CN114540694B - High-entropy alloy and preparation method thereof - Google Patents
High-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The application provides a high-entropy alloy and a preparation method thereof, belonging to the technical field of metal materials. The component of the high-entropy alloy is Nb a V b Ta c M d B e Wherein M is any one or more of Ti, mo, zr, cr, al and W, a, b, c, d and e respectively represent the mole percentage of the corresponding elements, a is more than or equal to 5 and less than or equal to 35,5 and less than or equal to b 35,5 and less than or equal to c is more than or equal to 35,0 and less than or equal to d is more than or equal to 35,5 and less than or equal to e is more than or equal to 25, and a +, b +, c +, d +, e =, and 100. The refractory metal in the high-entropy alloy of the application is easy to form (V, nb, ta, M) with B 3 B 2 The crystal structure of the ordered boride phase belongs to a tetragonal system, and the ordered boride phase and a BCC phase formed by refractory elements easily form a regular lamellar eutectic structure, so that the integral radiation resistance of the high-entropy alloy material is improved. And the high-entropy alloy shows excellent high-temperature softening resistance and can meet the requirement on the mechanical property of the alloy under the strong irradiation service condition.
Description
Technical Field
The application relates to the technical field of metal materials, in particular to a high-entropy alloy and a preparation method thereof.
Background
The radiation-resistant metal structure material is a key material applied to the nuclear power device of the advanced spacecraft. The development of the advanced spacecraft nuclear power device requires that the structural material of the nuclear power device has excellent radiation resistance (mainly helium brittleness and swelling resistance) and excellent high-temperature mechanical property, and the development of novel radiation-resistant alloy has great significance.
The high-entropy alloy has no specific solvent or solute because the contents of a plurality of main components are similar, and can be regarded as mutually high-concentration solutes. The radius difference exists between the atoms of any one component and the atoms of all other components, so that the degree of lattice distortion of the high-entropy alloy solid solution is large, the activation energy of atom/ion diffusion is greatly improved, and the atom/ion diffusion is relatively slow. The high-entropy alloy has high configuration entropy, serious lattice distortion effect, delayed diffusion and performance cocktail effect, is expected to improve the anti-irradiation performance of the alloy, and provides greater freedom for the research and development of anti-irradiation structural materials, the component design and the phase structure regulation.
Most of the existing high-temperature resistant refractory high-entropy alloys are single-phase solid solution alloys with a body-centered cubic (BCC) structure. Research on the high-temperature-resistant refractory high-entropy alloy of the type discovers that the high-temperature strength of the single-phase solid solution alloy is increased along with the increase of the melting point of the alloy. However, the ensuing large increase in alloy density greatly limits the applications of the alloy. And the content of high-melting-point heavy elements in the low-density refractory high-entropy alloy is not high enough, so that the high-temperature performance of the low-density refractory high-entropy alloy is poor. Meanwhile, the single matrix structure in the refractory high-entropy alloy with the single-phase body-centered cubic structure cannot inhibit the formation and growth of helium bubbles, so that the radiation resistance (particularly the helium brittleness resistance and the helium swelling resistance) of the alloy is insufficient.
Disclosure of Invention
The application provides a high-entropy alloy and a preparation method thereof, which have excellent radiation resistance.
The embodiment of the application is realized as follows:
in a first aspect, the present examples provide a high entropy alloy having a composition of Nb a V b Ta c M d B e Wherein M is any one or more of Ti, mo, zr, cr, al and W, a, b, c, d and e respectively represent the mole percentage of the corresponding elements, a is more than or equal to 5 and less than or equal to 35,5 and less than or equal to b 35,5 and less than or equal to c is more than or equal to 35,0 and less than or equal to d is more than or equal to 35,5 and less than or equal to e is more than or equal to 25, and a +, b +, c +, d +, e =, and 100.
In the technical scheme, the refractory metals V, nb, ta and M in the high-entropy alloy are easy to form (V, nb, ta and M) with B 3 B 2 An ordered phase of a boride,the crystal structure of the phase belongs to a tetragonal system, and the phase is easy to form a regular lamellar eutectic structure with a BCC phase formed by refractory elements V, nb, ta and M, so that the integral anti-irradiation performance of the high-entropy alloy material is improved. The high-entropy alloy has a high melting point, shows excellent high-temperature softening resistance and can meet the requirements on the mechanical properties of the alloy under the condition of strong irradiation service.
Meanwhile, compared with precipitation strengthening type refractory high-entropy alloy, the ordered boride phase content is high, the alloy has excellent softening resistance, structure stability and irradiation resistance under a high-temperature condition, and two phases in the alloy can form an eutectic structure along with the change of the content of the second phase, so that the flowability and the casting performance of the alloy are facilitated, element segregation and micro-porosity are not easy to occur, and the alloy is easy to machine and form.
In a first possible example of the first aspect of the present application in combination with the first aspect, 25. Ltoreq. A.ltoreq.35, 25. Ltoreq. B.ltoreq. 35,5. Ltoreq. C.ltoreq. 20,0. Ltoreq. D.ltoreq.20.
In a second possible example of the first aspect of the present application in combination with the first aspect, 30 ≦ a ≦ 35, 30 ≦ b ≦ 35, 10 ≦ c ≦ 15,0 ≦ d ≦ 10, and 10 ≦ e ≦ 20 as described above.
Alternatively, a =35, b =35, c =15, d =0, e =15, and the high-entropy alloy is Nb 35 V 35 Ta 15 B 15 。
Alternatively, a =33, b =33, c =11, d =5, e =18, and the high-entropy alloy is Nb 33 V 33 Ta 11 M 5 B 18 。
Alternatively, M is Mo, and the high-entropy alloy is Nb 33 V 33 Ta 11 Mo 5 B 18 。
Alternatively, a =33, b =33, c =15, d =7, e =12, and the high-entropy alloy is Nb 33 V 33 Ta 15 M 7 B 12 。
Alternatively, M is Ti and the high-entropy alloy is Nb 33 V 33 Ta 15 Ti 7 B 12 。
In a second aspect, the present examples provide a method of making a high entropy alloy, comprising: smelting the raw materials in an oxygen-free environment to prepare the high-entropy alloy.
The raw materials comprise a niobium precursor, a vanadium precursor, a tantalum precursor and an M precursor, wherein the niobium precursor is a niobium simple substance and/or niobium diboride, the vanadium precursor is a vanadium simple substance and/or vanadium diboride, the tantalum precursor is a tantalum simple substance and/or tantalum diboride, the M precursor is an M simple substance and/or boronized M, and the molar ratio of Nb, V, ta, M and B elements in the raw materials is a: B: c: d: e.
In the technical scheme, the preparation method is simple and convenient, and the prepared high-entropy alloy has excellent radiation resistance.
In a first possible example of the second aspect of the present application in combination with the second aspect, the above-mentioned raw material further includes elemental boron.
In the above example, the B element may also be introduced into the high-entropy alloy in the form of a boron simple substance.
In combination with the second aspect, in a second possible example of the second aspect of the present application, c > e/2, and the raw materials include elemental niobium, elemental vanadium, elemental tantalum, elemental M, and tantalum diboride.
In the above example, when c > e/2, the B element is introduced into the high entropy alloy in the form of tantalum diboride.
In a third possible example of the second aspect of the present application, in combination with the second aspect, the melting is performed in a vacuum arc furnace, an arc is directed to the upper raw material, a current is set to 150 to 200A to slightly dissolve the upper raw material, then the current is adjusted to 350 to 420A to melt all the raw materials into a melt, and after the melt is solidified, the melting operation is repeated to melt the raw materials 8 times or more.
In the above example, it is very convenient to adopt vacuum arc furnace to smelt, and the repeated melting operation makes raw materials melt more than 8 times and can guarantee that the alloy melts evenly.
In a fourth possible example of the second aspect of the present application in combination with the second aspect, in the placing of the above-described raw materials, the placing is performed from high to low in accordance with the melting point of the metal element and/or compound, and the metal element or compound having the highest melting point is placed on the topmost layer, and the metal element or compound having the lowest melting point is placed on the bottommost layer.
With reference to the second aspect, in a fifth possible example of the second aspect of the present application, after the above melt is solidified, the solidified button ingot is turned over and then subjected to a melting operation.
In a sixth possible example of the second aspect of the present application in combination with the second aspect, it is observed whether or not the sparingly soluble particles are produced during melting, and the sparingly soluble particles are directly acted on by an electric arc until melting.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
FIG. 1 is an SEM image of a high entropy alloy produced in example 1 of the present application;
FIG. 2 is an SEM image of a high-entropy alloy obtained in example 2 of the present application;
FIG. 3 is an SEM image of a high-entropy alloy obtained in example 3 of the present application;
FIG. 4 is an X-ray diffraction pattern of the high-entropy alloy obtained in examples 1 to 3 of the present application;
FIG. 5 is a stress-strain diagram of the high-entropy alloy obtained in example 1 of the present application under room temperature compression engineering;
FIG. 6 is a 850 ℃ compressive engineering stress-strain plot of a high entropy alloy made according to example 1 of the present application;
FIG. 7 is a 1000 ℃ compressive engineering stress strain plot of the high entropy alloy made in example 1 of the present application;
FIG. 8 is a room temperature compressive stress-strain plot of a high entropy alloy made in example 2 of the present application;
FIG. 9 is a 850 ℃ compressive engineering stress-strain plot of a high entropy alloy made according to example 2 of the present application;
FIG. 10 is a 1000 ℃ compressive engineering stress-strain plot of a high entropy alloy made according to example 2 of the present application;
FIG. 11 is a stress-strain diagram of the room temperature compressive engineering of the high entropy alloy made by example 3 of the present application;
FIG. 12 is a graph of the compressive engineering stress-strain at 850 ℃ for a high entropy alloy made in example 3 of the present application;
FIG. 13 is a 1000 ℃ compressive engineering stress strain plot of a high entropy alloy made according to example 3 of the present application;
FIG. 14 is a graph showing distribution of helium bubbles in a substrate after irradiation of helium ions at 850 ℃ of the high-entropy alloy prepared in example 1 of the present application;
FIG. 15 is a graph showing the comparison of the size of helium bubbles in a matrix after irradiation of helium ions at 850 ℃ with other irradiation-resistant alloy matrices under the same irradiation conditions for the high-entropy alloy prepared in example 1 of the present application;
FIG. 16 is a comparison of the number density of helium bubbles in the matrix after irradiation of helium ions at 850 ℃ of the high-entropy alloy prepared in example 1 of the present application and the number density of helium bubbles in other irradiation-resistant alloy matrices under the same irradiation conditions.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The inventor finds that in order to solve or improve the problem that the radiation resistance (especially the helium brittleness and swelling resistance) of the high-temperature-resistant refractory high-entropy alloy with a single-phase body-centered cubic structure is insufficient, a second phase can be introduced on the basis of the refractory high-entropy alloy. However, in order to improve the radiation resistance of the refractory high-entropy alloy, the size and volume fraction of the second phase in the matrix need to be increased as much as possible, so that the interface between the second phase and the matrix is large and complex, thereby greatly improving the trapping sites of high-energy particles (mainly helium ions) in the matrix and further improving the radiation resistance of the refractory high-entropy alloy. And the large-size and high-content second phase can bring great adverse effects on the room-temperature and high-temperature mechanical properties of the refractory high-entropy alloy, particularly the plasticity.
The following is a detailed description of a high-entropy alloy and a preparation method thereof according to embodiments of the present application:
the application provides a high-entropy alloy, the component of which is Nb a V b Ta c M d B e Wherein M is any one or more of Ti, mo, zr, cr, al and W, a, b, c, d and e respectively represent the mol percent of the corresponding elements, a is more than or equal to 5 and less than or equal to 35,5 and less than or equal to b and less than or equal to 35,5 and less than or equal to c and less than or equal to 35,0 and less than or equal to d and less than or equal to 35,5 and less than or equal to e and less than or equal to 25, and a +, b +, c +, d +, e =100.
The method obtains the ordered boride phase by introducing the B element into a solid solution phase of a BCC structure formed by refractory metals V, nb, ta and M, and obtains the refractory high-temperature-resistant high-strength irradiation-resistant high-entropy alloy reinforced by boride. V, nb and Ta are in the same group in the periodic table, have similar chemical properties, and are capable of forming borides with the same structure as element B. Namely, the high-entropy alloy of the present application is composed of a body-centered cubic VNbTaM solid solution phase and a tetragonal (Nb, V, ta, M) 3 B 2 Ordered boride phase composition. The high-entropy alloy has excellent radiation resistance, high melting point and excellent high-temperature softening resistance, and can meet the requirements on the mechanical properties of the alloy under the condition of strong irradiation service.
Meanwhile, compared with precipitation strengthening type refractory high-entropy alloy, the ordered boride phase content in the alloy is high, the alloy has excellent softening resistance, structure stability and irradiation resistance under the high-temperature condition, and two phases in the alloy can form an eutectic structure along with the change of the content of a second phase, so that the fluidity and casting performance of the alloy are facilitated, element segregation and micro-porosity are not easy to occur, and the alloy is easy to machine and form.
And when d is more than 0, a proper amount of elements such as M (Ti, cr, al, mo, W) and the like are added, so that the cocktail effect of the high-entropy alloy can be enhanced on the basis of not changing the two-phase structure, the consistency of the two phases in the alloy is ensured, the adjustment and control of the alloy solidification structure are facilitated, and the structural consistency of the high-entropy alloy is better.
In addition, in the high-entropy alloy, the addition of V, ti, al, cr, B and other elements is beneficial to reducing the alloy density, the addition of Ta can enhance the solid solution strengthening effect, and the high-entropy alloy has wide application prospect in the field of anti-irradiation structural materials due to the excellent comprehensive performance.
Optionally, 25 is less than or equal to a and less than or equal to 35, 25 is less than or equal to b and less than or equal to 35,5 and less than or equal to c and less than or equal to 20,0 and less than or equal to d and less than or equal to 20,5 and less than or equal to e and less than or equal to 25.
Optionally, a is more than or equal to 30 and less than or equal to 35, b is more than or equal to 30 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 15,0 and less than or equal to d is more than or equal to 10, and e is more than or equal to 10 and less than or equal to 20.
In one embodiment of the present application, a =35,b =35,c =15,d =0,e =15, and the high-entropy alloy is Nb 35 V 35 Ta 15 B 15 . In some other embodiments of the present application, a =33,b =33,c =11,d =5,e =18, and the high-entropy alloy is Nb 33 V 33 Ta 11 M 5 B 1 (ii) a In particular, when M is Mo, the high-entropy alloy is Nb 33 V 33 Ta 11 Mo 5 B 18 . Or a =33,b =33,c =15,d =7,e =12, the high-entropy alloy is Nb 33 V 33 Ta 15 M 7 B 12 (ii) a In particular, when M is Ti, the high-entropy alloy is Nb 33 V 33 Ta 15 Ti 7 B 12 。
The application also provides a preparation method of the high-entropy alloy, which comprises the following steps:
s1, preparing raw materials
The raw materials comprise a niobium precursor, a vanadium precursor, a tantalum precursor, an M precursor and optionally a boron simple substance, wherein the boron simple substance can be selectively added according to requirements, so that the molar ratio of Nb, V, ta, M and B elements in the raw materials is a: B: c: d: e.
In the high-entropy alloy, niobium (Nb) is introduced in a niobium precursor mode, and the niobium precursor is a niobium simple substance and/or niobium diboride; introducing vanadium (V) element in a mode of vanadium precursor, wherein the vanadium precursor is vanadium simple substance and/or vanadium diboride; the tantalum (Ta) element is introduced in a tantalum precursor mode, the tantalum precursor is a tantalum simple substance and/or tantalum diboride, the M element is introduced in an M precursor mode, the M precursor is a simple substance and/or M boride, and the boron (B) element is introduced in any one or more of niobium diboride, vanadium diboride, tantalum diboride, M boride and boron simple substance.
When the raw materials include various simple substances, the simple substances are required to be subjected to oxide layer removal treatment and then weighed, so that the purity of various components of the raw materials is ensured to be more than 99.95%.
Optionally, c is larger than e/2, the raw materials comprise a niobium simple substance, a vanadium simple substance, a tantalum simple substance, an M simple substance and tantalum diboride, and the boron element is introduced into the high-entropy alloy in the form of tantalum diboride.
S2, smelting
The weighed raw materials are put into a crucible, and when the raw materials are placed, the raw materials are placed from high to low according to the melting point of the metal simple substance and/or the melting point of the compound, namely, the raw materials with the lowest melting point are placed at the bottom of the crucible, then the raw materials with higher melting points are placed on the surface of the raw materials with the lower melting point, and the raw materials with the lower melting point are sequentially covered until the placement of the raw materials with the highest melting point is completed. And then putting the container into a vacuum electric arc furnace, aligning electric arcs to the upper layer raw materials, firstly setting small electric arcs to slightly dissolve the upper layer raw materials, then adjusting large current to melt all the raw materials into a melt, and after the melt is solidified, repeating the melting operation to melt the raw materials for more than 8 times.
The current of the small arc is 150-200A.
In one embodiment of the present application, the current of the small arc is 180A. In some other embodiments of the present application, the current of the small arc may also be 150A, 155A, 160A, 165A, 170A, 175A, 185A, 190A, 195A, or 200A.
The current is 350-420A after the large current is adjusted.
The current of the small arc is 150-200A.
In one embodiment of the present application, the current of the small arc is 180A. In some other embodiments of the present application, the current of the small arc may also be 150A, 155A, 160A, 165A, 170A, 175A, 185A, 190A, 195A or 200A.
The current after the increase is 350 to 420A.
In one embodiment of the present application, the adjusted current is 400A. In some other embodiments of the present application, the adjusted current may also be 350A, 355A, 360A, 365A, 370A, 375A, 380A, 385A, 390A, 395A, 405A, 410A, 415A, or 420A.
In order to ensure uniform melting of the alloy, after each time the melt is solidified, the button ingot formed by solidification needs to be turned over and then subjected to melting operation.
Optionally, after each melt solidification, the solidified button ingot is turned over by a manipulator until the top surface (plane) of the button ingot is 30-50 degrees to the horizontal plane.
In addition, during the melting process, it is necessary to observe whether or not the sparingly soluble particles are produced, and if the sparingly soluble particles are produced, if the arc is moved, to allow it to act directly on the sparingly soluble particles until they are melted.
Optionally, in order to ensure that the oxygen content in the alloy is low, the alloy is re-scrubbed after 4 times of melting is completed, and then the subsequent melting operation is carried out for multiple times.
The preparation method is simple and convenient, and the prepared high-entropy alloy has excellent irradiation resistance.
Of course, it should be noted that the process of melting the raw materials to obtain the high-entropy alloy may also be performed in other high-temperature furnaces, and the present application is not limited thereto.
The following describes a high-entropy alloy and a method for preparing the same in detail with reference to examples.
Example 1
The embodiment of the application provides a high-entropy alloy and a preparation method thereof, and the preparation method comprises the following steps:
s1, preparing raw materials
Preparing a niobium simple substance, a vanadium simple substance, a tantalum simple substance and tantalum diboride with the purity of more than 99.95%, removing an oxide layer on the surface by using sand paper, and then accurately weighing and calculating by using a balance to obtain the molar ratio of Nb, V, ta and B elements in the raw materials as 35.
S2, smelting
The weighed raw materials are put into a crucible and when the raw materials are placed, the raw materials are arranged from high to low according to the simple metal and/or compoundPlacing the raw materials with the lowest melting point at the bottom of the crucible, placing the raw materials with the higher melting point on the surface of the raw materials with the lower melting point, and sequentially covering the raw materials with the lower melting point until the placement of the raw materials with the highest melting point is finished. Then putting the container into a vacuum electric arc furnace, aligning electric arc with the upper layer raw material, firstly setting the current to be 180A to slightly dissolve the upper layer raw material, then regulating the current to be 400A to melt all the raw materials into a melt, after the melt is solidified, turning over the button ingot formed by solidification to the state that the top surface (plane) of the button ingot forms 30-50 degrees with the horizontal plane by adopting a manipulator, repeating the melting operation to melt the raw materials for 8 times, and preparing the high-entropy alloy V 35 Nb 35 Ta 15 B 15 。
Example 2
Embodiments of the present application provide + +, which includes the following steps:
s1, preparing raw materials
Preparing a niobium simple substance, a vanadium simple substance, a tantalum simple substance, a molybdenum simple substance and tantalum diboride with the purity of more than 99.95%, removing an oxide layer on the surface by using sand paper, and accurately weighing and calculating by using a balance to obtain the following components in the molar ratio of Nb, V, ta, mo and B elements in the raw materials of 33.
S2, smelting
Putting the weighed raw materials into a crucible, and placing the raw materials from high to low according to the melting point of a metal simple substance and/or a compound during placing, namely placing the raw material with the lowest melting point at the bottom of the crucible, placing the raw materials with higher melting points on the surface of the raw material with the lower melting point, and sequentially covering the raw materials with the lower melting points until the placing of the raw material with the highest melting point is completed. Then putting the container into a vacuum electric arc furnace, aligning electric arc with the upper layer raw material, firstly setting the current to be 180A to slightly dissolve the upper layer raw material, then regulating the current to be 400A to melt all the raw materials into a melt, after the melt is solidified, turning over the button ingot formed by solidification to the state that the top surface (plane) of the button ingot forms 30-50 degrees with the horizontal plane by adopting a manipulator, repeating the melting operation to melt the raw materials for 8 times, and preparing the high-entropy alloy V 33 Nb 33 Ta 11 Mo 5 B 18 。
Example 3
The embodiment of the application provides a high-entropy alloy and a preparation method thereof, and the preparation method comprises the following steps:
s1, preparing raw materials
Preparing a niobium simple substance, a vanadium simple substance, a tantalum simple substance, a titanium simple substance and tantalum diboride with the purity of more than 99.95%, removing an oxide layer on the surface by using sand paper, and accurately weighing and calculating by using a balance to obtain the following components in the molar ratio of Nb, V, ta, ti and B elements in the raw materials of 33.
S2, smelting
The weighed raw materials are put into a crucible, and when the raw materials are placed, the raw materials are placed from high to low according to the melting point of the metal simple substance and/or the melting point of the compound, namely, the raw materials with the lowest melting point are placed at the bottom of the crucible, then the raw materials with higher melting points are placed on the surface of the raw materials with the lower melting point, and the raw materials with the lower melting point are sequentially covered until the placement of the raw materials with the highest melting point is completed. Then putting the container into a vacuum electric arc furnace, aligning electric arc with the upper layer raw material, firstly setting the current to be 180A to slightly dissolve the upper layer raw material, then regulating the current to be 400A to melt all the raw materials into a melt, after the melt is solidified, turning over the button ingot formed by solidification to the state that the top surface (plane) of the button ingot forms 30-50 degrees with the horizontal plane by adopting a manipulator, repeating the melting operation to melt the raw materials for 8 times, and preparing the high-entropy alloy V 33 Nb 33 Ta 15 Ti 7 B 12 。
Comparative example 1
The application provides a high-entropy alloy and a preparation method thereof, and the preparation method comprises the following steps:
s1, preparing raw materials
Preparing a niobium simple substance, a vanadium simple substance, a tantalum simple substance, a boron simple substance and tantalum diboride with the purity of more than 99.95%, removing an oxide layer on the surface by using sand paper, and accurately weighing and calculating by using a balance to obtain the molar ratio of Nb, V, ta and B elements in the raw materials as 30.
S2, smelting
Putting the weighed raw materials into a crucible, and placing the raw materials from high to low according to the melting point of a metal simple substance and/or a compound during placing, namely placing the raw material with the lowest melting point at the bottom of the crucible, placing the raw materials with higher melting points on the surface of the raw material with the lower melting point, and sequentially covering the raw materials with the lower melting points until the placing of the raw material with the highest melting point is completed. And then putting the container into a vacuum electric arc furnace, aligning electric arc to the upper layer raw material, firstly setting the current to be 180A to slightly dissolve the upper layer raw material, then regulating the current to be 400A to melt all the raw materials into a melt, after the melt is solidified, overturning the button ingot formed by solidification to the state that the top surface (plane) of the button ingot forms 30-50 degrees with the horizontal plane by adopting a manipulator, and repeating the melting operation to melt the raw materials for 8 times, so that the raw materials cannot be successfully melted.
Test example 1
The high-entropy alloys prepared in examples 1 to 3 were subjected to performance characterization including phase composition in X-ray diffraction test, quasi-static room temperature compression test and quasi-static high temperature compression test.
Scanning electron micrographs of the high-entropy alloys produced in examples 1 to 3 are shown in FIGS. 1 to 3.
The X-ray diffraction test phase composition adopts an X-ray instrument model of Rigaku D/MAX-2250, the selected ray is a Cu (Kalpha) ray, the working voltage and the current are respectively 40kV and 200mA, the scanning angle is 10-90 degrees, the scanning speed is 5 degrees/min, and the working temperature is room temperature. The results are shown in fig. 4, which are obtained by cutting a sample into square pieces of 10mm × 5mm by wire cutting, finely flattening the cut pieces with 240#, 400#, 800#, and 1000# sandpaper, and then performing scanning analysis of the sample using an X-ray diffractometer.
The quasi-static room temperature compression test is carried out on a CMT4305 type electronic universal tester, the maximum load of the tester is 300KN, and the strain rate of a sample is kept at 10 in the test process -3 And(s) in the presence of a catalyst. The compression sample is a cylinder with the diameter of 5mm and the height of 10mm, the height-diameter ratio of the compression sample is 2:1, the side faces of the compression sample are ground by 240#, 400#, 600#, 1000# sandpaper, and the two ends of the compression sample are ground to be flat, so that inaccurate stress strain data caused by the geometry of the compression sample are avoided. Room temperature compression V obtained by experiment 35 Nb 35 Ta 15 B 15 、V 33 Nb 33 Ta 11 Mo 5 B 18 And V 33 Nb 33 Ta 15 Ti 7 B 12 The engineering stress-strain curves of the alloys are shown in figures 5, 8 and 11.
Quasi-static high temperatureThe compression test was performed on a SW3800Gleeble thermal simulation tester with a maximum load of 100KN and a strain rate of 10 for all samples during the test -3 (s) the maximum strain in compression is set at 50%. The test sample and the quasi-static compression experiment sample are subjected to the same treatment, and a K-type thermocouple is welded in the middle of the test sample in the experiment process, so that the accuracy of the test sample temperature in the test process is ensured. The test is carried out at high temperature, the temperature is rapidly increased at the speed of 20 ℃/s when the temperature is between room temperature and the target temperature of 200 ℃, the temperature is close to the target temperature at the speed of 5 ℃/s, the test is carried out after the target temperature is kept for 30 minutes, and the compression V at 850 ℃ and 1000 ℃ obtained in the experiment 35 Nb 35 Ta 15 B 15 、V 33 Nb 33 Ta 11 Mo 5 B 18 And V 33 Nb 33 Ta 15 Ti 7 B 12 The engineering stress-strain curves of the alloys are shown in FIGS. 6 to 7, 9 to 10, and 12 to 13.
As can be seen from FIGS. 1 to 3, the high-entropy alloys of examples 1 to 3 of the present application have a solid solution phase of VNbM of a volume-centered cubic structure and a solid solution phase of tetragonal structure (VNbM) 3 B 2 Ordered compound phase composition.
As can be seen from fig. 5 to 13, the high-entropy alloys of examples 1 to 3 of the present application have excellent compressive strength and good compression plasticity at both room temperature and high temperature.
Test example 2
The high-entropy alloy prepared in example 1 and the high-entropy alloy V were taken 35 Nb 35 Ta 15 Si 15 And Hastelloy N of NiMo-SiC and U.S. Hastelloy were subjected to the test of radiation resistance. Wherein the mass ratio of NiMo to SiC in NiMo-SiC is 100, and the mass ratio of Ni element to Mo element in NiMo is 84.
The method for testing the radiation resistance performance comprises the following steps: sampling at the maximum irradiation damage depth of the sample by using FIB, observing the distribution of helium bubbles in the matrix at the maximum irradiation damage depth by using TEM, measuring the diameter of the helium bubbles and counting the number of the helium bubbles in unit area, thereby obtaining the size and the number density of the helium bubbles.
As can be seen from fig. 14, the helium bubbles in the high-entropy alloy obtained in example 1 of the present application are smaller in size and smaller in number.
As can be seen from FIG. 15, the high-entropy alloy obtained in example 1 of the present application is compared with the high-entropy alloy V 35 Nb 35 Ta 15 Si 15 NiMo-SiC and Hastelloy N, which have the smallest bubble size.
As can be seen from FIG. 16, the high-entropy alloy obtained in example 1 of the present application is compared with the high-entropy alloy V 35 Nb 35 Ta 15 Si 15 NiMo-SiC and Hastelloy N, which have the lowest number density of helium bubbles.
In summary, in the high-entropy alloy and the preparation method thereof of the embodiments of the present application, the refractory metals V, nb, ta, M in the high-entropy alloy are easy to form (V, nb, ta, M) with B 3 B 2 The crystal structure of the ordered boride phase belongs to a tetragonal system, and the ordered boride phase is easy to form a regular lamellar eutectic structure with a BCC phase formed by refractory elements V, nb, ta and M, so that the integral anti-irradiation performance of the high-entropy alloy material is improved. The size and the number density of helium bubbles at the maximum irradiation damage part of the high-entropy alloy are respectively 1.94nm and 1.18 multiplied by 10 20 /m 3 The radiation resistance of the alloy is improved by more than 10 times compared with the prior nickel-based high-temperature alloy, and is also improved by more than 2 times compared with the novel nano SiC particle reinforced radiation resistant alloy (such as NiMo-SiC), thereby showing excellent radiation resistance. In addition, the melting point of the alloy exceeds 1900 ℃, the compressive yield strength at room temperature exceeds 1500MPa, the compressive strength exceeds 3000MPa, and the compressive strain at room temperature exceeds 35%; in addition, the melting point of the alloy exceeds 1900 ℃, the compressive yield strength at room temperature exceeds 1500MPa, the compressive strength exceeds 3000MPa, and the compressive strain at room temperature exceeds 35 percent; the compression strength at 850 ℃ is over 1200MPa, the compression strength at 1000 ℃ is about 950MPa, excellent high-temperature softening resistance is shown, and the requirement on the mechanical property of the alloy under the strong irradiation service condition can be met.
Meanwhile, compared with precipitation strengthening type refractory high-entropy alloy, the ordered boride phase content is high, the alloy has excellent softening resistance, structure stability and irradiation resistance under a high-temperature condition, and two phases in the alloy can form an eutectic structure along with the change of the content of the second phase, so that the flowability and the casting performance of the alloy are facilitated, element segregation and micro-porosity are not easy to occur, and the alloy is easy to machine and form.
In addition, in the high-entropy alloy, the addition of V, ti, al, cr, B and other elements is beneficial to reducing the alloy density, the addition of Ta can enhance the solid solution strengthening effect, and the high-entropy alloy has wide application prospect in the field of anti-irradiation structural materials due to the excellent comprehensive performance.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (15)
1. The high-entropy alloy is characterized in that the component of the high-entropy alloy is Nb a V b Ta c M d B e Wherein M is any one or more of Ti, mo, zr, cr, al and W, a, b, c, d and e respectively represent the mole percentage of the corresponding elements, a is more than or equal to 5 and less than or equal to 35,5 and less than or equal to b 35,5 and less than or equal to c is more than or equal to 35,0 and less than or equal to d is more than or equal to 35,5 and less than or equal to e is more than or equal to 25, and a +, b +, c +, d +, e =, and 100;
v, nb, ta, M and B form (V, nb, ta, M) 3 B 2 The ordered boride phase and a BCC phase formed by V, nb, ta and M form a regular lamellar eutectic structure.
2. A high entropy alloy as claimed in claim 1, wherein 25. Ltoreq. A.ltoreq.35, 25. Ltoreq. B.ltoreq. 35,5. Ltoreq. C.ltoreq. 20,0. Ltoreq.d 20.
3. A high entropy alloy as claimed in claim 1, wherein 30. Ltoreq. A.ltoreq.35, 30. Ltoreq. B.ltoreq.35, 10. Ltoreq. C.ltoreq. 15,0. Ltoreq. D.ltoreq.10, 10. Ltoreq. E.ltoreq.20.
4. A high entropy alloy as claimed in claim 3, wherein a =35, b =35, c =15, d =0, e =15, and the high entropy alloy is characterized by the high temperatureThe entropy alloy is Nb 35 V 35 Ta 15 B 15 。
5. A high entropy alloy as claimed in claim 3, wherein a =33, b =33, c =11, d =5, e =18, and the high entropy alloy is Nb 33 V 33 Ta 11 M 5 B 18 。
6. A high entropy alloy according to claim 3, wherein M is Mo and the high entropy alloy is Nb 33 V 33 Ta 11 Mo 5 B 18 。
7. A high entropy alloy as claimed in claim 3, wherein a =33, b =33, c =15, d =7, e =12, and the high entropy alloy is Nb 33 V 33 Ta 15 M 7 B 12 。
8. A high entropy alloy according to claim 3, wherein M is Ti and the high entropy alloy is Nb 33 V 33 Ta 15 Ti 7 B 12 。
9. A method for preparing a high-entropy alloy according to any one of claims 1 to 8, wherein the method for preparing the high-entropy alloy comprises: smelting the raw materials in an oxygen-free environment to prepare a high-entropy alloy;
the raw materials comprise a niobium precursor, a vanadium precursor, a tantalum precursor and an M precursor, wherein the niobium precursor is a niobium simple substance and/or niobium diboride, the vanadium precursor is a vanadium simple substance and/or vanadium diboride, the tantalum precursor is a tantalum simple substance and/or tantalum diboride, the M precursor is an M simple substance and/or M boride, and the molar ratio of Nb, V, ta, M and B elements in the raw materials is a: B: c: d: e.
10. A method of producing a high entropy alloy as claimed in claim 9, wherein the raw material further includes elemental boron.
11. A method for producing a high entropy alloy as claimed in claim 9, wherein c > e/2, and the raw materials include elemental niobium, elemental vanadium, elemental tantalum, elemental M, and tantalum diboride.
12. A method for preparing a high-entropy alloy according to claim 9, wherein the melting is performed in a vacuum arc furnace, an arc is directed at an upper raw material, a current is set to 150 to 200A to slightly dissolve the upper raw material, then the current is adjusted to 350 to 420A to melt all the raw materials into a melt, and after the melt is solidified, the melting operation is repeated to melt the raw materials more than 8 times.
13. A method for producing a high entropy alloy as claimed in claim 12, wherein the raw materials are placed from high to low in accordance with the melting point of the metal element and/or compound, the metal element or compound having the highest melting point is placed on the topmost layer, and the metal element or compound having the lowest melting point is placed on the bottommost layer.
14. A method for preparing a high entropy alloy according to claim 12, wherein after the melt is solidified, the solidified button ingot is turned over and then subjected to a melting operation.
15. A production method of a high entropy alloy as claimed in claim 12, wherein whether or not the sparingly soluble particles are produced is observed during melting, and the sparingly soluble particles are directly acted on by an electric arc until melting.
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