CN115710667B - 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 alloy. The refractory high-entropy alloy comprises V, nb, ta, ti, zr and rare earth elements, and the refractory high-entropy alloy which is mainly a BCC phase and contains a trace (RE, zr) rich phase or a RE rich second phase is obtained 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 smelting, cold rolling and high-temperature annealing processes, has simple preparation process, is easy to realize large-scale production, can better meet the severe requirements of advanced aerospace, nuclear reactor systems and the like on high-performance high-temperature structural materials, and has huge application potential.
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 alloy.
Background
The high-entropy alloy is a novel metal material prepared by mixing multiple principal elements with similar content, and shows various excellent performances 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 multiple principal elements effect, so that the high-entropy alloy is widely focused by researchers at home and abroad. Compared with a 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 of constituent elements, large lattice distortion and the like, and becomes one of candidates of novel high-temperature structural materials for future advanced aircrafts and nuclear reactors.
The stability of the alloy structural material in long-time service at high temperature is the guarantee of safe operation of advanced aircrafts, nuclear reactors and the like in the future, and the feasibility of processing, forming, transporting and installing the alloy structural material can be guaranteed by certain strength and plasticity at room temperature. Among the refractory high-entropy alloys reported so far, the Nb-Mo-Ta-W-Cr system alloy shows higher strength at high temperature, but room temperature brittleness (compression plasticity is lower than 20%) prevents further development; hf-Nb-Ta-Zr-Ti-V system alloys, although exhibiting a certain tensile plasticity at room temperature, such as HfNbZrTi, hf 0.5 Nb 0.5 Ta 0.5 ZrTi 1.5 、TiNbTa、VNbZr 2 Ti and the like, and the weak strain hardening capacity (uniform elongation is generally lower than 5%) of the Ti 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 worsens the mechanical property, so that the Ti-based high-temperature structural material is limited to be further applied as a high-temperature structural material. Therefore, the development of a novel refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature is a main development trend of high-performance high-temperature structural materials.
Disclosure of Invention
In view of the above, the invention provides a refractory high-entropy alloy with high strength and toughness at room temperature and high thermal stability and a preparation method thereof, and alloy phase composition is regulated and controlled by optimizing alloy components and content of each component, so that the refractory high-entropy alloy with excellent room temperature strong plasticity matching and high temperature stability is obtained, and the preparation process of the refractory high-entropy alloy is simple, is easy to realize large-scale production, can better meet the severe requirements of advanced aerospace, nuclear reactor systems and the like on high-performance high-temperature structural materials, and has huge application potential.
The aim of the invention is achieved by the following technical scheme.
A refractory high-entropy alloy with high strength and 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 (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 invention relates to a preparation method of refractory high-entropy alloy, which specifically comprises the following steps:
(1) Weighing corresponding simple substances of each element according to atomic percentage, putting into a smelting furnace, and vacuumizing to 5 multiplied by 10 -3 Under Pa, then introducing inert gas, and then carrying out alloying smelting to obtain alloy ingots;
(2) Rolling the alloy ingot at room temperature to obtain an alloy plate;
(3) And (3) under the protection of inert gas, performing 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 amount of each pass in the rolling treatment in the step (2) is less than or equal to 20 percent and the total deformation amount is 60 to 90 percent.
Further, in the step (3), the cooling medium is air, room temperature water, brine ice or quenching oil.
The beneficial effects are that:
(1) The invention obtains the refractory high-entropy alloy which is mainly based on BCC phase 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 is less than or equal to 8.5g/cm 3 The tensile strength at room temperature is more than 870MPa, the breaking elongation is more than 18 percent, the uniform elongation is more than 10 percent, and the high-performance high-temperature structural material has excellent structural stability and mechanical property stability at 900 ℃ under high-temperature environment, and can better meet the severe requirements of advanced aerospace, space nuclear reactor systems and the like on the high-performance high-temperature structural material.
(2) In the refractory high-entropy alloy, the main constituent elements V, nb and Ta of the alloy have high melting point and good plasticity, and the atomic size difference between the V element and other elements is large, so that the degree of lattice distortion 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 based on the strong metal bond brought by the high melting point of Nb and Ta elements. In addition, by adding a proper amount of low-density Ti element, the density of the alloy can be reduced, the alloy disorder degree can be increased, the strength is improved by preventing dislocation movement on one hand and reducing local stress concentration on the other hand by means of the pinning effect of the total atomic size caused by the multi-principal element effect of the high-entropy alloy, and the loss of plasticity is reduced, so that the alloy can maintain good strong plastic matching.
(3) In the refractory high-entropy alloy, trace RE and Zr elements can be combined with unavoidable impurity atoms such as C, N, O and the like in the alloy to form RE-rich or (RE, zr) -rich second phases, so that the stability of the mechanical properties of the alloy in a high-temperature service environment is ensured. Due to the trace RE added and the impurity source in the alloyDensity of the RE-rich phase formed by subcombination (5.0-7.5 g/cm) 3 ) Less than the density of the alloy, part of RE-rich phase floats on the surface of the melt in the smelting process to play a role in purifying the melt, and part of RE-rich phase existing in the matrix plays a role in strengthening the second phase, but when the RE content exceeds 1.0at%, RE-rich phase with larger size formed in the matrix is generally accumulated at the grain boundary to deteriorate the mechanical property of the alloy, so the RE content is controlled between 0.05 and 1.0at%. The added trace Zr element not only can be dissolved into the matrix to promote the solid solution strengthening effect, but also can be combined with RE element and impurity atoms to form a (RE, zr) -rich phase to promote the second-phase strengthening effect; if the Zr content is too high, the strength can be greatly improved, but the larger miscibility gap between Ta and Zr leads to amplitude modulation decomposition and structural instability, so that the mechanical property of the alloy can be deteriorated, and the Zr content is controlled between 0 and 1.5at percent.
(4) The refractory high-entropy alloy provided by the invention can greatly shorten the homogenization treatment time through a simple, easy, safe and reliable process of smelting, cold rolling and high-temperature annealing, is easy to realize large-scale production, and has a 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 a refractory high-entropy alloy prepared in example 1.
FIG. 3 is a graph showing the results of an X-ray energy spectrum analysis of a second phase in the refractory high-entropy alloy prepared in example 1.
FIG. 4 is a scanning electron microscope image of the refractory high-entropy alloy prepared in example 1 after heat treatment at 900℃for 500 hours.
FIG. 5 is a graph showing the results of an X-ray energy spectrum analysis of a second phase of the refractory high-entropy alloy prepared in example 1 after heat treatment at 900℃for 500 hours.
FIG. 6 is a scanning electron microscope image of the refractory high-entropy alloy prepared in example 2.
FIG. 7 is a graph of the results of an X-ray energy spectrum analysis of a second phase in the refractory high-entropy alloy prepared in example 2.
FIG. 8 is a scanning electron microscope image of the refractory high-entropy alloy prepared in comparative example 1 after heat treatment at 900℃for 500 hours.
FIG. 9 is a graph showing the result of an X-ray energy spectrum analysis of a 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 will be further described with reference to the following detailed description, wherein the processes are conventional, and wherein the starting materials are commercially available from the open market, unless otherwise specified.
In the following examples and comparative examples:
the purity (mass percent, wt%) of the simple substances corresponding to V, nb, ta, ti, Y, ce and Zr is more than 99.9 percent.
And (3) phase analysis: the phase analysis is carried out on the prepared refractory high-entropy alloy by adopting a Rigaku X-ray diffractometer of Japanese physics company, the X-ray source is Cu target K alpha rays, the working voltage is 40kV, the working current is 110mA, the scanning speed is 5 DEG/min, and the scanning angle range is 20 DEG-90 DEG and the step length is 0.02 deg.
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 the emission voltage is 15kV by using a back scattering electron signal.
Quasi-static tensile test: according to standard GB/T228.1-2010, a CMT4305 type electronic universal testing machine is adopted to test room temperature tensile mechanical properties of the prepared refractory high-entropy alloy and the refractory high-entropy alloy subjected to high-temperature long-time heat preservation treatment, a nonstandard I-shaped part with a sample size of 3X 10X 1mm is subjected to room temperature tensile mechanical properties testing, and the strain rate is controlled to be 1X 10 in the deformation process -3 /s。
Density testing: and (5) performing density test on the prepared refractory high-entropy alloy by using an Archimedes drainage method.
Carbon nitrogen oxygen content test: the carbon content was measured using a american LECO-CS844 carbon sulfur analyzer, and the nitrogen content and oxygen content were measured using a american LECO-TCH600 nitrogen oxygen hydrogen analyzer. Wherein the content of the element obtained by the test is the sum of the content of free impurity atoms present in the alloy matrix and the content of atoms in the second phase.
Example 1
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1300 ℃, the annealing time is 24 hours, and then rapidly cooling to room temperature in hot water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 1 had a density of 8.18g/cm 3 The contents of carbon, nitrogen and oxygen were 65wppm, 42wppm and 116wppm, respectively.
XRD analysis was performed on the refractory high-entropy alloy prepared in example 1, and as can be seen from the XRD spectrum of fig. 1, the refractory high-entropy alloy mainly consists of BCC phase, and diffraction peaks of the second phase are not detected due to the low content of the second phase.
The refractory high-entropy alloy prepared in example 1 was subjected to microstructure characterization, and as can be seen from fig. 2, the refractory high-entropy alloy has an equiaxed grain structure, the grain size is 37+ -5 μm, and granular second phases exist in the grain and at the grain boundary. In addition, EDS results in conjunction with FIG. 3 indicate that these second phases are the (Y, zr) rich phases.
After heat treatment of the refractory high-entropy alloy prepared in example 1at 900 ℃ for 500 hours under an argon protective atmosphere, microstructure characterization is performed, and as can be seen from fig. 4, the grain size of the refractory high-entropy alloy after heat treatment is 39+/-6 μm, and a second phase exists in the grain interior and at the grain boundary; at the same time, the second phase was subjected to elemental analysis, and it was found from the EDS result of fig. 5 that the second phase after heat treatment was unchanged and still a (Y, zr) -rich phase.
Mechanical properties of the refractory high-entropy alloy prepared in example 1 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 908±15MPa, the uniform elongation was 20±3%, and the elongation at break was 27±2%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in example 1 is subjected to mechanical property test, and according to the test results in table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Example 2
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 72h, and then rapidly cooling to room temperature in hot water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 2 had a density of 8.15g/cm 3 The contents of carbon, nitrogen and oxygen were 71wppm, 33wppm and 128wppm, respectively.
As can be seen from the XRD pattern of fig. 1, the refractory high-entropy alloy prepared in example 2 consisted mainly of BCC phase, and diffraction peaks of the second phase were not detected due to the low content of the second phase.
The refractory high-entropy alloy prepared in example 2 was subjected to microstructure characterization, and as can be seen from fig. 6, the refractory high-entropy alloy has an equiaxed grain structure, the grain size is 35±6μm, and granular second phases exist in the grain and at the grain boundary. In addition, the EDS results in conjunction with fig. 7 show that these second phases are (Y, zr) -rich phases.
Mechanical properties of the refractory high-entropy alloy prepared in example 2 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 939±18MPa, the uniform elongation was 15±4%, and the elongation at break was 24±3%.
After the refractory high-entropy alloy prepared in example 2 is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, mechanical property tests are carried out, and according to the test results in table 2, the high-entropy alloy has basically unchanged plasticity after being subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours.
Example 3
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements in percentage by atom: vanadium (V) 40at%, niobium (Nb) 45at%, tantalum (Ta) 6at%, titanium (Ti) 7at%, yttrium (Y) 0.5at%, zirconium (Zr) 1.5at%.
The specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 5 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1250 ℃, the annealing time is 36h, and then rapidly cooling to room temperature in hot water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 3 had a density of 7.88g/cm 3 The contents of carbon, nitrogen and oxygen were 67wppm, 51wppm and 133wppm, respectively.
As can be seen from the XRD pattern of fig. 1, the refractory high-entropy alloy prepared in example 3 consisted mainly of BCC phase, and diffraction peaks of the second phase were not detected due to the low content of the second phase.
The refractory high-entropy alloy prepared in example 3 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 45+ -5 μm, granular second phases were present in the grain interior and at the grain boundaries, and the second phases were found to be (Y, zr) -rich phases in combination with EDS.
Mechanical properties of the refractory high-entropy alloy prepared in example 3 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 925±12MPa, the uniform elongation was 15±5%, and the elongation at break was 22±4%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in the example 3 is subjected to mechanical property test, and according to the test results in the table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Example 4
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing the simple substances corresponding to the elements according to the atomic percentage and putting the simple substances into a non-solventIn a consumable arc melting furnace, the furnace interior is evacuated to a vacuum of 2.0X10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 60h, and then rapidly cooling to room temperature in hot water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 4 had a density of 8.05g/cm 3 The contents of carbon, nitrogen and oxygen were 81wppm, 42wppm and 112wppm, respectively.
As can be seen from the XRD pattern of fig. 1, the refractory high-entropy alloy prepared in example 4 consisted mainly of BCC phase, and diffraction peaks of the second phase were not detected due to the low content of the second phase.
The refractory high-entropy alloy prepared in example 4 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 44+ -3 μm, granular second phases were present in the grain interior and at the grain boundaries, and the second phase was found to be a Y-rich phase in combination with the EDS test results.
Mechanical properties of the refractory high-entropy alloy prepared in example 4 were tested, and according to the test results in table 1, it was found that the tensile strength of the refractory high-entropy alloy at room temperature was 955±24MPa, the uniform elongation was 15±3%, and the elongation at break was 25±3%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in example 4 is subjected to mechanical property test, and according to the test results in table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Example 5
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1250 ℃, the annealing time is 36h, and then rapidly cooling to room temperature in ice brine to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 5 had a density of 8.08g/cm 3 The contents of carbon, nitrogen and oxygen were 78wppm, 45wppm and 125wppm, respectively.
As can be seen from the XRD pattern of fig. 1, the refractory high-entropy alloy prepared in example 5 consisted mainly of BCC phase, and diffraction peaks of the second phase were not detected due to the low content of the second phase.
The refractory high-entropy alloy prepared in example 5 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 41.+ -.5 μm, granular second phases were present in the grain interior and at the grain boundaries, and the second phases were found to be rich (Ce, zr) phases in combination with the EDS test results.
Mechanical properties of the refractory high-entropy alloy prepared in example 5 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 962±21MPa, the uniform elongation was 16±3%, and the elongation at break was 24±2%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in example 5 is subjected to mechanical property test, and according to the test results in table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Example 6
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 72 hours, and then rapidly cooling to room temperature in ice brine to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 6 had a density of 7.92g/cm 3 The contents of carbon, nitrogen and oxygen were 62wppm, 36wppm and 108wppm, respectively.
As can be seen from the XRD pattern of fig. 1, the refractory high-entropy alloy prepared in example 6 consisted mainly of BCC phase, and diffraction peaks of the second phase were not detected due to the low content of the second phase.
The refractory high-entropy alloy prepared in example 6 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 34±6μm, granular second phases were present in the grain interior and at the grain boundaries, and the second phase was a Ce-rich phase as determined by the test results of EDS.
Mechanical properties of the refractory high-entropy alloy prepared in example 6 were tested, and according to the test results in table 1, it was found that the tensile strength of the refractory high-entropy alloy at room temperature was 919±15MPa, the uniform elongation was 18±2%, and the elongation at break was 27±2%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in example 6 is subjected to mechanical property test, and according to the test results in table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Example 7
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements in percentage by atom: 44.91at% of vanadium (V), 37.924at% of niobium (Nb), 9.98at% of tantalum (Ta), 6.986at% of titanium (Ti) and 0.2at% of yttrium (Y).
The specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1200 ℃, the annealing time is 72h, and then rapidly cooling to room temperature in hot water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 7 had a density of 8.18g/cm3 and carbon, nitrogen and oxygen contents of 85wppm, 52wppm and 124wppm, respectively.
From XRD characterization results, it is clear that the refractory high-entropy alloy prepared in example 7 mainly consists of BCC phase, and diffraction peak of the second phase is not detected due to the small content of the second phase.
The refractory high-entropy alloy prepared in example 7 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 40+ -4 μm, granular second phases were present in the grain interior and at the grain boundaries, and the second phase was found to be a Y-rich phase in combination with the EDS test results.
Mechanical properties of the refractory high-entropy alloy prepared in example 7 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 895±15MPa, the uniform elongation was 14±3%, and the elongation at break was 24±3%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in example 7 is subjected to mechanical property test, and according to the test results in table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Example 8
The refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1300 ℃, the annealing time is 48 hours, and then rapidly cooling to room temperature in hot water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in example 8 had a density of 8.18g/cm3 and carbon, nitrogen and oxygen contents of 82wppm, 22wppm and 106wppm, respectively.
From XRD characterization results, it is clear that the refractory high-entropy alloy prepared in example 8 mainly consists of BCC phase, and diffraction peak of the second phase is not detected due to the small content of the second phase.
The refractory high-entropy alloy prepared in example 8 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 61.+ -. 5 μm, granular second phases were present in the grain interior and at the grain boundaries, and the second phase was found to be a Y-rich phase in combination with the EDS test results.
Mechanical properties of the refractory high-entropy alloy prepared in example 8 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 891±14MPa, the uniform elongation was 17±2%, and the elongation at break was 25±4%.
After heat treatment at 700 ℃ and 900 ℃ for 500 hours, respectively, the refractory high-entropy alloy prepared in the example 8 is subjected to mechanical property test, and according to the test results in the table 2, the high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, and the plasticity of the alloy is basically kept unchanged.
Comparative example 1
The refractory high-entropy alloy comprises the following constituent elements in percentage by atom: vanadium (V) 40at%, niobium (Nb) 40at%, tantalum (Ta) 10at%, titanium (Ti) 10at%.
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1300 ℃, the annealing time is 36h, and then rapidly cooling to room temperature in ice brine to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in comparative example 1 had a density of 8.15g/cm 3 The contents of carbon, nitrogen and oxygen were 78wppm, 44wppm and 351wppm, respectively.
The refractory high-entropy alloy prepared in comparative example 1 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 218.+ -. 22 μm, and no second phase was found in the grain interior and at the grain boundary.
The refractory high-entropy alloy prepared in comparative example 1 was heat treated at 900 ℃ for 500 hours under an argon atmosphere, followed by microstructure characterization, and as can be seen from fig. 8, the inside of the heat treated refractory high-entropy alloy grains and the grain boundaries form granular or long-shaped second phases; also, as can be seen from the EDS analysis results of the second phases in fig. 9, these second phases are Ti-rich phases.
Mechanical properties of the refractory high-entropy alloy prepared in comparative example 1 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 907±15MPa, the uniform elongation was 16±4%, and the elongation at break was 25±5%.
After the refractory high-entropy alloy prepared in comparative example 1 is heat-treated at 700 ℃ and 900 ℃ for 500 hours, respectively, mechanical property tests are carried out, and according to the test results in table 2, it is known that the elongation at break of the refractory high-entropy alloy after heat treatment at 700 ℃ and 900 ℃ for 500 hours is 0, which indicates that the refractory high-entropy alloy cannot be used for a long time at high temperature.
Comparative example 2
The refractory high-entropy alloy comprises the following constituent elements in percentage by atom: vanadium (V) 40at%, niobium (Nb) 20at%, tantalum (Ta) 20at%, titanium (Ti) 20at%.
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 in an argon protective atmosphere, wherein the annealing temperature is 1350 ℃, the annealing time is 10 hours, and then rapidly cooling to room temperature in ice brine to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in comparative example 2 had a density of 8.63g/cm 3 The contents of carbon, nitrogen and oxygen were 86wppm, 56wppm and 328wppm, respectively.
The refractory high-entropy alloy prepared in comparative example 2 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 246.+ -.36 μm, and no second phase was found in the grain interior and at the grain boundary.
And carrying out microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 2 after heat treatment for 500 hours at 900 ℃ under the protection of argon, wherein according to test results, granular or long-strip second phases are formed in the grains and grain boundaries of the refractory high-entropy alloy after heat treatment, and according to test results of EDS, the second phases are Ti-rich phases.
Mechanical properties of the refractory high-entropy alloy prepared in comparative example 2 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 743±18MPa, the uniform elongation was 10±4%, and the elongation at break was 21±4%.
After the refractory high-entropy alloy prepared in 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 the test results in table 2, the elongation at break 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 used for a long time at high temperature.
Comparative example 3
The refractory high-entropy alloy comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per pass is 20% and the total deformation is 60%, so as to obtain an alloy plate;
(3) And (3) carrying out high-temperature annealing treatment on the alloy plate under the protection of argon, wherein the annealing temperature is 1300 ℃, the annealing time is 48 hours, and then rapidly cooling to room temperature in room temperature water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in comparative example 3 had a density of 8.13g/cm 3 The contents of carbon, nitrogen and oxygen were 69wppm, 50wppm and 124wppm, respectively.
The refractory high-entropy alloy prepared in comparative example 3 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure with a grain size of 98.+ -. 12 μm, and a granular second phase mainly enriched at grain boundaries was found, and according to the test results by EDS, the second phase was found to be a Y-rich phase.
Mechanical properties of the refractory high-entropy alloy prepared in comparative example 3 were tested, and according to the test results in table 1, it is known that the tensile strength of the refractory high-entropy alloy at room temperature is 825±15MPa, the uniform elongation is 3±3%, and the fracture elongation is only 5±2%, which indicates that the alloy cannot meet the requirement of large deformation.
After the refractory high-entropy alloy prepared in comparative example 3 is heat treated at 700 ℃ and 900 ℃ for 500 hours, respectively, mechanical property tests are carried out, and according to the test results in table 2, it is known that the refractory high-entropy alloy is basically unchanged in strength and plasticity after being heat treated at 700 ℃ and 900 ℃ for 500 hours, but the refractory high-entropy alloy cannot be serviced at high temperature for a long time due to lower elongation at break.
Comparative example 4
The refractory high-entropy alloy comprises the following constituent elements in percentage by atom: vanadium (V) 40at%, niobium (Nb) 30at%, tantalum (Ta) 15at%, titanium (Ti) 14at%, zirconium (Zr) 1.0at%.
The specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 protection of argon, wherein the annealing temperature is 1200 ℃, the annealing time is 60 hours, and then rapidly cooling to room temperature in room temperature water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in comparative example 4 had a density of 7.74g/cm 3 The contents of carbon, nitrogen and oxygen were 102wppm, 84wppm and 286wppm, respectively.
The refractory high-entropy alloy prepared in comparative example 4 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 186+ -39 μm, and no second phase was found in the grain interior and at the grain boundary.
And carrying out microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 4 after heat treatment for 500 hours at 900 ℃ under the protection of argon, and according to test results, 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.
Mechanical properties of the refractory high-entropy alloy prepared in comparative example 4 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 872±15MPa, the uniform elongation was 12±4%, and the elongation at break was 17±2%.
After the refractory high-entropy alloy prepared in comparative 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 elongation at break of the refractory high-entropy alloy is reduced to 6+/-3% and 4+/-2% after the refractory high-entropy alloy is subjected to heat treatment at 700 ℃ and 900 ℃ for 500 hours, which indicates that the alloy cannot be used for a long time at high temperature.
Comparative example 5
The refractory high-entropy alloy comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.0X10 -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy cast ingot, and then rolling at room temperature, wherein the deformation per pass is 20%, 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 protection of argon, wherein the annealing temperature is 1200 ℃, the annealing time is 60 hours, and then rapidly cooling to room temperature in room temperature water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in comparative example 5 had a density of 8.05g/cm 3 The contents of carbon, nitrogen and oxygen were 99wppm, 62wppm and 264wppm, respectively.
From the microstructure characterization result of the refractory high-entropy alloy prepared in comparative example 5, it is understood that the microstructure of the refractory high-entropy alloy prepared in comparative example 5 is an equiaxed grain structure, the grain size is 216±29 μm, and no second phase is found in the interior of the grains and at the grain boundaries.
And carrying out microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 5 after heat treatment for 500 hours at 900 ℃ under the protection of argon, and according to test results, forming irregularly-shaped Zr-rich phases in the grains and grain boundaries of the refractory high-entropy alloy after heat treatment.
Mechanical properties of the refractory high-entropy alloy prepared in comparative example 5 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 934±15MPa, the uniform elongation was 5±4%, and the elongation at break was 7±2%.
After the refractory high-entropy alloy prepared in comparative example 5 is heat-treated at 700 ℃ and 900 ℃ for 500 hours, respectively, mechanical property tests are performed, and according to the test results in table 2, it is known that the elongation at break of the refractory high-entropy alloy after heat treatment at 700 ℃ and 900 ℃ for 500 hours is 0, which indicates that the refractory high-entropy alloy cannot be used for a long time at high temperature.
Comparative example 6
The refractory high-entropy alloy comprises the following constituent elements 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 specific preparation steps of the refractory high-entropy alloy are as follows:
(1) Weighing corresponding simple substances of all elements according to atomic percent, putting the simple substances into a non-consumable arc melting furnace, and vacuumizing the furnace to 2.5X10 s -3 Introducing argon after Pa, then carrying out alloying smelting, cooling and solidifying alloy liquid formed by smelting in a water-cooling copper mold to form an alloy ingot, and then turning over and repeatedly smelting for 6 times to obtain the alloy ingot;
(2) Performing wire-cut electric discharge machining and surface milling on the alloy ingot, and then rolling at room temperature, wherein the deformation per 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 protection of argon, wherein the annealing temperature is 1250 ℃, the annealing time is 36h, and then rapidly cooling to room temperature in room temperature water to obtain the refractory high-entropy alloy.
The refractory high-entropy alloy prepared in comparative example 6 had a density of 8.18g/cm 3 The contents of carbon, nitrogen and oxygen were 115wppm, 52wppm and 325wppm, respectively.
The refractory high-entropy alloy prepared in comparative example 6 was subjected to microstructure characterization, and according to the test results, the refractory high-entropy alloy had an equiaxed grain structure, the grain size was 184.+ -. 29 μm, and no second phase was found in the grain interior and at the grain boundary.
And carrying out microstructure characterization on the refractory high-entropy alloy prepared in the comparative example 6 after heat treatment for 500 hours at 900 ℃ under the protection of argon, and forming needle-shaped Zr-rich phases in the grains and at the grain boundaries of the refractory high-entropy alloy after heat treatment according to test results.
Mechanical properties of the refractory high-entropy alloy prepared in comparative example 6 were tested, and according to the test results in table 1, the tensile strength of the refractory high-entropy alloy at room temperature was 892±15MPa, the uniform elongation was 15±3%, and the elongation at break was 21±4%.
After the refractory high-entropy alloy prepared in comparative example 6 is heat-treated at 700 ℃ and 900 ℃ for 500 hours, respectively, mechanical property tests are performed, and according to the test results in table 2, it is known that the elongation at break of the refractory high-entropy alloy after heat treatment at 700 ℃ and 900 ℃ for 500 hours is 0, which indicates that the refractory high-entropy alloy cannot be used for a long time at high temperature.
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 maintains excellent tissue and mechanical property stability after being subjected to high-temperature long-time heat treatment, and the refractory high-entropy alloy has a broad application prospect.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature is characterized in that: the chemical formula of the refractory high-entropy alloy is expressed 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 Y, ce, la, sc, dy and Er, 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 and high thermal stability at room temperature according to claim 1, wherein the refractory high-entropy alloy is characterized in that: f is more than or equal to 0.1 and less than or equal to 1.5.
3. A method for preparing the refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature according to claim 1 or 2, which is characterized in that: the method specifically comprises the following steps:
(1) Weighing corresponding simple substances of each element according to atomic percentage, putting into a smelting furnace, and vacuumizing to 5 multiplied by 10 -3 Under Pa, then introducing inert gas, and then carrying out alloying smelting to obtain alloy ingots;
(2) Rolling the alloy ingot at room temperature to obtain an alloy plate;
(3) And (3) under the protection of inert gas, performing 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.
4. The method for preparing the refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature according to claim 3, which is characterized by comprising the following steps: the smelting furnace in the step (1) is a non-consumable vacuum arc smelting furnace or a suspension smelting furnace.
5. The method for preparing the refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature according to claim 3, which is characterized by comprising the following steps: the deformation amount of each pass in the rolling treatment in the step (2) is less than or equal to 20 percent, and the total deformation amount is 60 to 90 percent.
6. The method for preparing the refractory high-entropy alloy with high strength and toughness and high thermal stability at room temperature according to claim 3, which is characterized by comprising the following steps: the cooling medium in the step (3) is air, room temperature water, brine 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 |
| CN108998715A (en) * | 2018-08-09 | 2018-12-14 | 北京理工大学 | Infusibility high entropy alloy material and preparation method thereof with large plastometric set ability |
| CN113462948A (en) * | 2021-06-30 | 2021-10-01 | 哈尔滨工程大学 | ZrTiNbAlV low-neutron absorption cross-section refractory high-entropy alloy and preparation method thereof |
| CN113667877A (en) * | 2021-08-12 | 2021-11-19 | 北京理工大学 | TiZrVNb-based high-entropy alloy containing rare earth elements and preparation method thereof |
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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 |
| CN108998715A (en) * | 2018-08-09 | 2018-12-14 | 北京理工大学 | Infusibility high entropy alloy material and preparation method thereof with large plastometric set ability |
| CN113462948A (en) * | 2021-06-30 | 2021-10-01 | 哈尔滨工程大学 | ZrTiNbAlV low-neutron absorption cross-section refractory high-entropy alloy and preparation method thereof |
| CN113667877A (en) * | 2021-08-12 | 2021-11-19 | 北京理工大学 | TiZrVNb-based high-entropy alloy containing rare earth elements and preparation method thereof |
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