CN118028680A - Refractory high-entropy alloy and preparation method thereof - Google Patents
Refractory high-entropy alloy and preparation method thereof Download PDFInfo
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- CN118028680A CN118028680A CN202410035765.2A CN202410035765A CN118028680A CN 118028680 A CN118028680 A CN 118028680A CN 202410035765 A CN202410035765 A CN 202410035765A CN 118028680 A CN118028680 A CN 118028680A
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- 239000000956 alloy Substances 0.000 title claims abstract description 70
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 24
- 238000003723 Smelting Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000012856 weighed raw material Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000006835 compression Effects 0.000 abstract 2
- 238000007906 compression Methods 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Abstract
The invention discloses a refractory high-entropy alloy and a preparation method thereof, wherein the chemical expression of the refractory high-entropy alloy is TiZrNbAl 0.2Ta0.1 (atomic mole percent at%). The low-density refractory high-entropy alloy TiZrNbAl 0.2Ta0.1 provided by the invention has low Al content, excellent strong plastic matching property, compression yield strength reaching 1001MPa, compression strain being more than 70%, tensile yield strength reaching 894MPa, and tensile strain being more than 13%, and has important application prospect in the field of high-temperature alloys.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a refractory high-entropy alloy and a preparation method thereof.
Background
The high-temperature alloy is a basic stone of an aero-engine and aerospace power system, and the strength level and stability of the high-temperature alloy directly determine the technical and warfare level of equipment of the high-temperature alloy. With the further development of the aerospace industry, the new generation of high thrust weight ratio/power weight ratio aero-engine hot end components and high Mach number aircraft key weight reduction materials are required to be lighter and higher in strength. At present, the development of titanium alloys, nickel-based high-temperature alloys and the like has been advanced, and the titanium alloys and the nickel-based high-temperature alloys are widely applied to the aerospace field, but have certain limitations. For example: the titanium alloy has lower density, can meet the low-density requirement of aerospace materials, but the use temperature is difficult to break through 600 ℃; although the traditional nickel-based, cobalt-based and iron-based high-temperature alloy has high-temperature strength and can meet the requirement of high-temperature performance, the density of the alloy is generally more than 8g/cm 3, and the requirement of low density cannot be met.
In recent years, the appearance of high-entropy alloy provides a new thought for the design of alloy components, and by selecting low-density alloy elements, a novel light-weight high Wen Gaoshang alloy with lighter weight and higher high-temperature performance than the traditional high-temperature alloy material can be prepared, so that the defects of titanium alloy, nickel-based high-temperature alloy and the like are overcome.
Therefore, research and development of a lighter high-entropy alloy with a working temperature of 650 ℃ or higher is urgently needed to meet the requirements of the alloy in the aerospace field.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a refractory high-entropy alloy and a preparation method thereof, so as to solve the problems of low working temperature and high density of the conventional high-entropy alloy.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect of the invention, there is provided a refractory high entropy alloy having a chemical formula TiZrNbAl 0.2Ta0.1.
In a second aspect of the present invention, there is provided a method for preparing the refractory high-entropy alloy described above, the method comprising the steps of:
calculating the weight of each element related to the required atomic number according to the required atomic number, and weighing raw materials;
And smelting the raw materials by adopting a vacuum arc smelting water-cooled copper crucible technology, and cooling to obtain the high-entropy alloy.
Preferably, the method adopts a vacuum arc melting water-cooled copper crucible technology to melt the raw materials, and the step of obtaining the high-entropy alloy after cooling comprises the following steps:
And (3) placing the weighed raw materials in a water-cooled copper crucible, adjusting the vacuum degree to be not less than 5 x 10 -3 Pa, filling argon to the air pressure to be 0.5Pa, increasing the current to 650A, repeatedly smelting, and cooling to obtain the refractory high-entropy alloy.
Preferably, the step of placing the weighed raw materials in a water-cooled copper crucible specifically comprises:
The raw materials are placed in a water-cooled copper crucible according to the melting point sequence, al materials are placed at the bottommost layer of the water-cooled copper crucible, ti and Zr materials are placed at the middle layer of the water-cooled copper crucible, and Nb and Ta materials are placed at the topmost layer of the water-cooled copper crucible.
Preferably, the purity of Ti in the raw material is 99.9wt%, the purity of Zr is 99.5wt%, the purity of Nb is 99.95wt%, the purity of Al is 99.996wt%, and the purity of Ta is 99.95wt%.
Preferably, the number of times of smelting is not less than 6.
Preferably, the time for smelting the raw materials is not less than 5min each time, and the alloy is turned over after being cooled.
The beneficial effects are that:
The invention discloses a refractory high-entropy alloy and a preparation method and application thereof, wherein a low-density metal element Ti, zr, nb, al is selected, a trace amount of Ta element is added, a vacuum arc melting water-cooled copper crucible technology is utilized to synthesize the low-density refractory high-entropy alloy TiZrNbAl 0.2Ta0.1 with a single-phase body-centered cubic solid solution structure, the low-density refractory high-entropy alloy has excellent strong plastic matching property, the compressive yield strength reaches 1001MPa, the compressive strain is more than 70%, the tensile yield strength reaches 894MPa, the tensile strain is more than 13%, and the low-density refractory high-entropy alloy has important application prospect in the field of high-temperature alloys.
Drawings
FIG. 1 is a schematic diagram of TiZrNbAl 0.2Ta0.1 prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of TiZrNbAl 0.2Ta0.1 prepared in example 1 of the present invention;
FIG. 3 is a compressive stress-strain curve of TiZrNbAl 0.2Ta0.1 prepared in example 1 of the present invention;
FIG. 4 is a plot of tensile true stress versus true strain for TiZrNbAl 0.2Ta0.1 prepared in example 1 of the present invention.
Detailed Description
The invention provides a refractory high-entropy alloy, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a refractory high-entropy alloy, and the chemical expression of the high-entropy alloy is TiZrNbAl 0.2Ta0.1.
The refractory high-entropy alloy provided by the embodiment of the invention has the advantages of light weight, high temperature resistance, high strength, good plasticity and the like of the Ti, zr and Nb elements in equal proportion, the added Al element can effectively reduce the density of the alloy and improve the strength and oxidation resistance of the alloy on the basis of the equal proportion TiZrNb, but the Al content is not too high, otherwise brittle phases are easy to separate out, the alloy becomes brittle, the plasticity is greatly reduced, the formability is reduced, ta has excellent plasticity, corrosion resistance and high melting point, and trace Ta element is added into the alloy to effectively improve the strength, specific strength, plasticity and thermal stability of the alloy, but the content of the Ta element is not too high, otherwise the mechanical property of the alloy is easy to deteriorate and the density of the alloy is too high.
In addition, in the refractory high-entropy alloy, the atomic radius difference of Ti, al, nb and Ta is small, but the atomic radius of Zr is relatively large, so that a good solid solution strengthening effect can be achieved, and the alloy has high strength and good plasticity.
The embodiment of the invention provides a preparation method of the refractory high-entropy alloy, which comprises the following steps:
calculating the weight of each element related to the required atomic number according to the required atomic number, and weighing raw materials;
And smelting the raw materials by adopting a vacuum arc smelting water-cooled copper crucible technology, and cooling to obtain the high-entropy alloy.
In some embodiments, the method adopts a vacuum arc melting water-cooled copper crucible technology to smelt the raw materials, and the step of obtaining the high-entropy alloy after cooling specifically comprises the following steps:
And (3) placing the weighed raw materials in a water-cooled copper crucible, adjusting the vacuum degree to be not less than 5 x 10 -3 Pa, filling argon to the air pressure to be 0.5Pa, increasing the current to 650A, repeatedly smelting, and cooling to obtain the refractory high-entropy alloy.
The high vacuum degree is used for preventing oxygen atom impurities from being doped in the smelting process, and argon is introduced because the type of arc smelting furnace utilizes argon to perform arc starting smelting and has the function of protective gas. The repeated smelting is to ensure that the components of the alloy ingot obtained by smelting are uniform.
In some embodiments, the step of placing the weighed raw materials into a water-cooled copper crucible specifically comprises:
The raw materials are placed in a water-cooled copper crucible according to the melting point sequence, al materials are placed at the bottommost layer of the water-cooled copper crucible, ti and Zr materials are placed at the middle layer of the water-cooled copper crucible, and Nb and Ta materials are placed at the topmost layer of the water-cooled copper crucible.
In some embodiments, the raw materials have a purity of 99.9wt% Ti, 99.5wt% Zr, 99.95wt% Nb, 99.996wt% Al, and 99.95wt% Ta.
In some embodiments, the number of times the smelting is not less than 6.
In some embodiments, the raw materials are melted for no less than 5 minutes each time, and are turned over after the alloy cools.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention, and are merely illustrative of the invention and in no way limiting of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A refractory high entropy alloy is prepared as shown in fig. 1, comprising the steps of:
Ti with the purity of 99.9wt percent, zr with the purity of 99.5wt percent, nb with the purity of 99.95wt percent, al with the purity of 99.996wt percent and Ta with the purity of 99.95wt percent are selected and proportioned according to an alloy expression. And sequentially placing the metal raw materials into a water-cooled copper crucible according to the melting point sequence, placing Al materials at the bottommost layer, placing Ti and Zr materials at the middle layer, placing Nb and Ta materials at the uppermost layer, vacuumizing an experiment chamber to 5 x 10 -3 Pa after the raw materials are placed, and introducing argon as protective gas until the air pressure in the chamber is 0.5Pa. After the protective gas is introduced, the Ti ingot placed in the other copper crucible is melted for at least one minute so as to absorb the residual oxygen in the cavity. After the waiting cavity is cooled, the raw materials are melted, during the melting process, the current is increased to 650A, the raw materials are gradually melted, and the raw materials are kept in a molten state for not less than 5 minutes by continuous heating. And after the ingot is cooled after the primary smelting is finished, turning over the ingot, repeating the steps for smelting, and repeatedly smelting for at least 6 times to finally smelt TiZrNbAl 0.2Ta0.1 low-density refractory high-entropy alloy with uniformly distributed components.
Comparative example 1
A TiZrNbAlTa 0.1 low-density refractory high-entropy alloy having a high aluminum concentration, which had a phase structure in which a brittle Al 3Zr5 intermetallic compound phase was precipitated in addition to the body-centered cubic solid solution phase due to an excessively high Al content, was melted in the same manner as in example 1; the compressive yield strength was 1185MPa, the compressive strain was-6%, and the compressive plasticity was greatly deteriorated compared with example 1; the tensile plasticity is almost 0, and measurement cannot be performed; the moldability is extremely poor.
Performance test
XRD detection was carried out on TiZrNbAl 0.2Ta0.1 prepared in example 1, as shown in FIG. 2, tiZrNbAl 0.2Ta0.1 had a single-phase body-centered cubic solid solution structure, and no precipitated phase was observed, exhibiting a multicomponent high entropy effect. As shown in FIG. 3, tiZrNbAl 0.2Ta0.1 has excellent strong plastic matching, the compressive yield strength reaches 1001MPa, and the compressive strain is more than 70%. As shown in FIG. 4, tiZrNbAl 0.2Ta0.1 has a tensile yield strength of 894MPa and a tensile strain of > 13% and is excellent in moldability.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (7)
1.A refractory high-entropy alloy, wherein the refractory high-entropy alloy has a chemical expression of TiZrNbAl 0.2Ta0.1.
2. A method of preparing a refractory high-entropy alloy according to claim 1, comprising the steps of:
calculating the weight of each element related to the required atomic number according to the required atomic number, and weighing raw materials;
And smelting the raw materials by adopting a vacuum arc smelting water-cooled copper crucible technology, and cooling to obtain the high-entropy alloy.
3. The method for preparing the refractory high-entropy alloy according to claim 2, wherein the step of melting the raw materials by using a vacuum arc melting water-cooled copper crucible technique and cooling the raw materials to obtain the high-entropy alloy comprises the following steps:
And (3) placing the weighed raw materials in a water-cooled copper crucible, adjusting the vacuum degree to be not less than 5 x 10 -3 Pa, filling argon to the air pressure to be 0.5Pa, increasing the current to 650A, repeatedly smelting, and cooling to obtain the refractory high-entropy alloy.
4. A method of producing a refractory high-entropy alloy according to claim 3, characterized in that the step of placing the weighed raw materials in a water-cooled copper crucible comprises in particular:
The raw materials are placed in a water-cooled copper crucible according to the melting point sequence, al materials are placed at the bottommost layer of the water-cooled copper crucible, ti and Zr materials are placed at the middle layer of the water-cooled copper crucible, and Nb and Ta materials are placed at the topmost layer of the water-cooled copper crucible.
5. The method for producing a refractory high-entropy alloy according to claim 2, wherein the purity of Ti, zr, and Ta in the raw materials is 99.9wt%, 99.5wt%, 99.95wt%, 99.996wt% respectively.
6. The method for producing a refractory high-entropy alloy according to claim 2, wherein the number of times of smelting is not less than 6.
7. The method for producing a refractory high-entropy alloy according to claim 2, wherein the time for melting the raw material each time is not less than 5 minutes, and the alloy is turned over after cooling.
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