CN110331322B - MoVNbTiZr for nuclear powerxHigh-entropy alloy and preparation method thereof - Google Patents
MoVNbTiZr for nuclear powerxHigh-entropy alloy and preparation method thereof Download PDFInfo
- Publication number
- CN110331322B CN110331322B CN201910673106.0A CN201910673106A CN110331322B CN 110331322 B CN110331322 B CN 110331322B CN 201910673106 A CN201910673106 A CN 201910673106A CN 110331322 B CN110331322 B CN 110331322B
- Authority
- CN
- China
- Prior art keywords
- alloy
- nbtizr
- entropy alloy
- nuclear power
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 168
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000003723 Smelting Methods 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 238000000265 homogenisation Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 230000004584 weight gain Effects 0.000 claims description 5
- 235000019786 weight gain Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000010297 mechanical methods and process Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000007769 metal material Substances 0.000 abstract description 3
- 230000008520 organization Effects 0.000 abstract description 2
- 239000010955 niobium Substances 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 238000013461 design Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 10
- 238000005498 polishing Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000010891 electric arc Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910003460 diamond Inorganic materials 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 229910000967 As alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910000979 O alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the field of metal materials and preparation thereof, in particular to Mo for nuclear power0.5V0.5NbTiZrxHigh-entropy alloy and a preparation method thereof. The high-entropy alloy material comprises Mo0.5V0.5NbTiZrxWherein x is a molar ratio and x is 0-2.0. Taking simple substances Mo, V, Nb, Ti and Zr, proportioning according to nominal chemical components, preparing the alloy by smelting in a vacuum arc furnace, putting a low-melting-point element below a copper crucible during smelting, putting a high-melting point element above the copper crucible, vacuumizing a working cavity of the arc furnace, introducing high-purity argon, and performing arc striking smelting to obtain Mo0.5V0.5NbTiZrxThe high-entropy alloy is cast into ingots, then subjected to hot isostatic pressing treatment and then subjected to homogenization annealing heat treatment. The alloy has a simple single-body-core cubic structure, is simple in organization structure, excellent in mechanical property, excellent in high-temperature steam corrosion resistance and has the potential application possibility in a nuclear power high-temperature environment. The method is simple and easy to implement, and has wide application prospect.
Description
Technical Field
The invention relates to the field of metal materials and preparation thereof, in particular to Mo for nuclear power0.5V0.5NbTiZrxHigh-entropy alloy and a preparation method thereof.
Background
The high-entropy alloy is a newly developed metal material, and breaks through the traditional design idea of the alloy with one or two main elements. The novel alloy design concept greatly expands the system of alloy design and provides a wide platform for exploring alloys with new components and new properties. Generally speaking, the high-entropy alloy means that the component number of the alloy is more than or equal to 5, the components of the alloy are proportioned in an equimolar ratio, and the mole percentage of each element is between 5% and 35%. Since the alloy does not mainly contain one element, the high-entropy alloy is also called multi-principal-element alloy. However, the latest research result shows that the high-entropy alloy with the equal molar ratio does not necessarily have the best performance, and the high-entropy alloy with the unequal molar ratio, namely the second-generation high-entropy alloy, can also be designed according to the multi-principal-element design idea of the high-entropy alloy.
Although the high-entropy alloy has multiple main elements, after reasonable and careful composition design, the alloy can form a simple solid solution phase, such as: face centered cubic, body centered cubic, or hexagonal close packed. The phase formed is much lower than predicted by the gibbs phase law, which may be due to the high entropy effect of high entropy alloys, especially at high temperatures.
The design and preparation work of the block high-entropy alloy for nuclear power is less, most of reported high-entropy alloys contain transition metal elements, particularly cobalt elements, and are not suitable for being used as nuclear power materials due to high thermal neutron absorption cross sections and high induced radioactivity. Therefore, the selection of the element with the low thermal neutron absorption cross section as the element for designing the high-entropy alloy has important practical significance.
Disclosure of Invention
The invention aims to provide Mo for nuclear power0.5V0.5NbTiZrxThe high-entropy alloy has high melting point, high strength, good plasticity and excellent corrosion resistance, and the structure of the high-entropy alloy is a single-phase body-centered cubic.
The technical scheme of the invention is as follows:
mo for nuclear power0.5V0.5NbTiZrxHigh-entropy alloy with Mo as component0.5V0.5NbTiZrxThe high-entropy alloy consists of five alloy elements of Mo, V, Nb, Ti and Zr with low thermal neutron absorption cross sections, wherein x is a molar ratio and is 0-2.0; according to the mol percentage, the content of Mo and V is respectively 9.0-18.0%, the content of Nb and Ti is respectively 19.0-34.0%, and the content of Zr is 0-40.0%.
Mo for nuclear power0.5V0.5NbTiZrxHigh entropy alloy, x is any one of 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0.
Mo for nuclear power0.5V0.5NbTiZrxA high entropy alloy having a single body-centered cubic structure.
Mo for nuclear power0.5V0.5NbTiZrxThe preparation method of the high-entropy alloy comprises the following specific preparation processes:
the method comprises the following steps: weighing the raw materials according to the nominal chemical composition of the alloy in proportion;
step two: putting raw materials into a copper crucible of a vacuum arc furnace according to the sequence of low melting point below and high melting point above; vacuum degree of vacuum arc furnace at 1 × 10-4～5×10-4After Pa, filling high-purity argon, arc striking and smelting, cooling after the alloy is fully melted, and smelting for more than 4 times after the solidified alloy ingot is turned over to ensure that the components are uniform;
step three: carrying out hot isostatic pressing treatment on an alloy ingot prepared by smelting in a vacuum arc furnace;
step four: and after hot isostatic pressing treatment, carrying out homogenization heat treatment annealing at the temperature of 1200 +/-50 ℃ for 10-30 hours.
Mo for nuclear power0.5V0.5NbTiZrxThe preparation method of the high-entropy alloy comprises the following steps of: removing oxide skin on the surface of Mo by adopting a mechanical method, and cleaning and drying the Mo; cleaning Nb and V with petroleum ether for 10-20 min, then ultrasonically cleaning with ethanol for 10-20 min, and then drying in a drying oven at the temperature of 50-100 ℃ for 1-3 h; and directly drying the Ti and the Zr in a drying oven at the temperature of 50-100 ℃ for 1-3 hours.
Mo for nuclear power0.5V0.5NbTiZrxIn the step one, the raw material Mo is in a square rod shape, the raw material V is in a tree shape, the raw material Nb is in a sheet shape, the raw material Ti is sponge titanium, the raw material Zr is nuclear grade sponge zirconium, and the purity of the raw materials Mo, V, Nb, Ti and Zr is not less than 99.5wt. -%)。
Mo for nuclear power0.5V0.5NbTiZrxThe preparation method of the high-entropy alloy has the following advantages that: 2.29 to 3.69 barn; has excellent mechanical properties: the yield strength is higher than 1200 MPa, the compressive strength is higher than 1500MPa, and the strain is higher than 10 percent; high-temperature steam corrosion resistance: the corrosion weight gain after 30 days of corrosion in superheated steam at 400 ℃ and 10.3MPa is less than 50mg/dm2。
The design concept of the alloy components and the preparation method of the invention is as follows:
the high-entropy alloy is a novel alloy which is rapidly developed in recent years, the design concept of the high-entropy alloy is to break through a design method of a traditional alloy which takes one or two metal elements as principal elements, and the design method of the multi-principal element greatly expands the system of the alloy, and provides a wide platform for researchers to search new components, research and develop new materials and explore new mechanisms. Due to the fact that the multiple main elements of the high-entropy alloy have different physical and chemical properties and atomic sizes, severe local lattice distortion and stress on an atomic scale can be caused, and the high-entropy alloy is beneficial to improving the irradiation resistance and the high-temperature performance of the high-entropy alloy, so that the high-entropy alloy becomes an attractive nuclear material. Recent research reports have also demonstrated this. The reactor type of a nuclear power station which is operated and built in China mainly comprises a pressurized water reactor, so that the nuclear power station can be operated safely and reliably, particularly, the safety of a fuel cladding material under an uncooled working condition is improved, the design and preparation of an accident fault-tolerant fuel cladding material different from zirconium alloy have great significance, and the high-entropy alloy provides the possibility. Most of high-entropy alloys reported in the literature contain cobalt element, and are not suitable for being used as fuel cladding materials due to high thermal neutron absorption cross section and induced radioactivity, so that five alloy elements of Mo, V, Nb, Ti and Zr are selected as alloy components by taking the thermal neutron absorption cross section of the element as an important reference basis in the screening process of the alloy elements. Mo is designed and prepared by using a design method of high-entropy alloy0.5V0.5NbTiZrx(x is 0 to 2.0) high entropy alloy, and combination of the alloy structure, mechanical properties and high temperature corrosionThe etching performance was investigated. The experimental result shows that Mo0.5V0.5NbTiZrxThe high-entropy alloy is composed of single-phase BCC solid solution, and when x is less than or equal to 1.5, the corrosion resistance of the alloy is superior to that of Zr-4 alloy; mo with too high Zr content0.5V0.5NbTiZr2.0The alloy has inferior high temperature corrosion resistance to Zr-4 alloy. Therefore, by utilizing the characteristics and advantages of the high-entropy alloy and through elaborate alloy element screening and a high-entropy alloy design method, the high-entropy alloy for nuclear power can be designed and prepared, and a solid foundation is laid for researching and developing a safer and more reliable fuel cladding material.
The invention has the advantages and beneficial effects that:
1. five elements of Mo, V, Nb, Ti and Zr are selected as alloy components, and the high-melting-point single-phase high-entropy alloy is prepared by smelting, has the advantages of high melting point, high strength, excellent mechanical property, excellent corrosion resistance and the like, and has wide application prospect.
2. The alloy has a simple single-body-core cubic structure, excellent mechanical property, high strength and good plasticity. Thus, potential applications in high temperature environments are possible.
3. The method comprises the steps of preparing simple substances Mo, V, Nb, Ti and Zr according to nominal chemical components, smelting the alloy in a vacuum arc furnace, putting a low-melting-point element below a copper crucible and a high-melting-point element above the copper crucible during smelting, vacuumizing a working cavity of the arc furnace, and then introducing high-purity argon. Then, the single-phase alloy is obtained through hot isostatic pressing and homogenization heat treatment. Except for Mo0.5V0.5Besides NbTi alloy, other alloys have equiaxed microstructure. The method is simple and easy to implement, and has wide application prospect.
Drawings
FIG. 1 shows Mo0.5V0.5NbTiZrx(x ═ 0, 0.25, 0.5, 0.75, 1.0, 1.5, 2.0) XRD pattern of high entropy alloy. In the figure, the abscissa 2 θ (degrees) represents the diffraction angle (degree); the ordinate intensity represents intensity (a.u.).
FIG. 2 is an enlarged view of the diffraction peak (110) in FIG. 1at an angle of 36 to 41. In the figure, the abscissa 2 θ (degrees) represents the diffraction angle (degree); the ordinate intensity represents intensity (a.u.).
FIG. 3 shows Mo0.5V0.5NbTiZrxMicrostructure of the high entropy alloy. Wherein: (a) represents Mo0.5V0.5NbTi alloy, (b) represents Mo0.5V0.5NbTiZr0.25Alloy, (c) represents Mo0.5V0.5NbTiZr0.5Alloy, (d) represents Mo0.5V0.5NbTiZr0.75And (e) represents Mo0.5V0.5NbTiZr1.0Alloy, (f) represents Mo0.5V0.5NbTiZr1.5Alloy, (g) represents Mo0.5V0.5NbTiZr2.0And (3) alloying.
FIG. 4 shows Mo0.5V0.5NbTiZrx(x ═ 0, 0.25, 0.5, 0.75, 1.0, 1.5, 2.0) vickers hardness average curve for high entropy alloys. In the figure, the abscissa x represents the molar content of zirconium element, and the ordinate Hardness represents the Vickers Hardness (Hv).
FIG. 5 shows Mo0.5V0.5NbTiZrx(x ═ 0, 0.25, 0.5, 0.75, 1.0, 1.5, 2.0) engineering stress-strain curves for the high entropy alloys.
FIG. 6 shows Mo0.5V0.5NbTiZrx(x ═ 0, 0.25, 0.5, 0.75, 1.0, 1.5, 2.0) corrosion weight gain curve for high entropy alloys in superheated steam.
Detailed Description
In the specific implementation process, the invention is oriented to Mo for nuclear power0.5V0.5NbTiZrxHigh-entropy alloy and preparation method thereof, and high-entropy alloy material component is Mo0.5V0.5NbTiZrxWherein x is a molar ratio and x is 0-2.0. The high-entropy alloy consists of five alloy elements of Mo, V, Nb, Ti and Zr with low thermal neutron absorption cross sections, and the preparation method comprises the following steps: taking simple substances Mo, V, Nb, Ti and Zr with the purity of not less than 99.5 wt.%, proportioning according to nominal chemical components, preparing the alloy by smelting in a vacuum arc furnace, and smelting low-melting pointThe point element is placed below the copper crucible, the high melting point is placed above the copper crucible, the working chamber of the electric arc furnace is vacuumized to the vacuum degree of 1 multiplied by 10-4～5×10-4Pa, then introducing high-purity argon with the volume purity of more than 99.99 wt.%, arc starting and smelting, wherein each alloy is smelted for more than 4 times to ensure the uniform components, and the alloy ingot obtained by smelting in the electric arc furnace is subjected to hot isostatic pressing treatment and then homogenization annealing heat treatment.
The present invention will be described in detail below with reference to specific examples.
Example 1
1. The alloy composition of example 1 was Mo0.5V0.5NbTiZr0.25. In this example, the content of each component is: mo 15.38 at.%, V15.38 at.%, Nb 30.77 at.%, Ti 30.77 at.%, and Zr 7.70 at.%.
The Mo0.5V0.5NbTiZr0.25The preparation method of the alloy comprises the following steps:
1) preparing materials: the high-entropy alloy elements developed by the invention are molybdenum (Mo), vanadium (V), niobium (Nb), titanium (Ti) and zirconium (Zr). The alloy is prepared according to nominal chemical composition, and the purity of the selected 5 element raw materials is higher than 99.5 wt.%. Mo is a square rod, V is a tree, Nb is a sheet, Ti is sponge titanium, and Zr is nuclear grade sponge zirconium. Firstly, pretreating raw materials: and removing oxide skin on the surface of the Mo by a mechanical method, cleaning and drying. And (3) cleaning Nb and V by using petroleum ether for 15min, then ultrasonically cleaning by using ethanol for 15min, and then drying in a drying oven (at the temperature of 80 ℃ for 2 hours), wherein the titanium sponge and the zirconium sponge are directly dried in the drying oven (at the temperature of 80 ℃ for 2 hours). After pretreatment, the mass of each element was accurately weighed in an equimolar ratio.
2) Preparing an alloy: the apparatus adopted for preparing the alloy is a WCE 300 type tungsten electrode magnetic control electric arc furnace produced by Shenyang scientific apparatus development center Limited company of Chinese academy of sciences, and a crucible used for smelting is a water-cooled copper crucible. Sequentially putting raw materials of molybdenum (Mo), vanadium (V), niobium (Nb), titanium (Ti) and zirconium (Zr) into a water-cooled copper crucible according to the sequence of melting points from low to high, putting the raw material with low melting point below and the raw material with high melting point above, and pumping the electric arc furnaceThe vacuum smelting equipment is WCE 300 type tungsten electrode magnetic control arc furnace. When the vacuum degree reaches 1 multiplied by 10-4～5×10-4After Pa, high-purity argon gas with the purity of 99.99 wt.% is filled. Firstly, smelting a titanium ingot in a cavity, further reducing the oxygen partial pressure, and preventing the oxidation in the alloy smelting process. In order to ensure the uniformity of the chemical components of the alloy, the alloy ingot is smelted for more than 4 times. And (3) finishing alloy smelting, filling air after the furnace body is cooled, opening the cavity, and taking out an alloy ingot to obtain the as-cast alloy.
3) Hot isostatic pressing treatment: and (3) placing the crucible into hot isostatic pressing equipment in an alloy ingot casting graphite crucible obtained by smelting in a vacuum arc furnace, and treating the crucible for 1-4 hours at 1200 +/-50 ℃ and under the pressure of 100-200 MPa. And cooling, and taking out the alloy cast ingot.
4) Homogenizing annealing heat treatment: and (3) cutting an appropriate amount of the ingot subjected to the hot isostatic pressing treatment, putting the ingot into a quartz tube, and carrying out homogenization heat treatment at 1200 +/-50 ℃ for 10-30 hours. And preparing samples for tissue structure characterization and mechanical property test by methods of linear cutting, rapid sawing and mechanical polishing.
2、Mo0.5V0.5NbTiZr0.25Structural characterization and mechanical property test of alloy
1) X-ray diffraction (XRD) analysis of the phase Structure of the alloy
Cutting blocks of 10mm multiplied by 10mm from an alloy ingot by utilizing linear cutting and rapid sawing, then cutting samples of 10mm multiplied by 1mm by utilizing the rapid sawing, sequentially polishing by using water grinding sand paper of No. 240, No. 600, No. 1000 and No. 2000, cleaning by alcohol and drying by cold air. XRD analysis is carried out by adopting an X' Pert Pro type diffractometer, the 2 theta range is 20-100 degrees, and the scanning speed is 4 degrees/min.
As shown in fig. 1 to 2, from the test results, it can be seen that the diffraction peak of XRD is sharp, indicating that the crystallinity of the alloy is high. From the four diffraction peaks, the alloy had a BCC crystal structure.
2) Scanning Electron Microscopy (SEM) tissue Observation and analysis
A10 mm. times.10 mm block was taken from the alloy ingot, and a 10 mm. times.10 mm. times.1 mm sample was cut out by a quick saw as a sample for SEM observation. The sample is sequentially ground by using No. 240, No. 600, No. 1000, No. 2000 and No. 3000 metallographic abrasive paper, mechanically polished by using diamond polishing pastes with the particle size of 2.5 microns and 1.0 micron, manually polished by using nano silicon dioxide for about 3 hours, sequentially ultrasonically cleaned by using a 1mol/L NaOH aqueous solution and pure water, and dried for later use. SEM model number FEIXL30, and backscattering mode was used for observation.
As shown in FIG. 3, the results of texture analysis and test showed Mo0.5V0.5NbTiZr0.25The alloy consists of BCC solid solution, the tissue morphology is equiaxed crystal, the nominal chemical composition is listed in Table 1, and the actual chemical composition is listed in Table 2.
TABLE 1Mo0.5V0.5NbTiZrxNominal chemical composition (at.%) of high entropy alloy
| Alloy (I) | Alloy number | Mo | V | Nb | Ti | Zr |
| Mo0.5V0.5NbTi | Zr0 | 16.67 | 16.67 | 33.33 | 33.33 | - |
| Mo0.5V0.5NbTiZr0.25 | Zr0.25 | 15.38 | 15.38 | 30.77 | 30.77 | 7.70 |
| Mo0.5V0.5NbTiZr0.5 | Zr0.5 | 14.28 | 14.28 | 28.58 | 28.58 | 14.28 |
| Mo0.5V0.5NbTiZr0.75 | Zr0.75 | 13.33 | 13.33 | 26.67 | 26.67 | 20.00 |
| Mo0.5V0.5NbTiZr1.0 | Zr1.0 | 12.50 | 12.50 | 25.00 | 25.00 | 25.00 |
| Mo0.5V0.5NbTiZr1.5 | Zr1.5 | 11.11 | 11.11 | 22.22 | 22.22 | 33.34 |
| Mo0.5V0.5NbTiZr2.0 | Zr2.0 | 10.00 | 10.00 | 20.00 | 20.00 | 40.00 |
TABLE 2 Mo0.5V0.5NbTiZrxMeasured chemical composition (at.%) of high entropy alloy
3) Vickers hardness analysis of alloys
The sample is used as a sample with the dimension of 10mm multiplied by 1mm for alloy Vickers hardness analysis, the sample is sequentially ground by 240#, 600#, 1000#, 2000# and 3000# metallographic abrasive paper, then mechanically polished by diamond polishing pastes with the thickness of 2.5 mu m and 1.0 mu m, then manually polished by nano silicon dioxide for about 3 hours, and then sequentially ultrasonically cleaned by 1mol/L NaOH aqueous solution and pure water, and dried for standby. As shown in figure 4, the Vickers hardness of the alloy is tested by using an MHVD-1000AP Vickers hardness tester, the loading force is 1000g during the test, the holding time is 15s, and 7 samples are collected during the testEffect data points, their average as final result, Mo0.5V0.5NbTiZr0.25The Vickers hardness test result of the alloy is 424.0 +/-2.8 Hv.
4) Analysis of compression mechanical Properties at Room temperature
The sample size for room temperature mechanical property analysis is phi 3mm multiplied by 6mm, the side surface of the cylinder is polished by a centerless grinder, and the end surface is polished to be flat by metallographic abrasive paper. The room temperature compression experiment adopts an Instron5582 electronic universal tester with the strain rate of 1 multiplied by 10-3The test employed 3 replicates.
As shown in fig. 5, the yield strength of the alloy was 1457MPa, the compressive strength was 2008MPa, and the strain was 24.6%, and it can be seen that the alloy has excellent room-temperature mechanical properties.
5) Analysis of superheated steam Corrosion Performance
The sample is used as a sample with the dimension of 10mm multiplied by 1mm for alloy Vickers hardness analysis, and is mechanically polished by diamond polishing pastes with the diameter of 2.5 mu m and the diameter of 1.0 mu m after being sequentially ground by metallographic abrasive paper of No. 240, No. 600, No. 1000, No. 2000 and No. 3000, and is dried for standby. As shown in FIG. 6, Mo0.5V0.5NbTiZr0.25The corrosion weight gain of the alloy after 30 days of corrosion in superheated steam at 400 ℃ and 10.3MPa is 22.87mg/dm2。
Example 2
1. The alloy composition of example 2 was Mo0.5V0.5NbTiZr1.5. In this example, the content of each component is: mo 11.11 at.%, V11.11 at.%, Nb 22.22 at.%, Ti 22.22 at.% and Zr 33.34 at.%.
The Mo0.5V0.5NbTiZr1.5The preparation method of the alloy comprises the following steps:
1) preparing materials: the high-entropy alloy elements developed by the invention are molybdenum (Mo), vanadium (V), niobium (Nb), titanium (Ti) and zirconium (Zr). The alloy is prepared according to nominal chemical composition, and the purity of the selected 5 element raw materials is higher than 99.5 wt.%. Mo is a square rod, V is a tree, Nb is a sheet, Ti is sponge titanium, and Zr is nuclear grade sponge zirconium. Firstly, pretreating raw materials: and removing oxide skin on the surface of the Mo by a mechanical method, cleaning and drying. And (3) cleaning Nb and V by using petroleum ether for 15min, then ultrasonically cleaning by using ethanol for 15min, and then drying in a drying oven (at the temperature of 80 ℃ for 2 hours), wherein the titanium sponge and the zirconium sponge are directly dried in the drying oven (at the temperature of 80 ℃ for 2 hours). After pretreatment, the mass of each element was accurately weighed in an equimolar ratio.
2) Preparing an alloy: the apparatus adopted for preparing the alloy is a WCE 300 type tungsten electrode magnetic control electric arc furnace produced by Shenyang scientific apparatus development center Limited company of Chinese academy of sciences, and a crucible used for smelting is a water-cooled copper crucible. Sequentially putting raw materials of molybdenum (Mo), vanadium (V), niobium (Nb), titanium (Ti) and zirconium (Zr) into a water-cooled copper crucible from low melting point to high melting point, putting the raw material with low melting point below and the raw material with high melting point above, vacuumizing an electric arc furnace, wherein the smelting equipment is a WCE 300 type tungsten electrode magnetic control electric arc furnace. When the vacuum degree reaches 1 multiplied by 10-4～5×10-4After Pa, high-purity argon gas with the purity of 99.99 wt.% is filled. Firstly, smelting a titanium ingot in a cavity, further reducing the oxygen partial pressure, and preventing the oxidation in the alloy smelting process. In order to ensure the uniformity of the chemical components of the alloy, the alloy ingot is smelted for more than 4 times. And (3) finishing alloy smelting, filling air after the furnace body is cooled, opening the cavity, and taking out an alloy ingot to obtain the as-cast alloy.
3) Hot isostatic pressing treatment: and (3) placing the crucible into hot isostatic pressing equipment in an alloy ingot casting graphite crucible obtained by smelting in a vacuum arc furnace, and treating the crucible for 1-4 hours at 1200 +/-50 ℃ and under the pressure of 100-200 MPa. And cooling, and taking out the alloy cast ingot.
4) Homogenizing annealing heat treatment: and (3) cutting an appropriate amount of the ingot subjected to the hot isostatic pressing treatment, putting the ingot into a quartz tube, and carrying out homogenization heat treatment at 1200 +/-50 ℃ for 10-30 hours. And preparing samples for tissue structure characterization and mechanical property test by methods of linear cutting, rapid sawing and mechanical polishing.
2、Mo0.5V0.5NbTiZr1.5Structural characterization and mechanical property test of alloy
1) X-ray diffraction (XRD) analysis of the phase Structure of the alloy
Cutting blocks of 10mm multiplied by 10mm from an alloy ingot by utilizing linear cutting and rapid sawing, then cutting samples of 10mm multiplied by 1mm by utilizing the rapid sawing, sequentially polishing by using water grinding sand paper of No. 240, No. 600, No. 1000 and No. 2000, cleaning by alcohol and drying by cold air. XRD analysis is carried out by adopting an X' Pert Pro type diffractometer, the 2 theta range is 20-100 degrees, and the scanning speed is 4 degrees/min.
As shown in fig. 1 to 2, from the test results, it can be seen that the diffraction peak of XRD is sharp, indicating that the crystallinity of the alloy is high. The alloy has a BCC crystal structure as can be seen from the four diffraction peaks.
2) Scanning Electron Microscopy (SEM) tissue Observation and analysis
A10 mm. times.10 mm block was taken from the alloy ingot, and a 10 mm. times.10 mm. times.1 mm sample was cut out by a quick saw as a sample for SEM observation. The sample is sequentially ground by using No. 240, No. 600, No. 1000, No. 2000 and No. 3000 metallographic abrasive paper, mechanically polished by using diamond polishing pastes with the particle size of 2.5 microns and 1.0 micron, manually polished by using nano silicon dioxide for about 3 hours, sequentially ultrasonically cleaned by using a 1mol/L NaOH aqueous solution and pure water, and dried for later use. SEM model number FEIXL30, and backscattering mode was used for observation.
As shown in FIG. 3, the results of texture analysis and test showed Mo0.5V0.5NbTiZr1.5The alloy consists of BCC solid solution, the structure form is isometric crystal, and the chemical components are listed in Table 2.
3) Vickers hardness analysis of alloys
The sample is used as a sample with the dimension of 10mm multiplied by 1mm for alloy Vickers hardness analysis, the sample is sequentially ground by 240#, 600#, 1000#, 2000# and 3000# metallographic abrasive paper, then mechanically polished by diamond polishing pastes with the thickness of 2.5 mu m and 1.0 mu m, then manually polished by nano silicon dioxide for about 3 hours, and then sequentially ultrasonically cleaned by 1mol/L NaOH aqueous solution and pure water, and dried for standby. Testing the Vickers hardness of the alloy by using an MHVD-1000AP Vickers hardness tester, wherein the loading force is 1000g during testing, the holding time is 15s, 7 effective data points are collected during testing, the average value of the effective data points is used as the final result, and Mo0.5V0.5NbTiZr1.5The Vickers hardness test result of the alloy is 412.9 +/-2.0 Hv.
4) Analysis of compression mechanical Properties at Room temperature
The sample size for room temperature mechanical property analysis is phi 3mm multiplied by 6mm, the side surface of the cylinder is polished by a centerless grinder, and the end surface is polished to be flat by metallographic abrasive paper. The room temperature compression experiment adopts an Instron5582 electronic universal tester with the strain rate of 1 multiplied by 10-3The test employed 3 replicates.
As shown in FIG. 5, the yield strength of the alloy was 1612MPa, the compressive strength was 1794MPa, and the strain was 13.0%, and it can be seen that the alloy had excellent room-temperature mechanical properties.
5) Analysis of superheated steam Corrosion Performance
The sample is used as a sample with the dimension of 10mm multiplied by 1mm for alloy Vickers hardness analysis, and is mechanically polished by diamond polishing pastes with the diameter of 2.5 mu m and the diameter of 1.0 mu m after being sequentially ground by metallographic abrasive paper of No. 240, No. 600, No. 1000, No. 2000 and No. 3000, and is dried for standby. As shown in FIG. 6, Mo0.5V0.5NbTiZr1.5The corrosion weight gain of the alloy after 30 days of corrosion in superheated steam at 400 ℃ and 10.3MPa is 26.11mg/dm2。
The embodiment result shows that the alloy has a simple single body-centered cubic structure, a simple organization structure, excellent mechanical property and excellent high-temperature steam corrosion resistance, and has the potential application possibility in the nuclear power high-temperature environment.
Claims (6)
1. Mo for nuclear power0.5V0.5NbTiZrxThe preparation method of the high-entropy alloy is characterized in that the component of the high-entropy alloy is Mo0.5V0.5NbTiZrxThe high-entropy alloy consists of five alloy elements of Mo, V, Nb, Ti and Zr with low thermal neutron absorption cross sections, wherein x is a molar ratio and = 0-2.0; according to the mol percentage, the content of Mo and V is respectively 10.00-16.67%, the content of Nb and Ti is respectively 20.00-33.33%, and the content of Zr is 0-40.0%;
mo for nuclear power0.5V0.5NbTiZrxThe specific preparation process of the high-entropy alloy is as follows:
the method comprises the following steps: weighing the raw materials according to the nominal chemical composition of the alloy in proportion;
step two: putting raw materials into a copper crucible of a vacuum arc furnace according to the sequence of low melting point below and high melting point above; vacuum degree of vacuum arc furnace at 1 × 10-4 ~ 5 × 10-4After Pa, filling high-purity argon, arc striking and smelting, cooling after the alloy is fully melted, and smelting for more than 4 times after the solidified alloy ingot is turned over to ensure that the components are uniform;
step three: carrying out hot isostatic pressing treatment on an alloy ingot prepared by smelting in a vacuum arc furnace;
step four: and after hot isostatic pressing treatment, carrying out homogenization heat treatment annealing at the temperature of 1200 +/-50 ℃ for 10-30 hours.
2. Mo for nuclear power in accordance with claim 10.5V0.5NbTiZrxA method for producing a high-entropy alloy, characterized in that x is any one of 0, 0.25, 0.5, 0.75, 1.0, 1.5 and 2.0.
3. Mo for nuclear power in accordance with claim 10.5V0.5NbTiZrxThe preparation method of the high-entropy alloy is characterized in that the high-entropy alloy has a single body-centered cubic structure.
4. Mo for nuclear power in accordance with claim 10.5V0.5NbTiZrxThe preparation method of the high-entropy alloy is characterized in that in the step one, raw materials are pretreated: removing oxide skin on the surface of Mo by adopting a mechanical method, and cleaning and drying the Mo; cleaning Nb and V with petroleum ether for 10-20 min, then ultrasonically cleaning with ethanol for 10-20 min, and then drying in a drying oven at the temperature of 50-100 ℃ for 1-3 h; and directly drying the Ti and the Zr in a drying oven at the temperature of 50-100 ℃ for 1-3 hours.
5. Mo for nuclear power in accordance with claim 10.5V0.5NbTiZrxThe preparation method of the high-entropy alloy is characterized by comprising the following stepsIn the first step, the raw material Mo is in a square rod shape, the raw material V is in a tree shape, the raw material Nb is in a sheet shape, the raw material Ti is sponge titanium, the raw material Zr is nuclear grade sponge zirconium, and the purity of the raw materials Mo, V, Nb, Ti and Zr is not lower than 99.5 wt.%.
6. Mo for nuclear power in accordance with claim 10.5V0.5NbTiZrxThe preparation method of the high-entropy alloy is characterized in that the prepared high-entropy alloy has a low thermal neutron absorption cross section: 2.29 to 3.69 barn; has excellent mechanical properties: the yield strength is higher than 1200 MPa, the compressive strength is higher than 1500MPa, and the strain is higher than 10 percent; high-temperature steam corrosion resistance: the corrosion weight gain after 30 days of corrosion in superheated steam at 400 ℃ and 10.3MPa is less than 50mg/dm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910673106.0A CN110331322B (en) | 2019-07-24 | 2019-07-24 | MoVNbTiZr for nuclear powerxHigh-entropy alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910673106.0A CN110331322B (en) | 2019-07-24 | 2019-07-24 | MoVNbTiZr for nuclear powerxHigh-entropy alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110331322A CN110331322A (en) | 2019-10-15 |
| CN110331322B true CN110331322B (en) | 2021-01-08 |
Family
ID=68147420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910673106.0A Active CN110331322B (en) | 2019-07-24 | 2019-07-24 | MoVNbTiZr for nuclear powerxHigh-entropy alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110331322B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113652593A (en) * | 2021-07-28 | 2021-11-16 | 中国科学院金属研究所 | MoxNbTayTiV high-entropy alloy and preparation method thereof |
| CN114774752B (en) * | 2022-03-25 | 2023-12-22 | 江苏理工学院 | High-strength high-toughness TiZrNbMoV refractory high-entropy alloy and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602872A (en) * | 2013-10-31 | 2014-02-26 | 北京科技大学 | TiZrNbVMo[x] high entropy alloy and preparation method thereof |
| CN107641751A (en) * | 2017-08-25 | 2018-01-30 | 中国科学院金属研究所 | A kind of MoNbCrVTi infusibilities high-entropy alloy and preparation method thereof |
| KR101884442B1 (en) * | 2017-02-10 | 2018-08-01 | 서울대학교산학협력단 | High entropy alloy overcoming strength-ductility trade-off |
| CN109402482A (en) * | 2018-12-10 | 2019-03-01 | 北京理工大学 | It is a kind of to have both high-intensitive and high-ductility lightweight high-entropy alloy and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101761009B1 (en) * | 2015-09-02 | 2017-07-24 | 한국과학기술원 | Hight-entropy multioelement alloy with single phase and process for preparing the same |
-
2019
- 2019-07-24 CN CN201910673106.0A patent/CN110331322B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602872A (en) * | 2013-10-31 | 2014-02-26 | 北京科技大学 | TiZrNbVMo[x] high entropy alloy and preparation method thereof |
| KR101884442B1 (en) * | 2017-02-10 | 2018-08-01 | 서울대학교산학협력단 | High entropy alloy overcoming strength-ductility trade-off |
| CN107641751A (en) * | 2017-08-25 | 2018-01-30 | 中国科学院金属研究所 | A kind of MoNbCrVTi infusibilities high-entropy alloy and preparation method thereof |
| CN109402482A (en) * | 2018-12-10 | 2019-03-01 | 北京理工大学 | It is a kind of to have both high-intensitive and high-ductility lightweight high-entropy alloy and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Phase composition and solid solution strengthening effect in TiZrNbMoV high-entropy alloys;Y.D. Wu et.al.;《Materials & Design》;20150619(第83期);651–660 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110331322A (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109402482B (en) | Light high-entropy alloy with high strength and high plasticity and preparation method thereof | |
| CN110358964B (en) | MoVNbTiCr for nuclear powerxHigh-entropy alloy and preparation method thereof | |
| CN107641751B (en) | A kind of MoNbCrVTi infusibility high-entropy alloy and preparation method thereof | |
| CN112981208B (en) | Light refractory high-temperature-resistant eutectic high-entropy alloy and preparation method thereof | |
| CN113789464B (en) | Ceramic phase reinforced refractory high-entropy alloy and preparation method thereof | |
| CN104498844B (en) | A kind of large scale TRIP amorphous composite material and preparation method thereof | |
| CN109023002B (en) | Silicon solid solution reinforced VNbMoTaSi high-entropy alloy and preparation method thereof | |
| CN114134385B (en) | Refractory medium-entropy alloy and preparation method thereof | |
| CN110331322B (en) | MoVNbTiZr for nuclear powerxHigh-entropy alloy and preparation method thereof | |
| CN113667875B (en) | MoNbTaTiVSix high-entropy alloy and preparation method thereof | |
| CN115198162B (en) | Entropy alloy in high-toughness heterogeneous multi-phase core-shell organization structure and preparation method thereof | |
| CN112962011B (en) | High-entropy alloy for corrosion-resistant nuclear power and preparation method thereof | |
| CN113621861B (en) | MoNbTaTiVCrxHigh-entropy alloy and preparation method thereof | |
| CN114318057B (en) | High-strength-toughness corrosion-resistant zirconium-cobalt binary alloy and preparation method thereof | |
| CN102230100B (en) | Method for preparing Ti-Nb-Zr-Sn alloy by using powder metallurgical process | |
| CN110923481A (en) | Amorphous film/high-entropy alloy composite material and preparation method thereof | |
| CN111676409B (en) | Preparation method of low-density low-cost Fe-Mn-Al-C intermediate entropy alloy | |
| CN111394665B (en) | TiCuZrPdFe amorphous composite material and preparation method thereof | |
| CN110016603B (en) | Ultra-high-strength and high-thermal-stability nanocrystalline ODS steel, and preparation method and application thereof | |
| CN107937840B (en) | A kind of titanium-aluminium alloy composite material and preparation method | |
| Li et al. | Microstructure and mechanical properties of Zr–Co–Al alloys prepared by rapid solidification | |
| CN110093546A (en) | A kind of AlFeMoNbZr core involucrum high entropy alloy material and preparation method thereof | |
| CN111411249B (en) | Preparation method of VNbMoTaW high-entropy alloy | |
| CN111004942A (en) | TiBw/Ti composite material with nano-network-like structure and preparation method thereof | |
| CN115386774B (en) | Refractory high-entropy alloy with high strength and high uniform elongation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |