CN114150206A - Tungsten-based columnar crystal high-entropy alloy surface-to-plasma material and preparation method thereof - Google Patents
Tungsten-based columnar crystal high-entropy alloy surface-to-plasma material and preparation method thereof Download PDFInfo
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- CN114150206A CN114150206A CN202111432526.3A CN202111432526A CN114150206A CN 114150206 A CN114150206 A CN 114150206A CN 202111432526 A CN202111432526 A CN 202111432526A CN 114150206 A CN114150206 A CN 114150206A
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000000956 alloy Substances 0.000 title claims abstract description 51
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 50
- 239000013078 crystal Substances 0.000 title claims abstract description 49
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010937 tungsten Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 33
- 238000010894 electron beam technology Methods 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 229910052715 tantalum Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- 229910052727 yttrium Inorganic materials 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 5
- 229910004546 TaF5 Inorganic materials 0.000 claims description 5
- 229910010348 TiF3 Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 5
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 6
- 230000004927 fusion Effects 0.000 abstract description 5
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 10
- 229910052805 deuterium Inorganic materials 0.000 description 10
- 238000003795 desorption Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
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- 230000004992 fission Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- 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
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/08—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal halides
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21B—FUSION REACTORS
- G21B1/00—Thermonuclear fusion reactors
- G21B1/11—Details
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Abstract
A tungsten-based columnar crystal high-entropy alloy surface plasma material and a preparation method thereof belong to the field of nuclear fusion energy application. The tungsten-based columnar crystal high-entropy alloy has (001) -oriented columnar crystal grains, and the grain size is 10-70 mu m. The atomic percentage range of each element in the high-entropy alloy is as follows: 20-35% of W, 10-25% of Ta, 10-25% of Cr, 10-20% of V, 5-20% of Ti and 5-20% of Y. The density of the tungsten-based columnar crystal high-entropy alloy can reach more than 99 percent, the purity of the tungsten-based columnar crystal high-entropy alloy also exceeds 99.9 percent, the size of columnar crystals can be controlled to be 10-70 mu m, and the fuel retention in the irradiated material can be obviously reduced. Due to the high entropy effect, the migration energy of the interstitials and the vacancies in the material after irradiation is closer, so that the recombination rate of the interstitials and the vacancies is higher, and the neutron irradiation resistance of the material can be obviously improved.
Description
Technical Field
The invention belongs to the field of nuclear fusion energy application, and particularly relates to a plasma material facing design, namely a tungsten-based columnar crystal high-entropy alloy.
Background
High-efficiency clean energy has gradually become the final trend of future energy development. The nuclear fusion energy is expected to become the ultimate energy in future society due to abundant reserves, no radioactivity compared with fission, cleanness and high efficiency. Nuclear fusion refers to the process of polymerization of two or more light nuclei, such as deuterium and tritium, to produce a heavier nucleus and release a large amount of energy. However, currently, controlled nuclear fusion has not been achieved due to technical limitations. Among them, boundary plasma interaction with materials is one of the difficulties. The tungsten materials currently used produce microstructural changes such as bubbles, holes and other nanostructure generation under neutron, plasma irradiation. Meanwhile, the irradiation can also cause the material to be hardened and embrittled, and the service performance of the material is seriously influenced, so that the development of the plasma material by the high-performance tungsten basal plane is imperative.
The high-entropy alloy is generally defined as an alloy with a plurality of alloy elements in equal atomic ratio or near equal atomic ratio according to components, and the atomic fraction of each component is between 5% and 35%, and the alloy has excellent thermodynamic properties and can improve the properties of strength, hardness, high temperature resistance, corrosion resistance and the like of the material to a certain extent. In addition, because the migration energy of the vacancies and the interstitials in the high-entropy alloy is closer, and the recombination rate of the vacancies and the interstitials is higher, the high-entropy alloy has stronger dislocation damage resistance and better irradiation resistance.
Due to the columnar structure of the columnar crystal material perpendicular to the surface of the material, grain boundaries are mostly perpendicular to the surface of the material and can be used as transport channels, so that hydrogen and helium entering the material in the plasma irradiation process return to plasma along the grain boundaries, and the fuel retention in the material is reduced, and the utilization rate of fuel is improved.
At present, most researches are carried out in a tungsten-based high-entropy alloy system, and columnar crystal high-entropy alloy is not reported. The invention relates to a tungsten-based high-entropy alloy material with a body-centered cubic (BCC) phase columnar crystal structure.
Disclosure of Invention
The invention aims to provide a tungsten-based columnar crystal high-entropy alloy plasma facing material.
The tungsten-based columnar crystal high-entropy alloy is characterized by having (001) -oriented columnar crystal grains with the grain size of 10-70 mu m. The atomic percentage range of each element in the high-entropy alloy is as follows: 20-35% of W, 10-25% of Ta, 10-25% of Cr, 10-20% of V, 5-20% of Ti and 5-20% of Y.
The tungsten-based columnar crystal high-entropy alloy is a block material.
The invention relates to a preparation method of a tungsten-based columnar crystal high-entropy alloy, which is characterized by comprising the following steps of: the tungsten-based columnar crystal high-entropy alloy provided by the invention can be prepared by adopting methods of chemical vapor deposition, vacuum induction melting and electron beam melting, and can be used for preparing alloys with various components according to requirements.
The preparation method adopting the chemical vapor deposition method comprises the following steps: by passing gaseous WF6、TaF5、CrF3、VF4、TiF3、YF3Fully mixing the materials according to the required element proportion, adopting a rolled tungsten plate as a deposition matrix, electrifying and heating the matrix to 600-1000 ℃, controlling the mixed fluorinated gas and the hydrogen through a needle valve and a flowmeter, mixing the mixed fluorinated gas and the hydrogen according to the volume ratio of 1:2.0-2.28, and introducing the mixed fluorinated gas and the hydrogen into a reaction chamber. After full reaction, the reaction product is deposited on a rolled tungsten plate, and the obtained columnar crystal high-entropy alloy can be cooled and taken out after the reaction product is deposited to the required thickness.
The preparation method adopting the vacuum induction melting method comprises the following steps: w, Ta powder with the purity of more than 99.9 percent and the average grain diameter of 1 mu m is fully mixed according to the required proportion and then is put into a crucible of a vacuum induction furnace, and V, Cr, Ti and Y powder with the purity of more than 99.9 percent and the average grain diameter of 1 mu m is mixed according to the required proportion and then is put into a feeding bin. After the charging is finished, vacuumizing is started, when the pressure of a vacuum chamber is 0.6-1.0Pa, the power of the smelting furnace is increased to 15-20kW, after the surface of a molten pool is calm, the power is continuously increased to 17-22kW after no bubbles escape, and the vacuum degree of the device is kept lower than 50Pa in the period. After 30-60min, V, Cr, Ti and Y powder in the feeding bin is added, and after the powder is reddened, the power is increased to 20-25 kW. Controlling the vacuum degree to be lower than 100Pa, and keeping the vacuum environment for 50-70 min. After the furnace burden is melted down, adding blocky graphite for carbon-oxygen reaction, and increasing the power to 25-30kW after adding the blocky graphite and stirring for 1-2 min. And (3) casting the metal liquid in the crucible into a mould, and then cooling and demoulding. The obtained block material can be divided into a surface layer chilling crystal area, an equiaxed crystal area, a central fine crystal area and a columnar crystal area according to the characteristics of the structure and the morphology, and the tungsten-based columnar crystal high-entropy alloy can be obtained by a later-stage linear cutting technology.
The preparation method adopting the electron beam melting method comprises the following steps: purity of>99.9 percent of W, Ta, V, Cr, Ti and Y powder material with the average grain diameter of 1 mu m is uniformly mixed with a small amount of carbon powder according to the required proportion, wherein the mass fraction of the alloy powder is 98.5 percent, and the mass fraction of the carbon powder is 1.5 percent. The mixed powder of the alloy and the carbon powder is put into a high-temperature high-pressure sintering furnace and sintered for 1 to 2 hours at the temperature of 1800 plus materials and 2000 ℃ under the pressure of 24 to 30MPa to obtain the pre-formed block material. Then placing the preformed block material in an electron beam melting furnace, starting a circulating water cooling system and a vacuum system, wherein the vacuum degree is 1-3 multiplied by 10-3And when Pa, starting an electron gun, increasing the power to 15-20kW, and adjusting the beam spot of the electron beam to uniformly scan on the surface of the material. And after the material is completely melted, increasing the power of the electron beam to 18-23kW, closing the electron gun after 30-60min, and taking out the material after cooling. The obtained block material can be divided into an equiaxed crystal area, a central fine crystal area and a columnar crystal area according to the characteristics of the tissue morphology, and the tungsten-based columnar crystal high-entropy alloy can be obtained through later-stage linear cutting treatment.
Compared with the prior art, the invention has the advantages that:
the density of the tungsten-based columnar crystal high-entropy alloy can reach more than 99 percent, the purity of the tungsten-based columnar crystal high-entropy alloy also exceeds 99.9 percent, the size of columnar crystals can be controlled to be 10-70 mu m, and the fuel retention in the irradiated material can be obviously reduced.
Due to the high entropy effect, the migration energy of the interstitials and the vacancies in the material after irradiation is closer, so that the recombination rate of the interstitials and the vacancies is higher, and the neutron irradiation resistance of the material can be obviously improved.
Compared with the reported high-entropy alloy containing Nb and Mo elements, the tungsten-based columnar crystal high-entropy alloy disclosed by the invention has the advantages that the composition elements W, Ta, V, Cr, Ti and Y are all low-activation elements, and the requirements of an irradiation environment can be better met.
The tungsten-based columnar crystal high-entropy alloy adopts a columnar crystal structure, and the structure is characterized in that crystal grains in the material are in a strip shape, and the long axes of the crystal grains are distributed according to the preferred orientation perpendicular to the surface, namely, the columnar crystal grains with the (001) orientation. In the plasma irradiation process, hydrogen and helium entering the material can return to the plasma by using a grain boundary as a short-circuit diffusion channel, so that the retention of fuel in the material is reduced, and the utilization rate of the fuel is greatly improved.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The chemical vapor deposition method is adopted, and the implementation steps are as follows:
the required fluorinated gas is mixed according to the atomic percentage WF6 35％、TaF5 20％、CrF3 15％、VF4 10％、TiF310％、YF3After 10 percent of the mixture is fully mixed, the mixture is led into a leading-in device, and a rolled tungsten plate is placed in a reaction chamber to be used as a deposition matrix. Electrifying to heat the substrate to 600 ℃, and introducing the mixed gas and hydrogen into the reaction chamber in a ratio of 1: 2.28. After chemical reaction, a deposition layer is obtained on the substrate, and the substrate is cooled and taken out after deposition to the required thickness. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentages: 35% of W, 20% of Ta, 15% of Cr, 10% of V, 10% of Ti and 10% of Y, and the columnar grain size is 50 μm. After deuterium plasma irradiation, the retention rate is 3 multiplied by 10 as measured by thermal desorption spectroscopy-6。
Example 2
The chemical vapor deposition method is adopted, and the implementation steps are as follows:
the required fluorinated gas is added according to atomic percentSpecific WF6 30％、TaF5 25％、CrF3 25％、VF4 10％、TiF35％、YF3After fully mixing 5 percent of the mixture, introducing the mixture into a guiding device, and placing a rolled tungsten plate as a deposition matrix in a reaction chamber. And electrifying to heat the substrate to 800 ℃, and introducing the mixed gas and hydrogen into the reaction chamber according to the volume ratio of 1: 2.25. After chemical reaction, a deposition layer is obtained on the substrate, and the substrate is cooled and taken out after deposition to the required thickness. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentages: 30% of W, 25% of Ta, 25% of Cr, 10% of V, 5% of Ti and 5% of Y, and the columnar grain size is 30 μm. After deuterium plasma irradiation, the retention rate is 1 × 10 as measured by thermal desorption spectroscopy-6。
Example 3
The chemical vapor deposition method is adopted, and the implementation steps are as follows:
the fluorinated gas is mixed according to the atomic percentage WF6 20％、TaF5 10％、CrF3 10％、VF4 20％、TiF320％、YF3After fully mixing 20 percent of the mixture, introducing the mixture into a guiding device, and putting the rolled tungsten plate deposition matrix into a reaction chamber. Electrifying to heat the substrate to 1000 ℃, and introducing the mixed gas and hydrogen into the reaction chamber according to the volume ratio of 1: 2.0. After chemical reaction, a deposition layer is obtained on the substrate, and the substrate is cooled and taken out after deposition to the required thickness. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentages: w20%, Ta 10%, Cr 20%, V20%, Ti 20%, Y20%, and a columnar grain size of 10 μm. After deuterium plasma irradiation, the retention rate is 5 multiplied by 10 as measured by thermal desorption spectroscopy-7。
Example 4
The vacuum induction melting method is adopted, and the implementation steps are as follows:
purity of>99.9% of W, Ta, Cr, V, Ti and Y powder with the average grain diameter of 1 mu m, and the components are mixed according to the atomic ratio of W20%, Ta 20%, Cr 10%, V20%, Ti 20% and Y10%. W, Ta powder is mixed evenly and put into a vacuum induction furnace crucible, and Cr, V, Ti and Y powder are put into a feeding grid. After the charging is finished, vacuumizing is started, when the pressure of a vacuum chamber is 1Pa, the power of the smelting furnace is increased to 15kW, and when the surface of a molten pool is calmAnd continuously increasing the power to 17kW after no bubbles escape, and keeping the vacuum degree of the device below 50 Pa. After 30min, adding the raw material powder in the feeding bin, and increasing the power to 20kW after the additional powder turns red. Controlling the vacuum degree to be lower than 100Pa, and keeping the vacuum environment for 50 min. After furnace burden is melted down, adding blocky graphite for carbon-oxygen reaction, and increasing power to 25kW after adding the blocky graphite and stirring for 2 min. Pouring the mixed liquid in the crucible into a mold, staying in a vacuum environment until the cast ingot is cooled, breaking the vacuum and taking out. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentage components: w20%, Ta 20%, Cr 10%, V20%, Ti 20%, Y10%, and a columnar grain size of 40 μm. After deuterium plasma irradiation, the retention rate is 2 multiplied by 10 as measured by thermal desorption spectroscopy-6。
Example 5
The vacuum induction melting method is adopted, and the implementation steps are as follows:
purity of>99.9 percent of W, Ta, Cr, V, Ti and Y powder with the average grain diameter of 1 mu m are mixed according to the atomic ratio of W25 percent, Ta 10 percent, Cr 25 percent, V15 percent, Ti 5 percent and Y20 percent, W, Ta powder is evenly mixed and then put into a vacuum induction furnace crucible, and the Cr, V, Ti and Y powder is put into a feeding grid. And after the charging is finished, vacuumizing, when the pressure of a vacuum chamber is 0.8Pa, increasing the power of the smelting furnace to 18kW, continuing increasing the power to 20kW after the surface of a molten pool is calm and no bubbles escape, and keeping the vacuum degree of the device to be lower than 50 Pa. After 45min, adding the raw material powder in the feeding bin, and increasing the power to 22kW after the additional powder turns red. Controlling the vacuum degree to be lower than 100Pa, and keeping the vacuum environment for 60 min. After the furnace burden is melted down, adding blocky graphite for carbon-oxygen reaction, and increasing the power to 27kW after adding the blocky graphite and stirring for 2 min. Pouring the mixed liquid in the crucible into a mold, staying in a vacuum environment until the cast ingot is cooled, breaking the vacuum and taking out. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentage components: 25% of W, 10% of Ta, 25% of Cr, 15% of V, 5% of Ti and 20% of Y, and the columnar grain size is 50 μm. After deuterium plasma irradiation, the retention rate is 3 multiplied by 10 as measured by thermal desorption spectroscopy-6。
Example 6
The vacuum induction melting method is adopted, and the implementation steps are as follows:
purity of>99.9 percent of W, Ta, Cr, V, Ti and Y powder with the average grain diameter of 1 mu m are mixed according to the atomic ratio of W35 percent, Ta 25 percent, Cr 15 percent, V10 percent, Ti 10 percent and Y5 percent, W, Ta powder is evenly mixed and then put into a vacuum induction furnace crucible, and the Cr, V, Ti and Y powder is put into a feeding grid. And after the charging is finished, vacuumizing, when the pressure of a vacuum chamber is 0.6Pa, increasing the power of the smelting furnace to 20kW, continuing to increase the power to 22kW after the surface of a molten pool is calm and no bubble escapes, and keeping the vacuum degree of the device to be lower than 50Pa in the period. After 60min, adding the raw material powder in the feeding bin, and increasing the power to 25kW after the additional powder turns red. Controlling the vacuum degree to be lower than 100Pa, and keeping the vacuum environment for 70 min. After the furnace burden is melted down, adding blocky graphite for carbon-oxygen reaction, and increasing the power to 30kW after adding the blocky graphite and stirring for 1 min. Pouring the mixed liquid in the crucible into a mold, staying in a vacuum environment until the cast ingot is cooled, breaking the vacuum and taking out. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentage components: 35% of W, 25% of Ta, 15% of Cr, 10% of V, 10% of Ti and 5% of Y, and the columnar grain size is 70 μm. After deuterium plasma irradiation, the retention rate is 5 multiplied by 10 as measured by thermal desorption spectroscopy-6。
Example 7
An electron beam melting method is adopted, and the implementation steps are as follows:
purity of>99.9% of W, Ta, Cr, V, Ti and Y powder with the average grain diameter of 1 μm, and the components are mixed according to the atomic ratio of W20%, Ta 15%, Cr 20%, V20%, Ti 20% and Y5%. The alloy powder with the mass fraction of 98.5 percent and the carbon powder with the mass fraction of 1.5 percent are fully mixed and then put into a high-temperature high-pressure sintering furnace to be sintered for 2 hours at the temperature of 1800 ℃ under the pressure of 24MPa, so as to obtain the pre-formed block material. Then placing the preformed block material in a water-cooled copper crucible of an electron beam melting furnace, starting a circulating water cooling system and a vacuum system until the vacuum degree is lower than 3 multiplied by 10-3And when Pa, starting an electron gun, increasing the power to 15kW and adjusting the beam spot of the electron beam to uniformly scan on the surface of the material. And after the material is completely melted, increasing the power of the electron beam to 18kW, keeping for 30min, closing the electron gun, and cooling and taking out the material. To obtainThe tungsten-based columnar crystal high-entropy alloy comprises the following components in percentage by atom: w20%, Ta 15%, Cr 20%, V20%, Ti 20%, Y5%, and a columnar grain size of 30 μm. After deuterium plasma irradiation, the retention rate is 1 × 10 as measured by thermal desorption spectroscopy-6。
Example 8
An electron beam melting method is adopted, and the implementation steps are as follows:
purity of>99.9 percent of W, Ta, Cr, V, Ti and Y powder with the average grain diameter of 1 mu m are mixed according to the atomic ratio of W30 percent, Ta 25 percent, Cr 10 percent, V10 percent, Ti 5 percent and Y20 percent. The alloy powder with the mass fraction of 98.5 percent and the carbon powder with the mass fraction of 1.5 percent are fully mixed and then put into a high-temperature high-pressure sintering furnace to be sintered for 1.5 hours under the conditions of 2000 ℃ and 27MPa, so as to obtain the preformed block material. Then placing the preformed block material in a water-cooled copper crucible of an electron beam melting furnace, starting a circulating water cooling system and a vacuum system until the vacuum degree is lower than 2 multiplied by 10-3And when Pa, starting an electron gun, increasing the power to 18kW and adjusting the beam spot of the electron beam to uniformly scan on the surface of the material. And after the material is completely melted, increasing the power of the electron beam to 21kW, keeping for 45min, closing the electron gun, and cooling and taking out the material. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentage components: 30% of W, 25% of Ta, 10% of Cr, 10% of V, 5% of Ti and 20% of Y, and the columnar grain size is 50 μm. After deuterium plasma irradiation, the retention rate is 3 multiplied by 10 as measured by thermal desorption spectroscopy-6。
Example 9
An electron beam melting method is adopted, and the implementation steps are as follows:
purity of>99.9 percent of W, Ta, Cr, V, Ti and Y powder with the average grain diameter of 1 mu m are mixed according to the atomic ratio of W35 percent, Ta 10 percent, Cr 25 percent, V10 percent, Ti 15 percent and Y5 percent. The alloy powder with the mass fraction of 98.5 percent and the carbon powder with the mass fraction of 1.5 percent are fully mixed and then put into a high-temperature high-pressure sintering furnace to be sintered for 1h under the conditions of 2000 ℃ and 30MPa, so as to obtain the preformed block material. Then placing the preformed block material in a water-cooled copper crucible of an electron beam melting furnace, starting a circulating water cooling system and a vacuum system until the vacuum degree is lower than 1 multiplied by 10-3When the electron gun is started at Pa,the power was increased to 20kW and the beam spot of the electron beam was adjusted to scan uniformly over the surface of the material. And after the material is completely melted, increasing the power of the electron beam to 23kW, keeping for 60min, closing the electron gun, and cooling and taking out the material. The obtained tungsten-based columnar crystal high-entropy alloy comprises the following atomic percentage components: 35% of W, 10% of Ta, 25% of Cr, 10% of V, 15% of Ti and 5% of Y, and the columnar grain size is 70 μm. After deuterium plasma irradiation, the retention rate is 5 multiplied by 10 as measured by thermal desorption spectroscopy-6。
Claims (2)
1. A tungsten-based columnar crystal high-entropy alloy face-to-plasma material is characterized by having (001) -oriented columnar crystal grains having a grain size of 10 to 70 μm. The atomic percentage range of each element in the high-entropy alloy is as follows: 20-35% of W, 10-25% of Ta, 10-25% of Cr, 10-20% of V, 5-20% of Ti and 5-20% of Y.
2. The method of claim 1, wherein: adopts the methods of chemical vapor deposition, vacuum induction melting or electron beam melting,
the preparation method adopting the chemical vapor deposition method comprises the following steps: by passing gaseous WF6、TaF5、CrF3、VF4、TiF3、YF3Fully mixing the materials according to the required element proportion to obtain a fluorinated gas, adopting a rolled tungsten plate as a deposition matrix, electrifying and heating the matrix to 600-1000 ℃, mixing the mixed fluorinated gas and hydrogen in a volume ratio of 1:2.0-2.28, and introducing the mixture into a reaction chamber; depositing the reaction product on a rolled tungsten plate, depositing to the required thickness, and cooling and taking out the obtained columnar crystal high-entropy alloy;
the preparation method adopting the vacuum induction melting method comprises the following steps: w, Ta powder with the purity of more than 99.9 percent and the average grain diameter of 1 mu m is fully mixed according to the required proportion and then is put into a crucible of a vacuum induction furnace, and V, Cr, Ti and Y powder with the purity of more than 99.9 percent and the average grain diameter of 1 mu m is put into a feeding bin after being mixed according to the required proportion; after the charging is finished, starting vacuumizing, when the pressure of a vacuum chamber is 0.6-1.0Pa, increasing the power of the smelting furnace to 15-20kW, continuing to increase the power to 17-22kW after the surface of a molten pool is calm and no bubbles escape, and keeping the vacuum degree of the device lower than 50Pa in the period; after 30-60min, adding V, Cr, Ti and Y powder in a feeding bin, and increasing the power to 20-25kW after the powder is reddened; controlling the vacuum degree to be lower than 100Pa, and keeping the vacuum degree for 50-70min in a vacuum environment; after furnace burden is melted down, adding blocky graphite for carbon-oxygen reaction, increasing power to 25-30kW after adding, and stirring for 1-2 min; pouring the metal liquid in the crucible into a mold, and then cooling and demolding;
the preparation method adopting the electron beam melting method comprises the following steps: purity of>99.9 percent of W, Ta, V, Cr, Ti and Y powder material with the average grain diameter of 1 mu m is mixed with carbon powder uniformly according to the required proportion, wherein the mass fraction of the alloy powder is 98.5 percent, and the mass fraction of the carbon powder is 1.5 percent; putting the mixed powder of the alloy and the carbon powder into a high-temperature high-pressure sintering furnace, and sintering for 1-2h under the conditions of 1800-2000 ℃ and 24-30MPa to obtain a pre-formed block material; then placing the preformed block material in an electron beam melting furnace, starting a circulating water cooling system and a vacuum system, wherein the vacuum degree is 1-3 multiplied by 10-3When Pa, starting an electron gun, increasing the power to 15-20kW, and adjusting the beam spot of an electron beam to uniformly scan on the surface of the material; and after the material is completely melted, increasing the power of the electron beam to 18-23kW, closing the electron gun after 30-60min, and taking out the material after cooling.
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