CN114752794A - High-entropy alloy and preparation method and application thereof - Google Patents
High-entropy alloy and preparation method and application thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 167
- 239000000956 alloy Substances 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 56
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 50
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 53
- 238000003723 Smelting Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 4
- 239000007769 metal material Substances 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 description 49
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000006835 compression Effects 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 238000012669 compression test Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000002923 metal particle Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910000905 alloy phase Inorganic materials 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910008652 TiZrHf Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910007880 ZrAl Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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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
- 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
Abstract
The invention provides a high-entropy alloy and a preparation method and application thereof, and relates to the technical field of preparation of special metal materials. The high-entropy alloy consists of Zr, Al, Ti and Hf; wherein the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.1-0.5: 1.0 to 2.0: 0.5 to 1.0. Through the synergistic compounding of the components, the high-entropy alloy has excellent comprehensive mechanical properties, and through detection, the high-entropy alloy has ultrahigh strength and good plasticity. The high-entropy alloy can be widely applied to the preparation process of high-strength structural materials.
Description
Technical Field
The invention relates to the technical field of preparation of special metal materials, in particular to a high-entropy alloy and a preparation method and application thereof.
Background
The high-entropy alloy has a brand-new alloy design concept, any element in the alloy can not be used as a leading element of an alloy system, the characteristic of the whole alloy is the result of the combined action of multiple elements, a single-phase solid solution structure is easy to form, and in addition, the high-entropy alloy has four effects due to the unique design thought: namely the high entropy effect, the lattice distortion effect, the delayed diffusion effect and the "cocktail" effect. Therefore, the high-entropy alloy has better research prospect, and greatly expands the research limit in the field of materials.
Studies have shown that it is difficult to achieve an optimal combination of strength and plasticity for high entropy alloys, such as: the reported TiZrHf serving as a newly designed high-entropy alloy with a single-phase HCP structure has the yield strength of only 773MPa, the compressive strength of 1184MPa and the fracture strain of 17%, is difficult to meet the use requirement under some complex working conditions, and greatly limits the use of the high-entropy alloy as an ultrahigh-strength structural member.
Therefore, it is necessary and urgent to develop a high-entropy alloy with excellent comprehensive mechanical properties, ultra-high strength and good plasticity.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a high-entropy alloy which has excellent comprehensive mechanical properties, ultrahigh strength and good plasticity.
The second purpose of the invention is to provide a preparation method of the high-entropy alloy, which has the advantages of simple process operation and easy application.
The third purpose of the invention is to provide application of the high-entropy alloy, and the high-entropy alloy can be widely applied to the preparation process of high-strength structural materials.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a high-entropy alloy which is composed of Zr, Al, Ti and Hf;
the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.1-0.5: 1.0-2.0: 0.5 to 1.0.
Further, the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.25-0.5: 1.0-1.5: 0.5 to 1.0;
preferably, the atomic ratio of Zr, Al, Ti and Hf in the high entropy alloy is 1.0: 0.5: 1.0: 1.0.
further, the phase structure of the high-entropy alloy is an HCP phase.
Furthermore, the yield strength of the high-entropy alloy is 1129 MPa-1597 MPa, the compressive strength is 1854 MPa-2170 MPa, and the fracture strain is 16.7% -27.3%.
The invention provides a preparation method of the high-entropy alloy, which comprises the following steps:
weighing Zr, Al, Ti and Hf raw materials, mixing, and then smelting under a vacuum condition to obtain the high-entropy alloy.
Furthermore, the purities of the Zr, Al, Ti and Hf raw materials are all more than or equal to 99 wt%.
Further, the method for smelting under the vacuum condition is an energy beam smelting method or an induction smelting method.
Further, the preparation method also comprises the step of respectively pretreating raw materials of Zr, Al, Ti and Hf before mixing.
Further, the step of pretreating each of the Zr, Al, Ti and Hf raw materials comprises:
firstly, removing surface oxide layers of Zr, Al, Ti and Hf raw materials respectively, and then sequentially cleaning and drying to finish pretreatment.
The invention provides application of the high-entropy alloy in preparation of a high-strength structural material.
Compared with the prior art, the invention has the beneficial effects that:
the high-entropy alloy provided by the invention consists of Zr, Al, Ti and Hf; wherein the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.1-0.5: 1.0-2.0: 0.5 to 1.0. Through the synergistic compounding of the components, the high-entropy alloy has excellent comprehensive mechanical properties, and through detection, the high-entropy alloy has ultrahigh strength and good plasticity.
According to the preparation method of the high-entropy alloy, the raw materials of Zr, Al, Ti and Hf are weighed and mixed at first, and then smelting is carried out under the vacuum condition to obtain the high-entropy alloy.
The high-entropy alloy provided by the invention can be widely applied to the preparation process of high-strength structural materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an X-ray diffraction pattern of a high-entropy alloy prepared in examples 1 to 5 of the present application;
FIG. 2 is a stress-strain curve of room temperature quasi-static compression engineering of the high-entropy alloy prepared in examples 1 to 5 of the present application.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the invention, a high entropy alloy consists of Zr, Al, Ti and Hf;
the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.1-0.5: 1.0-2.0: 0.5 to 1.0.
The high-entropy alloy provided by the invention consists of Zr, Al, Ti and Hf; wherein the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.1-0.5: 1.0-2.0: 0.5 to 1.0. Through the synergistic compounding of the components, the high-entropy alloy has excellent comprehensive mechanical properties, and through detection, the high-entropy alloy has ultrahigh strength and good plasticity.
The invention introduces Al element with obvious solid solution strengthening effect and effectively improves the comprehensive mechanical property of the high-entropy alloy by changing the proportion of each component element aiming at the problem that the existing TiZrHf high-entropy alloy has poor strength and plastic fit at room temperature.
In a preferred embodiment of the present invention, the atomic ratio of Zr, Al, Ti and Hf in the high entropy alloy is 1.0: 0.25-0.5: 1.0 to 1.5: 0.5 to 1.0;
preferably, the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.5: 1.0: 1.0.
in a preferred embodiment of the invention, the phase structure of the high entropy alloy is a HCP phase.
In a preferred embodiment, the phase structure of the high-entropy alloy is an HCP phase, and the microstructure is uniform.
In a preferred embodiment of the invention, the high-entropy alloy has a yield strength of 1129 MPa-1597 MPa, a compressive strength of 1854 MPa-2170 MPa and a fracture strain of 16.7% -27.3%.
As a preferable embodiment, the yield strength of the high-entropy alloy is 1129 MPa-1597 MPa, the compressive strength is 1854 MPa-2170 MPa, and the fracture strain is 16.7% -27.3%.
According to one aspect of the invention, a preparation method of the high-entropy alloy comprises the following steps:
weighing Zr, Al, Ti and Hf raw materials, mixing, and then smelting under a vacuum condition to obtain the high-entropy alloy.
According to the preparation method of the high-entropy alloy, raw materials of Zr, Al, Ti and Hf are weighed and mixed at first, and then smelting is carried out under the vacuum condition to obtain the high-entropy alloy.
In a preferred embodiment of the present invention, the purities of the Zr, Al, Ti and Hf raw materials are all 99 wt% or more.
In a preferred embodiment of the present invention, the melting method under vacuum is an energy beam melting method or an induction melting method.
As a preferred embodiment, the ZrAlxTiyHfz high-entropy alloy is obtained by adopting an energy beam melting technology or an induction melting technology under the melting vacuum condition, and has the advantages of low technical difficulty and low cost.
In a preferred embodiment of the present invention, the manufacturing method further comprises the step of pretreating each of the Zr, Al, Ti and Hf raw materials before mixing.
As a preferred embodiment, the pretreatment is: before mixing, oxide layers on the surfaces of Zr, Al, Ti and Hf raw materials are removed, and then the Zr, Al, Ti and Hf raw materials are cleaned and dried.
Preferably, the step of pretreating each of the Zr, Al, Ti and Hf raw materials comprises:
firstly, removing surface oxide layers of Zr, Al, Ti and Hf raw materials respectively, and then sequentially cleaning and drying to finish pretreatment.
According to one aspect of the invention, the high-entropy alloy is applied to preparing a high-strength structural material.
The high-entropy alloy provided by the invention can be widely applied to the preparation process of high-strength structural materials.
The technical solution of the present invention will be further described with reference to the following examples.
Example 1
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of three elements of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: the molar ratio of Ti to Hf is 1.0: 0.1: 1.5: 1.0, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (zr) -26.5%, wt (al) -0.78%, wt (ti) -20.86%, wt (hf) -51.85%, respectively, of the mass of each element in the total mass of the alloy, and each element is dosed in the total mass of the prepared alloy.
(2) And (3) pretreatment: removing surface oxide skin of raw material metals Zr, Al, Ti and Hf by using a mechanical and chemical combined method, cleaning and drying for later use, namely removing the surface oxide skin of the raw material metals Zr, Al, Ti and Hf by using sand paper for polishing, ultrasonically cleaning by using an organic solution, and then drying for later use.
The mechanical and chemical combined method comprises the following steps: and (3) polishing with sand paper to remove surface oxide skin, cleaning with an acetone solution, ultrasonically oscillating for 5 minutes, cleaning with alcohol, and drying for later use.
(3) Placing all metal raw materials in a water-cooled copper crucible from low melting point to high melting point; then closing the furnace door, and vacuumizing the furnace to 10 ℃ by using a vacuum pump and a molecular pump-2Pa, then high-purity argon gas is filled as protective gas to 0.5 Pa.
(4) And arc striking smelting is carried out under the atmosphere of high-purity argon, and before formal smelting, high-purity titanium is pre-smelted in the furnace to reduce the residual oxygen in the furnace in order to reduce the oxidation of the alloy as much as possible. And (3) in formal smelting, selecting proper current intensity, starting magnetic stirring, shaking the tungsten pole rod in a small amplitude, controlling the single smelting time to be more than 2 minutes, and repeatedly smelting the alloy until the alloy is uniform to obtain the high-entropy alloy.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the high-entropy alloy obtained in examples 1 to 5 of the present application;
as shown in FIG. 1, ZrAl shown in FIG. 10.1Ti1.5The Hf curve is the XRD pattern of the high-entropy alloy in example 1, and the alloy phase structure is an HCP phase; according to GB/T7314-2017 metal material chamberThe related requirements of the warm compression test method are that a room temperature compression test is implemented, and the compression loading rate of the test is 0.36 mm/min;
FIG. 2 is a stress-strain curve of room temperature quasi-static compression engineering of the high-entropy alloy prepared in examples 1 to 5 of the present application;
as shown in FIG. 2, the curve 1 in FIG. 2 is the room temperature compressive engineering stress strain curve of the high entropy alloy of ZrAl0.1Ti1.5Hf embodiment, the yield strength of the alloy is 1129MPa, the compressive strength is 1950MPa, and the fracture strain is 27.3%.
Example 2
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 1.0: 0.25: 1: 1.0, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (zr) -28.13%, wt (al) -2.08%, wt (ti) -14.76%, wt (hf) -55.03%, respectively, of the mass of each element in the total mass of the alloy, and each element is dosed in the total mass of the prepared alloy.
(2) And (3) pretreatment: removing surface oxide skin of raw material metals Zr, Al, Ti and Hf by using a mechanical and chemical combined method, cleaning and drying for later use.
The mechanical and chemical combined method comprises the following steps: and (3) polishing by using sand paper to remove surface oxide skin, cleaning by using an acetone solution, ultrasonically oscillating for 5 minutes, and cleaning and drying by using alcohol for later use.
(3) Putting all metal raw materials into a water-cooled copper crucible from low melting point to high melting point, then closing a furnace door, and vacuumizing the furnace to 10 ℃ by using a vacuum pump and a molecular pump-2Pa, then high-purity argon gas is filled as protective gas to 0.5 Pa.
(4) And arc striking smelting is carried out under the atmosphere of high-purity argon, and before formal smelting, high-purity titanium is pre-smelted in the furnace to reduce the residual oxygen in the furnace in order to reduce the oxidation of the alloy as much as possible. And (3) in formal smelting, selecting proper current intensity, starting magnetic stirring, shaking the tungsten pole rod in a small amplitude, controlling the single smelting time to be more than 2 minutes, and repeatedly smelting the alloy until the alloy is uniform to obtain the high-entropy alloy.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the high-entropy alloy obtained in examples 1 to 5 of the present application;
as shown in FIG. 1, the ZrAl0.25TiHf curve shown in FIG. 1 is the XRD pattern of the high-entropy alloy of example 2, and the alloy phase structure is the HCP phase; according to the relevant requirements of the GB/T7314-2017 metal material room temperature compression test method, a room temperature compression test is carried out, and the compression loading rate of the test is 0.36 mm/min;
FIG. 2 is a room temperature quasi-static compressive engineering stress-strain curve of the high entropy alloy prepared in examples 1-5 of the present application;
as shown in FIG. 2, the curve 2 in FIG. 2 is the room temperature compressive engineering stress-strain curve of the ZrAl0.25TiHf high entropy alloy of example, wherein the yield strength of the alloy is 1335MPa, the compressive strength is 2070MPa, and the fracture strain is 25.7%.
Example 3
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 1.0: 0.5: 1.0: 1.0, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (zr) -27.55%, wt (al) -4.07%, wt (ti) -14.46%, wt (hf) -53.91% respectively, by mass of each element based on the total mass of the alloy, and each element is dosed in the total mass of the alloy.
(2) And (3) pretreatment: removing the oxide skin on the surface of the raw material metal by a mechanical and chemical combined method, cleaning and drying for later use.
The mechanical and chemical combined method comprises the following steps: and (3) polishing with sand paper to remove surface oxide skin, cleaning with an acetone solution, ultrasonically oscillating for 5 minutes, cleaning with alcohol, and drying for later use.
(3) Melting all the metal raw materialsThe dots are placed in a water-cooled copper crucible from low to high; then closing the furnace door, and vacuumizing the furnace to 10 ℃ by using a vacuum pump and a molecular pump-2Pa, then filling high-purity argon as protective gas to 0.5 Pa.
(4) And arc striking smelting is carried out under the atmosphere of high-purity argon, and before formal smelting, high-purity titanium is pre-smelted in the furnace to reduce the residual oxygen in the furnace in order to reduce the oxidation of the alloy as much as possible. And (3) in formal smelting, selecting proper current intensity, starting magnetic stirring, shaking the tungsten pole rod in a small amplitude, controlling the single smelting time to be more than 2 minutes, and repeatedly smelting the alloy until the alloy is uniform.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the high-entropy alloy prepared in examples 1-5 of the present application;
as shown in FIG. 1, the ZrAl0.5TiHf curve in FIG. 1 is the XRD pattern of the three-high entropy alloy of the embodiment, and the alloy phase structure is the HCP phase; according to the relevant requirements of the GB/T7314-2017 metal material room temperature compression test method, a room temperature compression test is carried out, and the compression loading rate of the test is 0.36 mm/min;
FIG. 2 is a stress-strain curve of room temperature quasi-static compression engineering of the high-entropy alloy prepared in examples 1 to 5 of the present application;
as shown in FIG. 2, the curve 3 in FIG. 2 is the room temperature compressive engineering stress strain curve of the three ZrAl0.5TiHf high entropy alloy of the embodiment, the yield strength of the alloy is 1540MPa, the compressive strength is 2170MPa, and the fracture strain is 24.4%.
Example 4
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 1.0: 0.5: 2: 0.5, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (zr) ═ 31.49%, wt (al) ═ 4.66%, wt (ti) ═ 33.05%, wt (hf) ═ 30.81%, respectively, of the mass of each element in the total mass of the alloy, and each element is dosed in the total mass of the alloy.
(2) And (3) pretreatment: removing surface oxide skin of raw material metals Zr, Al, Ti and Hf by using a mechanical and chemical combined method, cleaning and drying for later use.
The mechanical and chemical combined method comprises the following steps: and (3) polishing with sand paper to remove surface oxide skin, cleaning with an acetone solution, ultrasonically oscillating for 5 minutes, cleaning with alcohol, and drying for later use.
(3) Placing all metal raw materials in a water-cooled copper crucible from low melting point to high melting point; then closing the furnace door, vacuumizing the furnace to 10-2Pa by using a vacuum pump and a molecular pump, and then filling high-purity argon as protective gas to 0.5 Pa.
(4) And arc striking smelting is carried out under the atmosphere of high-purity argon, and before formal smelting, high-purity titanium is pre-smelted in the furnace to reduce the residual oxygen in the furnace in order to reduce the oxidation of the alloy as much as possible. And (3) in formal smelting, selecting proper current intensity, starting magnetic stirring, shaking the tungsten pole rod in a small amplitude, controlling the single smelting time to be more than 2 minutes, and repeatedly smelting the alloy until the alloy is uniform.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the high-entropy alloy prepared in examples 1-5 of the present application;
as shown in fig. 1, the zral0.5ti2hf0.5 curve in fig. 1 is the XRD spectrum of the four-high entropy alloy of the example, and it is seen that the alloy phase structure is HCP phase; according to the relevant requirements of the GB/T7314-2017 metal material room temperature compression test method, a room temperature compression test is carried out, and the compression loading rate of the test is 0.36 mm/min.
FIG. 2 is a stress-strain curve of room temperature quasi-static compression engineering of the high-entropy alloy prepared in examples 1 to 5 of the present application;
as shown in FIG. 2, the curve 4 in FIG. 2 is the room temperature compressive engineering stress strain curve of the four ZrAl0.5Ti2Hf0.5 high entropy alloy of the example, the yield strength of the alloy is 1597MPa, the compressive strength is 1854MPa, and the fracture strain is 16.7%.
Example 5
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 1.0: 0.5: 2: 1.0, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (zr) -24.07%, wt (al) -3.56%, wt (ti) -25.27%, wt (hf) -47.1% by mass of each element, respectively, based on the total mass of the alloy, and each element is dosed in the total mass of the alloy.
(2) And (3) pretreatment: removing surface oxide skin of raw material metals Zr, Al, Ti and Hf by using a mechanical and chemical combined method, cleaning and drying for later use.
The mechanical and chemical combined method comprises the following steps: and (3) polishing by using sand paper to remove surface oxide skin, cleaning by using an acetone solution, ultrasonically oscillating for 5 minutes, and cleaning and drying by using alcohol for later use.
(3) Placing all metal raw materials in a water-cooled copper crucible from low melting point to high melting point; then closing the furnace door, vacuumizing the furnace to 10-2Pa by using a vacuum pump and a molecular pump, and then filling high-purity argon gas serving as protective gas to 0.5 Pa.
(4) And arc striking smelting is carried out under the atmosphere of high-purity argon, and before formal smelting, high-purity titanium is pre-smelted in the furnace to reduce the residual oxygen in the furnace in order to reduce the oxidation of the alloy as much as possible. And (3) during formal smelting, selecting proper current intensity, starting magnetic stirring, shaking the tungsten electrode rod in a small amplitude, controlling the single smelting time to be more than 2 minutes, and repeatedly smelting the alloy until the alloy is uniform.
FIG. 1 is an X-ray diffraction pattern (XRD pattern) of the high-entropy alloy prepared in examples 1-5 of the present application;
as shown in FIG. 1, the ZrAl0.5Ti2Hf curve in FIG. 1 is the XRD pattern of the five-high-entropy alloy of the example, and the alloy phase structure is an HCP phase; according to the relevant requirements of the GB/T7314-2017 metal material room temperature compression test method, a room temperature compression test is carried out, and the compression loading rate of the test is 0.36 mm/min;
FIG. 2 is a stress-strain curve of room temperature quasi-static compression engineering of the high-entropy alloy prepared in examples 1 to 5 of the present application;
as shown in FIG. 2, the curve 5 in FIG. 2 is the room temperature compressive stress strain curve of the high entropy alloy of example WZrAl0.5Ti2Hf, the yield strength of the alloy is 1558MPa, the compressive strength is 1938MPa, and the fracture strain is 19.1%.
Comparative example 1
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 1.0: 0.75: 0.5: 1.5, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of the mass of each element in the total mass of the alloy, namely wt (zr) -22.63%, wt (al) -5%, wt (ti) -5.93% and wt (hf) -66.44%, respectively, and each element is proportioned according to the total mass of the prepared alloy.
(2) Examples 5 were repeated as in (1) to (4).
Comparative example 2
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 0.5: 1: 1.5: according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (Zr) -14.13%, wt (Al) -8.36%, wt (Ti) -22.24% and wt (Hf) -55.28% of the total mass of the alloy, and the elements are mixed according to the total mass of the prepared alloy.
(2) Examples (4) to (5) are the same as examples.
Example 6
A preparation method of a high-entropy alloy comprises the following steps:
(1) weighing the raw materials: metal particles of Zr, Al, Ti and Hf are selected as raw materials, and the purity of all the metal raw materials is higher than 99.0 wt.%.
Zr of the alloy: al: ti: the mole ratio of Hf is 1.0: 0.5: 2: 1.0, according to the naming characteristics of the high-entropy alloy, the atomic molar ratio of each element is converted into the percentages of wt (zr) -24.07%, wt (al) -3.56%, wt (ti) -25.27%, wt (hf) -47.1% by mass of each element, respectively, based on the total mass of the alloy, and each element is dosed in the total mass of the alloy.
(2) Placing all metal raw materials into a water-cooled copper crucible from low melting point to high melting point; then closing the furnace door, vacuumizing the furnace to 10-2Pa by using a vacuum pump and a molecular pump, and then filling high-purity argon as protective gas to 0.5 Pa.
(3) And arc striking smelting is carried out under the atmosphere of high-purity argon, and before formal smelting, high-purity titanium is pre-smelted in the furnace to reduce the residual oxygen in the furnace in order to reduce the oxidation of the alloy as much as possible. And (3) during formal smelting, selecting proper current intensity, starting magnetic stirring, shaking the tungsten electrode rod in a small amplitude, controlling the single smelting time to be more than 2 minutes, and repeatedly smelting the alloy until the alloy is uniform.
This example is the same as example 5 except that it does not include a "pretreatment" step.
In summary, the detection data of the yield strength, the compressive strength and the fracture strain of the high-entropy alloy prepared in the above examples 1 to 6 and comparative examples 1 and 2 are as follows:
according to the invention, the high-entropy alloy has excellent comprehensive mechanical properties through the synergistic compounding of the Zr, Al, Ti and Hf components, and the high-entropy alloy has ultrahigh strength and good plasticity through detection.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A high entropy alloy, characterized in that it consists of Zr, Al, Ti and Hf;
the atomic ratio of Zr, Al, Ti and Hf in the high-entropy alloy is 1.0: 0.1-0.5: 1.0-2.0: 0.5 to 1.0.
2. A high entropy alloy as claimed in claim 1, wherein the atomic ratio of Zr, Al, Ti and Hf in the high entropy alloy is 1.0: 0.25-0.5: 1.0-1.5: 0.5 to 1.0;
preferably, the atomic ratio of Zr, Al, Ti and Hf in the high entropy alloy is 1.0: 0.5: 1.0: 1.0.
3. a high entropy alloy according to claim 1, wherein the phase structure of the high entropy alloy is HCP phase.
4. A high entropy alloy as claimed in claim 1, wherein the high entropy alloy has a yield strength of 1129 MPa-1597 MPa, a compressive strength of 1854 MPa-2170 MPa, and a strain at break of 16.7-27.3%.
5. A method for preparing a high entropy alloy as claimed in any one of claims 1-4, the method includes the following steps:
weighing Zr, Al, Ti and Hf raw materials, mixing, and then smelting under a vacuum condition to obtain the high-entropy alloy.
6. A method for preparing a high-entropy alloy according to claim 5, wherein the purities of the Zr, Al, Ti and Hf raw materials are all equal to or greater than 99 wt%.
7. A method of producing a high entropy alloy as claimed in claim 5, wherein the melting under vacuum is an energy beam melting method or an induction melting method.
8. A method of producing a high entropy alloy as claimed in claim 5, further comprising a step of pretreating each of the raw materials of Zr, Al, Ti and Hf before mixing.
9. A method of producing a high entropy alloy as claimed in claim 8, wherein the step of pre-treating comprises:
firstly, removing surface oxide layers of Zr, Al, Ti and Hf raw materials respectively, and then sequentially cleaning and drying to finish pretreatment.
10. Use of the high-entropy alloy of any one of claims 1 to 4 in the preparation of a high-strength structural material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188876A (en) * | 1993-12-28 | 1995-07-25 | Takeshi Masumoto | Amorphous alloy for biological use |
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| CN107419154A (en) * | 2017-07-24 | 2017-12-01 | 北京科技大学 | One kind has hyperelastic TiZrHfNbAl high-entropy alloys and preparation method thereof |
| CN108359877A (en) * | 2018-04-24 | 2018-08-03 | 南昌大学 | A kind of high-ductility AlCoCuFeNi1.5High-entropy alloy and preparation method thereof |
| CN112111685A (en) * | 2020-09-21 | 2020-12-22 | 西北工业大学 | Wear-resistant refractory high-entropy alloy and preparation method thereof |
| US20210301375A1 (en) * | 2020-03-27 | 2021-09-30 | Seoul National University R&Db Foundation | Bcc dual phase refractory superalloy with high phase stability and manufacturing method therefore |
-
2022
- 2022-05-23 CN CN202210562599.2A patent/CN114752794A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07188876A (en) * | 1993-12-28 | 1995-07-25 | Takeshi Masumoto | Amorphous alloy for biological use |
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| CN107419154A (en) * | 2017-07-24 | 2017-12-01 | 北京科技大学 | One kind has hyperelastic TiZrHfNbAl high-entropy alloys and preparation method thereof |
| CN108359877A (en) * | 2018-04-24 | 2018-08-03 | 南昌大学 | A kind of high-ductility AlCoCuFeNi1.5High-entropy alloy and preparation method thereof |
| US20210301375A1 (en) * | 2020-03-27 | 2021-09-30 | Seoul National University R&Db Foundation | Bcc dual phase refractory superalloy with high phase stability and manufacturing method therefore |
| CN112111685A (en) * | 2020-09-21 | 2020-12-22 | 西北工业大学 | Wear-resistant refractory high-entropy alloy and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| PRASHANT SINGH等: "Vacancy-mediated complex phase selection in high entropy alloys", 《ACTA MATERIALIA》 * |
| 刘泽等: "新型多元高熵合金的研究与进展", 《大众科技》 * |
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