scissors, the simple substance particles are subjected to surface oxide skin removal by means of grinding wheels and the like, the Nb foil and the simple substance particles are cleaned by ultrasonic oscillation in alcohol, high-purity graphite is prepared into smaller particles by means of mechanical crushing, and C particles with the size of about 3mm are screened by metal. 5.356g of Nb foil, 1.844g of Mo particles, 10.432g of Ta particles, 10.599g of W particles, 1.547g of Zr particles and 0.204g of C particles (22.5:7.5:22.5:22.5:12.5:12.5 atomic percent of Nb/Mo/Ta/W/Zr/C) were weighed.
(2) Vacuum arc melting: and wrapping the C particles by using Nb foil, placing the C particles at the bottom of a water-cooled crucible of a vacuum arc melting furnace, and then placing the Mo particles, the Ta particles, the W particles and the Zr particles into the water-cooled crucible in sequence from low melting point to high melting point. Vacuum is applied to the sample chamber when the vacuum degree is higher than 5 multiplied by 10 -3 After Pa, high-purity argon with the purity of 99.999% is filled as a protective gas and an arcing medium, the smelting current is 350-450A to ensure that all raw materials can be completely melted, the smelting is performed for 6 times, the electric arc is kept for 3min in each smelting process, the ingot is turned over and inclined for 50 degrees before each smelting, and finally the ingot is rapidly cooled to room temperature, so that refractory high-entropy alloy ingots with uniform components are obtained.
FIG. 2 curve (c) is Nb obtained in example 3 22.5 Mo 7.5 Ta 22.5 W 22.5 Zr 12.5 C 12.5 XRD patterns of the refractory high-entropy alloy components show that the prepared refractory high-entropy alloy mainly comprises a refractory high-entropy alloy phase with a BCC structure and a strengthening phase with an FCC structure; as can be seen from SEM, FIG. 3 (c) shows the microstructureMainly comprises eutectic structures which are alternately distributed in lamellar form and are distributed with finer dendrite primary phases; as can be seen from the curve (c) in FIG. 4, the compressive strength of the alloy at room temperature exceeds 2400MPa, and the room temperature plasticity is approximately 10%.
Example 4:
preparation of Nb 19.5 Mo 6.5 Ta 19.5 W 19.5 Zr 17.5 C 17.5 A compositionally refractory high entropy alloy. The method comprises the following specific steps:
(1) Raw material preparation: the alloy smelting raw materials adopted by the invention are high-purity (more than or equal to 99.9%) Nb, mo, W, zr element simple substance particles and Ta foil, the Ta foil is sheared into small blocks with the size of 4mm multiplied by 4mm by scissors, the simple substance particles are subjected to surface oxide skin removal by means of grinding wheels and the like, the Ta foil and the simple substance particles are cleaned by ultrasonic oscillation in alcohol, high-purity graphite is prepared into smaller particles by means of mechanical crushing, and C particles with the size of about 3mm are screened by metal. 9.315g of Ta foil, 4.783g of Nb particles, 1.646g of Mo particles, 9.464g of W particles, 4, 214g of Zr particles and 0.555g of C particles (atomic percent of Nb/Mo/Ta/W/Zr/C: 19.5:6.5:19.5:17.5:17.5) were weighed out.
(2) Vacuum arc melting: and wrapping the C particles with Ta foil, placing the wrapped C particles at the bottom of a water-cooled crucible of a vacuum arc melting furnace, and then placing Mo particles, nb particles, W particles and Zr particles into the water-cooled crucible in sequence from low melting point to high melting point. Vacuum is applied to the sample chamber when the vacuum degree is higher than 5 multiplied by 10 -3 After Pa, high-purity argon with the purity of 99.999% is filled as a protective gas and an arcing medium, the smelting current is 400A to ensure that all raw materials can be completely melted, smelting is carried out for 8 times, an electric arc is kept for 3min in each smelting process, the ingot is turned over and inclined for 45 degrees before each smelting, and finally the ingot is rapidly cooled to room temperature, so that refractory high-entropy alloy ingots with uniform components are obtained.
FIG. 1 curve (d) shows Nb obtained in example 4 19.5 Mo 6.5 Ta 19.5 W 19.5 Zr 17.5 C 17.5 XRD patterns of the refractory high-entropy alloy components show that the prepared refractory high-entropy alloy mainly comprises a refractory high-entropy alloy phase with a BCC structure and a strengthening phase with an FCC structure; can observe itThe microstructure is formed by alternately distributing refractory high-entropy alloy phases and second phases (shown in fig. 2 (d)); the compressive strength of the component alloy at room temperature exceeds 2400MPa, and the room temperature plasticity is more than 5 percent (shown in figure 3 (d)).
The refractory high-entropy alloy and the in-situ preparation method thereof provided by the embodiment of the application are described in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (10)
1. A refractory high-entropy alloy of Nb-Mo-Ta-W-Zr-C system is characterized in that the refractory high-entropy alloy has a chemical formula of Nb a Mo b Ta c W d Zr e C f Wherein 0 < a.ltoreq.35at%, 0 < b.ltoreq.35at%, 0 < c.ltoreq.35at%, 0 < d.ltoreq.35at%, 5.ltoreq.e.ltoreq.35at%, 5.ltoreq.f.ltoreq.35at%, and a+b+c+d+e+f=100.
2. The refractory high-entropy alloy according to claim 1, wherein the refractory high-entropy alloy comprises a high-entropy alloy matrix having a body-centered cubic structure and a uniformly dispersed reinforcing phase having a face-centered cubic structure.
3. The refractory high-entropy alloy according to claim 1, wherein when a=27, b=9, c=27, d=27, e=5, f=5, the refractory high-entropy alloy has the formula Nb 27 Mo 9 Ta 27 W 27 Zr 5 C 5 The room temperature compression strength is more than 2000MPa, and the room temperature compression is carried outThe plastic strain is greater than 15%.
4. The refractory high-entropy alloy according to claim 1, wherein when a=24, b= 8,c =24, d=24, e=10, f=10, the refractory high-entropy alloy has the formula Nb 24 Mo 8 Ta 24 W 24 Zr 10 C 10 The compression strength at room temperature is more than 2400MPa, and the compressive plastic strain is more than 8%.
5. The refractory high-entropy alloy according to claim 1, wherein when a=22.5, b=7.5, c=22.5, d=22.5, e=12.5, f=12.5, the refractory high-entropy alloy has the formula Nb 22.5 Mo 7.5 Ta 22.5 W 22.5 Zr 12.5 C 12.5 The compression strength at room temperature is more than 2400MPa, and the compression plastic strain at room temperature is more than 9%.
6. The refractory high-entropy alloy according to claim 1, wherein when a=19.5, b=6.5, c=19.5, d=19.5, e=17.5, f=17.5, the refractory high-entropy alloy has the formula Nb 19.5 Mo 6.5 Ta 19.5 W 19.5 Zr 17.5 C 17.5 The compression strength at room temperature is more than 2400MPa, and the compression plastic strain at room temperature is 8%.
7. A method for preparing a refractory high-entropy alloy according to any one of claims 1 to 6, characterized in that it comprises in particular the steps of:
s1) batching: preprocessing Nb, mo, ta, W, zr and C raw materials to obtain Nb, mo, ta, W, zr and C raw materials meeting the proportioning quality;
s2) alloy smelting: and (3) carrying out alloy smelting on the metal raw materials meeting the proportioning quality prepared in the step S1) for multiple times in inert gas under the vacuumizing condition, turning over and tilting the cast ingot by 40-60 degrees before each smelting, and finally obtaining the Nb-Mo-Ta-W-Zr-C refractory high-entropy alloy.
8. The method of claim 7, wherein Nb, mo, ta, W and Zr in S1) are elemental particles having a purity greater than 99.9%; the raw material C is high-purity graphite.
9. The method of claim 7, wherein the refractory high-entropy alloy has a compressive strength of not less than 2000MPa at room temperature and a compressive plastic strain of not less than 8%; the compressive strength at 1600 ℃ is not less than 600MPa.
10. Use of a refractory high-entropy alloy according to any one of claims 1 to 6 in the field of ultra-high temperature structural materials.
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