CN115710667A - Refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature and preparation method thereof - Google Patents
Refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a refractory high-entropy alloy with high strength and toughness at room temperature and high thermal stability and a preparation method thereof, belonging to the technical field of high-entropy alloys. The refractory high-entropy alloy comprises V, nb, ta, ti, zr and rare earth elements, and is mainly a BCC phase and contains a trace (RE, zr) rich phase or a RE-rich second phase by optimizing the content of each component, so that the refractory high-entropy alloy has excellent room-temperature strong plasticity matching and high-temperature stability; the refractory high-entropy alloy is prepared by adopting the processes of smelting, cold rolling and high-temperature annealing, the preparation process is simple, large-scale production is easy to realize, the harsh requirements of advanced aerospace, nuclear reactor systems and the like on high-performance high-temperature structural materials can be better met, and the application potential is huge.
Description
Technical Field
The invention relates to a refractory high-entropy alloy with high strength and toughness at room temperature and high thermal stability and a preparation method thereof, belonging to the technical field of high-entropy alloys.
Background
The high-entropy alloy is a novel metal material prepared by mixing a plurality of principal elements with similar contents, and shows a plurality of excellent properties such as higher strength and hardness, better corrosion resistance and wear resistance and the like by virtue of the structure and physical characteristics brought by the multi-principal element effect, thereby gaining wide attention of researchers at home and abroad. Compared with the Face Centered Cubic (FCC) structure high-entropy alloy composed of 3d transition group metal elements, the Body Centered Cubic (BCC) structure refractory high-entropy alloy has higher high-temperature strength due to the characteristics of high melting point, large lattice distortion and the like of the constituent elements, and becomes one of candidates of novel high-temperature structural materials for advanced aircrafts and nuclear reactors in the future.
The stability of the alloy structural material in service at high temperature for a long time is the guarantee of the safe operation of future advanced aircrafts, nuclear reactors and the like, and certain strong plasticity at room temperature can ensure the processing, forming, transportation and installation of the alloy structural materialThe feasibility of (2). Among the refractory high-entropy alloys reported at present, nb-Mo-Ta-W-Cr system alloy shows higher strength at high temperature, but the room temperature brittleness (the compression plasticity is lower than 20%) prevents the further development of the alloy; the Hf-Nb-Ta-Zr-Ti-V system alloy shows a certain tensile plasticity at room temperature, such as HfNbZrTi and Hf 0.5 Nb 0.5 Ta 0.5 ZrTi 1.5 、TiNbTa、VNbZr 2 And the weak strain hardening capacity (the uniform elongation is generally lower than 5%) of Ti and the like at room temperature causes local stress concentration in the processing and preparation process, so that the material is unevenly deformed or broken, the requirement of large deformation processing cannot be met, and the phase instability at high temperature seriously deteriorates the mechanical property, so that the further application of Ti as a high-temperature structural material is limited. Therefore, the development of a novel refractory high-entropy alloy with high strength and toughness at room temperature and high thermal stability is a main development trend of high-performance high-temperature structural materials.
Disclosure of Invention
In view of the above, the invention provides the refractory high-entropy alloy with high strength, toughness and high thermal stability at room temperature and the preparation method thereof, the alloy phase composition is regulated and controlled by optimizing the alloy components and the content of each component, so that the refractory high-entropy alloy with excellent room-temperature strong plasticity matching and high-temperature stability is obtained.
The purpose of the invention is realized by the following technical scheme.
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature has a chemical formula of V according to the atomic percentage content (at%) of each element a Nb b Ta c Ti d RE e Zr f Wherein RE is at least one of rare earth elements, 35<a≤45，35<b≤45，5≤c≤20，5≤d≤20，0.05≤e≤1.0，0≤f≤1.5，75≤a+b≤85，0.2≤e+f≤2.0，a+b+c+d+e+f＝100。
Preferably, RE is at least one of Y, ce, la, sc, dy and Er.
Preferably, the refractory high-entropy alloy contains rare earth elements and Zr elements at the same time, and f is more than or equal to 0.1 and less than or equal to 1.5.
The preparation method of the refractory high-entropy alloy specifically comprises the following steps:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a smelting furnace, and firstly vacuumizing to 5 multiplied by 10 -3 Below Pa, introducing inert gas, and then performing alloying smelting to obtain an alloy ingot;
(2) Rolling the alloy cast ingot at room temperature to obtain an alloy plate;
(3) Under the protection of inert gas, carrying out high-temperature annealing treatment on the alloy plate, wherein the annealing temperature is 1100-1400 ℃, the annealing time is 12-80 h, and then rapidly cooling in a cooling medium to obtain the refractory high-entropy alloy.
Further, the smelting furnace in the step (1) is a non-consumable vacuum arc smelting furnace or a suspension smelting furnace.
Further, the deformation of each pass in the rolling treatment in the step (2) is less than or equal to 20 percent, and the total deformation is 60 to 90 percent.
Further, the cooling medium in the step (3) is air, room temperature water, brine ice or quenching oil.
Has the beneficial effects that:
(1) The invention obtains the refractory high-entropy alloy which takes BCC phase as main component and contains trace (RE, zr) rich phase or RE rich second phase by optimizing the alloy components and the content of each component, and the density of the refractory high-entropy alloy is less than or equal to 8.5g/cm 3 The tensile strength at room temperature is more than 870MPa, the elongation at break is more than 18 percent, the uniform elongation is more than 10 percent, and the material has excellent structural stability and mechanical property stability at the high temperature of 900 ℃, can better meet the rigorous requirements of advanced aerospace, space nuclear reactor systems and the like on high-performance high-temperature structural materials.
(2) In the refractory high-entropy alloy, the main constituent elements V, nb and Ta of the alloy have high melting points and good plasticity, and the atomic size difference of the element V and other elements is large, so that the lattice distortion degree of the alloy is improved, the solid solution strengthening effect is further enhanced, and the strength of the alloy at room temperature is ensured; the strength of the alloy at high temperature is ensured by the strong metal bond caused by the high melting point of the Nb and Ta elements. In addition, a proper amount of low-density Ti element is added, so that the density of the alloy can be reduced, the dislocation motion is hindered and the strength is improved by increasing the chaos of the alloy and the pinning effect of the whole atomic size brought by the multi-principal element effect of the high-entropy alloy, the local stress concentration is avoided, the loss of plasticity is reduced, and the alloy keeps good strong plasticity matching.
(3) In the refractory high-entropy alloy, trace RE and Zr elements can be combined with inevitable impurity atoms such as C, N, O and the like in the alloy to form a RE-rich or (RE, zr-rich) second phase, so that the stability of the mechanical property of the alloy in a high-temperature service environment is ensured. The added trace RE combines with impurity atoms in the alloy to form a RE-rich phase with a density of 5.0-7.5 g/cm 3 ) Less than the density of the alloy, part of the RE-rich phase floats on the surface of the melt during smelting to play a role in purifying the melt, and part of the RE-rich phase existing in the matrix plays a role in strengthening the second phase, but when the RE content exceeds 1.0at%, the RE-rich phase with larger size formed in the matrix is generally aggregated at the grain boundary, which can deteriorate the mechanical property of the alloy, so that the RE content is controlled between 0.05 and 1.0at%. The added trace Zr element can be dissolved in the matrix to improve the solid solution strengthening effect, and can also be combined with the RE element and impurity atoms to form a rich (RE, zr) phase to improve the second phase strengthening effect; if the Zr content is too high, although the strength can be greatly improved, the larger mixing and dissolving gap between Ta and Zr causes the spinodal decomposition of the Ta and the Zr to cause the instability of the structure, thereby deteriorating the mechanical property of the alloy, so the Zr content is controlled between 0 and 1.5at percent.
(4) The refractory high-entropy alloy can greatly shorten the homogenization treatment time by a simple, easy, safe and reliable process of 'smelting, cold rolling and high-temperature annealing', is easy to realize large-scale production, and has good application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the refractory high entropy alloys prepared in examples 1-6.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the refractory high entropy alloy prepared in example 1.
FIG. 3 shows the result of X-ray energy spectrum analysis of the second phase in the refractory high-entropy alloy prepared in example 1.
FIG. 4 is a scanning electron microscope photograph of the refractory high entropy alloy prepared in example 1 after heat treatment at 900 deg.C for 500 h.
FIG. 5 shows the result of X-ray energy spectrum analysis of the second phase of the refractory high-entropy alloy prepared in example 1 after heat treatment at 900 ℃ for 500 h.
FIG. 6 is a scanning electron microscope image of a refractory high entropy alloy prepared in example 2.
FIG. 7 shows the result of X-ray energy spectrum analysis of the second phase in the refractory high-entropy alloy prepared in example 2.
FIG. 8 is a scanning electron microscope photograph of the refractory high-entropy alloy prepared in comparative example 1 after heat treatment at 900 ℃ for 500 hours.
FIG. 9 shows the result of X-ray energy spectrum analysis of the second phase of the refractory high-entropy alloy prepared in comparative example 1 after heat treatment at 900 ℃ for 500 hours.
Detailed Description
The present invention is further illustrated with reference to specific embodiments, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public source unless otherwise specified.
In the following examples and comparative examples:
the purities (mass percentage, wt%) of the simple substances corresponding to V, nb, ta, ti, Y, ce and Zr are all more than 99.9%.
Phase analysis: the phase analysis of the prepared refractory high-entropy alloy is carried out by a Rigaku X-ray diffractometer of Japan science company, an X-ray source is a Cu target Kalpha ray, the working voltage is 40kV, the working current is 110mA, the scanning speed is 5 degrees/min, the scanning angle range is 20 degrees to 90 degrees, and the step length is 0.02 degree.
And (3) microstructure characterization: the microstructure of the prepared refractory high-entropy alloy is characterized by adopting an American FEI-Apreo C field emission scanning electron microscope, and a back scattering electron signal is used, wherein the emission voltage is 15kV.
Quasi-static tensile test: according to the standard GB/T228.1-2010, a CMT4305 type electronic universal testing machine is adopted to carry out room temperature tensile mechanical property tests on the prepared refractory high-entropy alloy and the refractory high-entropy alloy subjected to high-temperature long-time heat preservation treatment, a non-standard I-shaped piece with the sample size of 3 multiplied by 10 multiplied by 1mm is used for controlling the strain rate to be 1 multiplied by 10 in the deformation process -3 /s。
And (3) testing the density: and carrying out density test on the prepared refractory high-entropy alloy by using an Archimedes drainage method.
C, testing the content of nitrogen and oxygen: carbon content was measured using a U.S. LECO-CS844 carbon and sulfur analyzer, and nitrogen and oxygen content were measured using a U.S. LECO-TCH600 Nitrogen oxygen and Hydrogen analyzer. Wherein the content of the element obtained by the test is the sum of the atom content of the free impurities existing in the alloy matrix and the atom content in the second phase.
Example 1
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 39at% of vanadium (V), 36at% of niobium (Nb), 10at% of tantalum (Ta), 14at% of titanium (Ti), 0.3at% of yttrium (Y) and 0.7at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 85%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1300 ℃, the annealing time is 24h, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in example 1 is 8.18g/cm 3 The contents of carbon, nitrogen and oxygen were 65wppm, 42wppm and 116wppm, respectively.
When the XRD analysis was performed on the refractory high-entropy alloy prepared in example 1, it can be seen from the XRD spectrum of fig. 1 that the refractory high-entropy alloy is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 1 is characterized, and as can be seen from fig. 2, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 37 +/-5 μm, and granular second phases exist in the grain interior and at the grain boundary. In addition, the EDS results in conjunction with fig. 3 indicate that these second phases are (Y, zr) -rich phases.
Under the protection of argon, the refractory high-entropy alloy prepared in example 1 is subjected to heat treatment at 900 ℃ for 500 hours, and then microstructure characterization is carried out, as can be seen from fig. 4, the grain size of the refractory high-entropy alloy subjected to heat treatment is 39 +/-6 microns, and second phases exist in the grain interior and at the grain boundary; meanwhile, the elemental analysis of the second phase revealed that the second phase after heat treatment was not changed and remained rich in (Y, zr) according to the EDS result of fig. 5.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 1, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 908 +/-15 MPa, the uniform elongation is 20 +/-3%, and the elongation at break is 27 +/-2%.
After the refractory high-entropy alloy prepared in example 1 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, mechanical property tests are carried out, and according to the test results in table 2, the strength and plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Example 2
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 39.64at% of vanadium (V), 39.64at% of niobium (Nb), 9.91at% of tantalum (Ta), 9.91at% of titanium (Ti), 0.1at% of yttrium (Y) and 0.8at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould into an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 80%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 72 hours, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in example 2 is 8.15g/cm 3 The contents of carbon, nitrogen and oxygen were 71wppm, 33wppm and 128wppm, respectively.
As can be seen from the XRD spectrum of FIG. 1, the refractory high-entropy alloy prepared in example 2 is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 2 is characterized, and as can be seen from fig. 6, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 35 ± 6 μm, and granular second phases exist in the grain interior and at the grain boundary. In addition, the EDS results in conjunction with fig. 7 indicate that these second phases are (Y, zr) rich phases.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 2, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 939 +/-18 MPa, the uniform elongation is 15 +/-4%, and the elongation at break is 24 +/-3%.
After the refractory high-entropy alloy prepared in example 2 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, mechanical property tests are carried out, and according to the test results in table 2, the strength and plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Example 3
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 40at% of vanadium (V), 45at% of niobium (Nb), 6at% of tantalum (Ta), 7at% of titanium (Ti), 0.5at% of yttrium (Y) and 1.5at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould into an alloy ingot, turning over and repeatedly smelting for 5 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 10%, and the total deformation is 75%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1250 ℃, the annealing time is 36h, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in example 3 is 7.88g/cm 3 The contents of carbon, nitrogen and oxygen were 67wppm, 51wppm and 133wppm, respectively.
As can be seen from the XRD spectrum of FIG. 1, the refractory high-entropy alloy prepared in example 3 is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 3 is characterized, and according to the test results, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 45 +/-5 microns, granular second phases exist in the grain interior and the grain boundary, and the second phases are rich in (Y, zr) phases according to the test results of EDS.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 3, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 925 +/-12 MPa, the uniform elongation is 15 +/-5%, and the elongation at break is 22 +/-4%.
After the refractory high-entropy alloy prepared in example 3 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, mechanical property tests are carried out, and according to test results in table 2, after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, the strength and the plasticity are basically kept unchanged.
Example 4
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 44.685at% of vanadium (V), 39.72at% of niobium (Nb), 7.944at% of tantalum (Ta), 6.951at% of titanium (Ti) and 0.7at% of yttrium (Y).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.0 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 15%, and the total deformation is 85%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 60 hours, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in example 4 is 8.05g/cm 3 The contents of carbon, nitrogen and oxygen were 81wppm, 42wppm and 112wppm, respectively.
As can be seen from the XRD spectrum of FIG. 1, the refractory high-entropy alloy prepared in example 4 is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 4 is characterized, and according to the test results, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 44 +/-3 μm, granular second phases exist in the grain interior and the grain boundary, and the second phase is a Y-rich phase according to the test results of EDS.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 4, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 955 +/-24 MPa, the uniform elongation is 15 +/-3%, and the elongation at break is 25 +/-3%.
After the refractory high-entropy alloy prepared in example 4 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, mechanical property tests are carried out, and according to the test results in table 2, the strength and plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Example 5
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 38at% of vanadium (V), 45at% of niobium (Nb), 8at% of tantalum (Ta), 8at% of titanium (Ti), 0.2at% of cerium (Ce) and 0.8at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould into an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 15%, and the total deformation is 82%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1250 ℃, the annealing time is 36 hours, and then rapidly cooling the alloy plate to room temperature in ice brine to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in example 5 is 8.08g/cm 3 The contents of carbon, nitrogen and oxygen were 78wppm, 45wppm and 125wppm, respectively.
As can be seen from the XRD spectrum of FIG. 1, the refractory high-entropy alloy prepared in example 5 is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 5 is characterized, and according to the test results, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 41 +/-5 microns, granular second phases exist in the grain interior and at the grain boundary, and the second phases are rich in (Ce, zr) phases according to the test results of EDS.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 5, and according to test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 962 +/-21 MPa, the uniform elongation is 16 +/-3%, and the breaking elongation is 24 +/-2%.
After the refractory high-entropy alloy prepared in example 5 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, mechanical property tests are carried out, and according to test results in table 2, after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, the strength and the plasticity are basically kept unchanged.
Example 6
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 39.88at% of vanadium (V), 44.85at% of niobium (Nb), 9.97at% of tantalum (Ta), 5at% of titanium (Ti) and 0.3at% of cerium (Ce).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 15%, and the total deformation is 85%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 72 hours, and then rapidly cooling the alloy plate to the room temperature in ice brine to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in example 6 is 7.92g/cm 3 The carbon, nitrogen and oxygen contents were 62wppm, 36wppm and 108wppm, respectively.
As can be seen from the XRD spectrum of FIG. 1, the refractory high-entropy alloy prepared in example 6 is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 6 is characterized, and according to the test results, the structure of the refractory high-entropy alloy is an equiaxial crystal structure, the grain size is 34 +/-6 microns, granular second phases exist in the grain interior and the grain boundary, and the second phase is a Ce-rich phase according to the test results of EDS.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in the example 6, and according to test results in the table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 919 +/-15 MPa, the uniform elongation is 18 +/-2%, and the breaking elongation is 27 +/-2%.
After the refractory high-entropy alloy prepared in example 6 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, mechanical property tests are carried out, and according to the test results in table 2, the strength and the plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Example 7
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 44.91at% vanadium (V), 37.924at% niobium (Nb), 9.98at% tantalum (Ta), 6.986at% titanium (Ti) and 0.2at% yttrium (Y).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting into an alloy ingot in a water-cooled copper die, turning over and repeatingSmelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 80%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 72 hours, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in the example 7 is 8.18g/cm < 3 >, and the contents of carbon, nitrogen and oxygen are 85wppm, 52wppm and 124wppm respectively.
From the XRD characterization results, it is clear that the refractory high-entropy alloy prepared in example 7 is mainly composed of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 7 is characterized, and according to the test results, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 40 +/-4 microns, granular second phases exist in the grain interior and the grain boundary, and the second phase is a Y-rich phase according to the test results of EDS.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 7, and according to test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 895 +/-15 MPa, the uniform elongation is 14 +/-3%, and the breaking elongation is 24 +/-3%.
After the refractory high-entropy alloy prepared in example 7 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, mechanical property tests are carried out, and according to the test results in table 2, the strength and the plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Example 8
The refractory high-entropy alloy with high strength, toughness and thermal stability at room temperature comprises the following components in percentage by atom: 39.88at% of vanadium (V), 39.88at% of niobium (Nb), 9.97at% of tantalum (Ta), 9.97at% of titanium (Ti) and 0.3at% of yttrium (Y).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould into an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 80%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1300 ℃, the annealing time is 48h, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in the example 8 is 8.18g/cm3, and the contents of carbon, nitrogen and oxygen are 82wppm, 22wppm and 106wppm respectively.
According to the XRD characterization result, the refractory high-entropy alloy prepared in example 8 mainly consists of BCC phase, and no diffraction peak of the second phase is detected due to the small content of the second phase.
The microstructure of the refractory high-entropy alloy prepared in example 8 was characterized, and according to the test results, the structure of the refractory high-entropy alloy was equiaxial, the grain size was 61 ± 5 μm, and granular second phases existed in the grain interior and at the grain boundary, and the second phase was Y-rich phase according to the test results of EDS.
Mechanical property tests are carried out on the refractory high-entropy alloy prepared in example 8, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature is 891 +/-14 MPa, the uniform elongation is 17 +/-2%, and the elongation at break is 25 +/-4%.
After the refractory high-entropy alloy prepared in example 8 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, mechanical property tests are performed, and according to the test results in table 2, the strength and the plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Comparative example 1
The refractory high-entropy alloy comprises the following components in percentage by atom: 40at% of vanadium (V), 40at% of niobium (Nb), 10at% of tantalum (Ta) and 10at% of titanium (Ti).
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould into an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 15%, and the total deformation is 90%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1300 ℃, the annealing time is 36 hours, and then rapidly cooling the alloy plate to the room temperature in ice brine to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in comparative example 1 is 8.15g/cm 3 The carbon, nitrogen and oxygen contents are respectively 78wppm, 44wppm and 351wppm.
The microstructure of the refractory high-entropy alloy prepared by comparative example 1 is characterized, and according to the test result, the structure of the refractory high-entropy alloy is an equiaxed crystal structure, the grain size is 218 +/-22 mu m, and no second phase is found in the grain interior and the grain boundary.
The refractory high-entropy alloy prepared in the comparative example 1 is subjected to heat treatment at 900 ℃ for 500 hours under the argon protective atmosphere, and then microstructure characterization is carried out, so that a granular or strip-shaped second phase is formed inside grains and at grain boundaries of the refractory high-entropy alloy after heat treatment, as can be seen from FIG. 8; meanwhile, it is understood from the EDS analysis results of the second phases in fig. 9 that these second phases are Ti-rich phases.
The mechanical property test of the refractory high-entropy alloy prepared in the comparative example 1 is carried out, and the test result in the table 1 shows that the tensile strength of the refractory high-entropy alloy at room temperature is 907 +/-15 MPa, the uniform elongation is 16 +/-4%, and the elongation at break is 25 +/-5%.
The refractory high-entropy alloy prepared by the comparative example 1 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, and then is subjected to mechanical property test, and according to the test results in the table 2, after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, the fracture elongation is 0, and the refractory high-entropy alloy can not be in service at high temperature for a long time.
Comparative example 2
The refractory high-entropy alloy comprises the following components in percentage by atom: 40at% of vanadium (V), 20at% of niobium (Nb), 20at% of tantalum (Ta) and 20at% of titanium (Ti).
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 15%, and the total deformation is 85%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the argon protective atmosphere, wherein the annealing temperature is 1350 ℃, the annealing time is 10 hours, and then rapidly cooling the alloy plate to the room temperature in ice brine to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared by the comparative example 2 is 8.63g/cm 3 The contents of carbon, nitrogen and oxygen were 86wppm, 56wppm and 328wppm, respectively.
And (3) performing microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 2, wherein the microstructure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 246 +/-36 microns, and no second phase is found in the grain interior and the grain boundary.
And (3) performing microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 2 after heat treatment at 900 ℃ for 500 hours in an argon protective atmosphere, wherein according to the test result, granular or strip-shaped second phases are formed inside grains and at grain boundaries of the refractory high-entropy alloy after heat treatment, and the second phase is a Ti-rich phase according to the test result of EDS.
The mechanical properties of the refractory high-entropy alloy prepared in comparative example 2 are tested, and the test results in table 1 show that the refractory high-entropy alloy has tensile strength of 743 +/-18 MPa, uniform elongation of 10 +/-4% and elongation at break of 21 +/-4% at room temperature.
After the refractory high-entropy alloy prepared by the comparative example 2 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, mechanical property tests are carried out, and according to test results in table 2, the fracture elongation of the refractory high-entropy alloy is reduced to 5 +/-4% and 2 +/-2% after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, which indicates that the refractory high-entropy alloy cannot be in service at high temperature for a long time.
Comparative example 3
The refractory high-entropy alloy comprises the following components in percentage by atom: 39.4at% of vanadium (V), 39.4at% of niobium (Nb), 9.85at% of tantalum (Ta), 9.85at% of titanium (Ti) and 1.5at% of yttrium (Y).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 60%, so as to obtain an alloy plate;
(3) And under the protection of argon, carrying out high-temperature annealing treatment on the alloy plate, wherein the annealing temperature is 1300 ℃, the annealing time is 48h, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in comparative example 3 is 8.13g/cm 3 The contents of carbon, nitrogen and oxygen are 69wppm, 50wppm and 124wppm respectively.
The microstructure of the refractory high-entropy alloy prepared by the comparative example 3 is characterized, and according to the test result, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 98 +/-12 mu m, meanwhile, a granular second phase mainly enriched at a grain boundary is found, and the second phase is a Y-rich phase according to the test result of EDS.
The mechanical property test of the refractory high-entropy alloy prepared by the comparative example 3 is carried out, and the test result in the table 1 shows that the tensile strength of the refractory high-entropy alloy at room temperature is 825 +/-15 MPa, the uniform elongation is 3 +/-3%, and the elongation at break is only 5 +/-2%, which indicates that the alloy can not meet the requirement of large deformation.
The refractory high-entropy alloy prepared by the comparative example 3 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, and then is subjected to mechanical property test, and according to the test results in the table 2, the strength and plasticity of the refractory high-entropy alloy are basically kept unchanged after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, but the elongation at break is low, so that the refractory high-entropy alloy cannot be used at high temperature for a long time.
Comparative example 4
The refractory high-entropy alloy comprises the following components in percentage by atom: 40at% of vanadium (V), 30at% of niobium (Nb), 15at% of tantalum (Ta), 14at% of titanium (Ti) and 1.0at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 15%, and the total deformation is 85%, so as to obtain an alloy plate;
(3) And under the protection of argon, carrying out high-temperature annealing treatment on the alloy plate, wherein the annealing temperature is 1200 ℃, the annealing time is 60 hours, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in comparative example 4 is 7.74g/cm 3 The contents of carbon, nitrogen and oxygen were 102wppm, 84wppm and 286wppm, respectively.
The microstructure of the refractory high-entropy alloy prepared by the comparative example 4 is characterized, and according to the test result, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 186 +/-39 mu m, and no second phase is found in the grain interior and the grain boundary.
And (3) performing microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 4 after heat treatment at 900 ℃ for 500 hours in an argon protective atmosphere, and according to a test result, forming granular or needle-shaped Zr-rich phases in the grains and at the grain boundaries of the refractory high-entropy alloy after heat treatment.
The mechanical properties of the refractory high-entropy alloy prepared in the comparative example 4 are tested, and the test results in the table 1 show that the tensile strength of the refractory high-entropy alloy at room temperature is 872 +/-15 MPa, the uniform elongation is 12 +/-4%, and the breaking elongation is 17 +/-2%.
After the refractory high-entropy alloy prepared by the comparative example 4 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, mechanical property tests are carried out, and according to test results in table 2, after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, the fracture elongation is reduced to 6 +/-3% and 4 +/-2%, which indicates that the alloy cannot be in service at high temperature for a long time.
Comparative example 5
The refractory high-entropy alloy comprises the following components in percentage by atom: 38at% of vanadium (V), 38at% of niobium (Nb), 9.5at% of tantalum (Ta), 9.5at% of titanium (Ti) and 5at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.0 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying the alloy liquid formed by smelting in a water-cooled copper mould to form an alloy ingot, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 82%, so as to obtain an alloy plate;
(3) And under the protection of argon, carrying out high-temperature annealing treatment on the alloy plate, wherein the annealing temperature is 1200 ℃, the annealing time is 60 hours, and then rapidly cooling the alloy plate to the room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in the comparative example 5 is 8.05g/cm 3 The contents of carbon, nitrogen and oxygen are respectively 99wppm, 62wppm and 264wppm.
According to the microstructure characterization result of the refractory high-entropy alloy prepared by the comparative example 5, the microstructure of the refractory high-entropy alloy prepared by the comparative example 5 is an equiaxed crystal structure, the grain size is 216 +/-29 mu m, and no second phase is found in the grain interior and the grain boundary.
And (3) performing microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 5 after heat treatment for 500 hours at 900 ℃ in an argon protective atmosphere, wherein according to a test result, the Zr-rich phase with an irregular shape is formed in the refractory high-entropy alloy grain after heat treatment and at the grain boundary.
The mechanical properties of the refractory high-entropy alloy prepared in the comparative example 5 are tested, and the test results in the table 1 show that the tensile strength of the refractory high-entropy alloy at room temperature is 934 +/-15 MPa, the uniform elongation is 5 +/-4%, and the elongation at break is 7 +/-2%.
The refractory high-entropy alloy prepared by the comparative example 5 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, and then is subjected to mechanical property test, and according to the test results in the table 2, after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, the fracture elongation is 0, and the refractory high-entropy alloy can not be in service at high temperature for a long time.
Comparative example 6
The refractory high-entropy alloy comprises the following components in percentage by atom: 45at% of vanadium (V), 40at% of niobium (Nb), 7at% of tantalum (Ta), 7at% of titanium (Ti) and 1at% of zirconium (Zr).
The refractory high-entropy alloy comprises the following specific preparation steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a non-consumable electric arc melting furnace, and vacuumizing the furnace to 2.5 multiplied by 10 -3 Introducing argon after Pa, then carrying out alloying smelting, and carrying out water-cooling copper on the alloy liquid formed by smeltingCooling and solidifying the alloy ingot in the mold, turning over and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) Performing wire cut electrical discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation of each pass is 20%, and the total deformation is 80%, so as to obtain an alloy plate;
(3) And under the protection of argon, carrying out high-temperature annealing treatment on the alloy plate, wherein the annealing temperature is 1250 ℃, the annealing time is 36 hours, and then rapidly cooling the alloy plate to room temperature in room-temperature water to obtain the refractory high-entropy alloy.
The density of the refractory high-entropy alloy prepared in comparative example 6 is 8.18g/cm 3 The contents of carbon, nitrogen and oxygen were 115wppm, 52wppm and 325wppm, respectively.
The microstructure of the refractory high-entropy alloy prepared by the comparative example 6 is characterized, and according to the test result, the structure of the refractory high-entropy alloy is an isometric crystal structure, the grain size is 184 +/-29 mu m, and no second phase is found in the grain interior and the grain boundary.
And (3) performing microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 6 after heat treatment at 900 ℃ for 500 hours in an argon protective atmosphere, and according to a test result, forming a needle-shaped Zr-rich phase in the grain and in the grain boundary of the refractory high-entropy alloy after heat treatment.
The mechanical properties of the refractory high-entropy alloy prepared in comparative example 6 are tested, and the test results in table 1 show that the tensile strength of the refractory high-entropy alloy at room temperature is 892 +/-15 MPa, the uniform elongation is 15 +/-3%, and the elongation at break is 21 +/-4%.
The refractory high-entropy alloy prepared in comparative example 6 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours respectively, and then is subjected to mechanical property test, and according to the test results in table 2, after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, the fracture elongation is 0, which indicates that the refractory high-entropy alloy cannot be in service at high temperature for a long time.
TABLE 1
| Tensile strength (MPa) | Uniform elongation (%) | Elongation at Break (%) | |
| Example 1 | 908±15 | 20±3 | 27±2 |
| Example 2 | 939±18 | 15±4 | 24±3 |
| Example 3 | 925±12 | 15±5 | 22±4 |
| Example 4 | 955±24 | 15±3 | 25±3 |
| Example 5 | 962±21 | 16±3 | 24±2 |
| Example 6 | 919±15 | 18±2 | 27±2 |
| Example 7 | 895±15 | 14±3 | 24±3 |
| Example 8 | 891±14 | 17±2 | 25±4 |
| Comparative example 1 | 907±15 | 16±4 | 25±5 |
| Comparative example 2 | 743±18 | 10±4 | 21±4 |
| Comparative example 3 | 825±24 | 3±3 | 5±2 |
| Comparative example 4 | 872±15 | 12±4 | 17±2 |
| Comparative example 5 | 934±15 | 5±4 | 7±2 |
| Comparative example 6 | 892±15 | 15±3 | 21±4 |
TABLE 2
From the results, the refractory high-entropy alloy still keeps excellent structural and mechanical property stability after being subjected to high-temperature long-time heat treatment, and has a broad application prospect.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A refractory high-entropy alloy with high toughness and high thermal stability at room temperature is characterized in that: the chemical formula of the refractory high-entropy alloy is marked as V according to the atomic percentage content of each element a Nb b Ta c Ti d RE e Zr f Wherein RE is at least one of rare earth elements, 35<a≤45，35<b≤45，5≤c≤20，5≤d≤20，0.05≤e≤1.0，0≤f≤1.5，75≤a+b≤85，0.2≤e+f≤2.0，a+b+c+d+e+f＝100。
2. The refractory high-entropy alloy with high strength and toughness at room temperature and high thermal stability as claimed in claim 1, wherein: RE is at least one of Y, ce, la, sc, dy and Er.
3. The refractory high-entropy alloy with high strength and toughness at room temperature and high thermal stability as claimed in claim 1 or 2, wherein: f is more than or equal to 0.1 and less than or equal to 1.5.
4. The preparation method of the refractory high-entropy alloy with room temperature, high toughness and high thermal stability as claimed in claim 1 or 2, is characterized in that: the method specifically comprises the following steps:
(1) Weighing simple substances corresponding to each element according to atomic percentage, putting the simple substances into a smelting furnace, and firstly vacuumizing to 5 multiplied by 10 -3 Below Pa, introducing inert gas, and then performing alloying smelting to obtain an alloy ingot;
(2) Rolling the alloy cast ingot at room temperature to obtain an alloy plate;
(3) Under the protection of inert gas, carrying out high-temperature annealing treatment on the alloy plate, wherein the annealing temperature is 1100-1400 ℃, the annealing time is 12-80 h, and then rapidly cooling in a cooling medium to obtain the refractory high-entropy alloy.
5. The preparation method of the refractory high-entropy alloy with room temperature, high toughness and high thermal stability according to claim 4, is characterized in that: the smelting furnace in the step (1) is a non-consumable vacuum arc smelting furnace or a suspension smelting furnace.
6. The preparation method of the refractory high-entropy alloy with room temperature, high toughness and high thermal stability according to claim 4, is characterized in that: the deformation of each pass during the rolling treatment in the step (2) is less than or equal to 20 percent, and the total deformation is 60 to 90 percent.
7. The preparation method of the refractory high-entropy alloy with room temperature, high toughness and high thermal stability according to claim 4, is characterized in that: and (4) in the step (3), the cooling medium is air, room temperature water, brine ice or quenching oil.
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| CN105734312A (en) * | 2016-03-10 | 2016-07-06 | 北京科技大学 | Biomedical TiZrNbTa high-entropy alloy and preparation method thereof |
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