CN116162842A - High Jiang Gaoshang alloy and preparation method thereof - Google Patents

High Jiang Gaoshang alloy and preparation method thereof Download PDF

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CN116162842A
CN116162842A CN202310142595.3A CN202310142595A CN116162842A CN 116162842 A CN116162842 A CN 116162842A CN 202310142595 A CN202310142595 A CN 202310142595A CN 116162842 A CN116162842 A CN 116162842A
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entropy alloy
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CN116162842B (en
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李才巨
韦建平
邢辕
李江南
高鹏
易健宏
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Kunming University of Science and Technology
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Abstract

The invention discloses a high Jiang Gaoshang alloy and a preparation method thereof, and belongs to the technical field of alloys. The invention comprises the following elements in atom percent: 24-26% Mn, 24-26% Fe, 24-26% Co, 24-26% Ni. Performing solid-phase sintering on the ball-milled high-entropy alloy powder material in a vacuum hot-pressing sintering furnace to obtain an initial-state high-strength high-entropy alloy; then carrying out cryogenic deformation treatment in liquid nitrogen to obtain the variable-form high-entropy alloy; annealing the deformed high-entropy alloy at 500-800 ℃ for 30min. The high-strength high-entropy alloy crystal structure provided by the invention is face-centered cubic under room temperature environment, and a large amount of submicron scale precipitated phases exist; the grains can be refined through the deep cold deformation treatment process, and then the subsequent annealing treatment is carried out to enable part of alloy grains to grow up, so that the strain hardening capacity and ductility of the alloy are improved, and the provided high-strength high-entropy alloy has extremely high yield strength and good plasticity.

Description

High Jiang Gaoshang alloy and preparation method thereof
Technical Field
The invention relates to a high Jiang Gaoshang alloy and a preparation method thereof, and belongs to the technical field of alloys.
Background
The high-entropy alloy is a novel alloy system different from the traditional alloy design concept, is a solid solution alloy composed of four or more than five components, has the characteristics of high mixed entropy, difficult atomic diffusion, high lattice distortion and the like, so that the high-entropy alloy is easy to obtain solid solution and nano-structure with high thermal stability, even can obtain amorphous structure, and has excellent strength, good plasticity, irradiation resistance, corrosion resistance, wear resistance, excellent ultralow-temperature and high-temperature mechanical properties and the like. The high-entropy alloy is used as a novel metal material, the special performance of the high-entropy alloy plays an increasingly important role in actual production and life, and the high-entropy alloy has huge application potential. However, high entropy alloys also face the same problem as conventional alloys, namely mismatch of strength and plasticity. For example, at room temperature, the high-entropy alloy of FCC phase structure taking Cr, mn, fe, co, ni as main element has an elongation rate of more than 50%, but the yield strength of the high-entropy alloy is not more than 400MPa, while the high-entropy alloy of BCC phase structure has high strength and hardness but poor plasticity, which greatly limits the development and application of the high-entropy alloy in engineering. Therefore, it is of great economic and industrial importance to provide a low cost high entropy alloy with high strength and high plasticity matching at room temperature.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a high-strength high-entropy alloy, which maintains excellent strength and improves plasticity of the high-entropy alloy, and adopts the following technical scheme: the high-strength high-entropy alloy provided by the invention comprises the following elements in atom percent: 24-26% Mn, 24-26% Fe, 24-26% Co, 24-26% Ni.
The invention also aims to provide a preparation method of the high-strength high-entropy alloy, which comprises the following steps:
(1) Respectively weighing high-purity Mn powder, fe powder, co powder and Ni powder according to atomic ratio, and alloying the high-purity simple-substance metal powder by adopting a high-energy ball milling method to obtain the high-entropy alloy powder material with the average particle diameter of 21.07+/-8.8 mu m.
(2) And (3) performing solid-phase sintering on the prepared high-entropy alloy powder material by using a vacuum hot-pressing sintering system to obtain the initial-state high-strength high-entropy alloy.
(3) Soaking the initial state high-strength high-entropy alloy in liquid nitrogen, fully cooling the alloy to the liquid nitrogen temperature, and performing cryogenic deformation treatment to obtain the deformed state high-strength high-entropy alloy.
(4) And carrying out vacuum annealing treatment on the deformed high-strength high-entropy alloy sample, and cooling to room temperature.
Preferably, the purity of the high-purity Mn powder in the step (1) is more than or equal to 99.99%; the purity of the high-purity Fe powder is more than or equal to 99.99 percent; the purity of the high-purity Co powder is more than or equal to 99.99 percent; the purity of the high-purity Ni powder is more than or equal to 99.99 percent.
Preferably, the high purity Mn powder in the step (1) has a particle size of 25 to 45 μm; the grain diameter of the high-purity Fe powder is 25-45 mu m; the grain diameter of the high-purity Co powder is 25-45 mu m; the grain diameter of the high-purity Ni powder is 25-45 mu m.
Preferably, in the step (1), the powder is uniformly mixed and alloyed by adopting a high-energy ball milling method, and the conditions of the high-energy ball milling are as follows: the rotating speed is 100-300 rpm, the ball-material ratio is 5:1-15:1, and the ball milling time is 10-30 h.
Preferably, the sintering temperature in the step (2) is 950-1150 ℃, the sintering pressure is 30-70 MPa, and the vacuum degree is less than or equal to 10Pa.
Preferably, the total deformation in step (3) is 5 to 30%.
Preferably, the annealing temperature in the step (4) is 500-800 ℃, the annealing time is 5-60 min, and the cooling mode is water cooling.
The invention provides a high-strength high-entropy alloy, which comprises the following elements in atomic percent: 24-26% Mn, 24-26% Fe, 24-26% Co, 24-26% Ni. The stacking fault energy value of the obtained high-strength high-entropy alloy is about 21.20mJ/m through the synergistic interaction of the element types and the element contents 2 While lower stacking fault energy is beneficial to the early arrival of twin crystal stress in room temperature environment and the occurrence of nanometer twin crystal in longer strain rangeThis allows the high entropy alloy to more effectively delay necking instability; the high-strength high-entropy alloy has a large amount of submicron-scale precipitated phases (sigma phase rich in Mn element) besides the matrix of the FCC structure; on the one hand, the existence of the precipitated phase can obstruct the movement of dislocation due to interaction of the precipitated phase, thereby improving the deformation resistance (precipitation strengthening) of the alloy; on the other hand, the growth of alloy crystal grains is hindered to refine the alloy crystal grains, so that the number of alloy crystal boundaries is increased; a large number of dislocation packing phenomena (grain boundary strengthening) occur at the grain boundaries due to the fact that the grain boundaries block the movement of dislocations.
In the invention, the Fe element is a matrix element of the high-strength high-entropy alloy, and the higher content of Fe element is beneficial to reducing the cost; the Co element can increase the system mixing entropy and improve the stability of an alloy system; the Ni element is a matrix element of the high-strength high-entropy alloy, and the higher content of the Ni element is beneficial to reducing the cost; the Mn element can increase the system mixing entropy and improve the strength of the alloy.
In addition, the high-strength high-entropy alloy prepared by the method is subjected to cryogenic deformation treatment at the liquid nitrogen temperature, twin crystals can be generated in advance to play a role in strengthening the twin crystals, and alloy strengthening potential is exerted, so that the high-entropy alloy has more excellent strength and plasticity matching; therefore, when the high-strength high-entropy alloy bears stress load, the high-strength high-entropy alloy has extremely high yield strength and good plasticity by jointly contributing to the improvement of the strength of the high-strength high-entropy alloy material through precipitation strengthening, twin crystal strengthening, grain boundary strengthening and the like; the high-strength high-entropy alloy provided by the invention is prepared by adopting a powder metallurgy method, the sintering temperature is lower than the melting point temperature of the alloy, the loss of low-melting-point elements is avoided to a certain extent, and the uniformity of alloy components is ensured.
The invention also provides a preparation method of the high-strength high-entropy alloy, which comprises the following steps: providing a high-entropy alloy powder material; sequentially performing solid-phase sintering, deep-cooling deformation, annealing treatment and the like on the high-entropy alloy powder to finally obtain the high-strength high-entropy alloy; the preparation method provided by the invention combines mechanical alloying, solid phase sintering, deep cold deformation and annealing treatment technologies, and prepares the matrix with heterogeneous phase FCC structure and a large amount of high-strength high-entropy alloy with submicron scale precipitated phases through reasonably adjusting each process step and parameter, so that when the obtained high-strength high-entropy alloy bears stress load, the strength of the high-strength high-entropy alloy material is improved through the common contribution of precipitation strengthening, twin crystal strengthening, grain boundary strengthening and the like, and the obtained high-strength high-entropy alloy has extremely high yield strength, tensile strength and good plastic deformation capability.
Experimental results show that the high-strength high-entropy alloy provided by the invention has tensile yield strength of 967-1400 MPa, tensile strength of 1132-1525 MPa and tensile elongation of 2.85-12.36% at room temperature. Compared with the traditional high-entropy alloy and the preparation method, the invention has extremely high strength and plasticity matched with the alloy, so that the alloy has great application potential in engineering; as can be seen by comparison of the examples, the comprehensive mechanical properties of the alloy are optimal after hot-press sintering, cryogenic deformation treatment and 600 ℃ annealing treatment, the tensile yield strength is 1229MPa, the ultimate tensile strength is 1368MPa, and the tensile elongation is 7.11%; the excellent matching between the strength and the plasticity of the high-strength high-entropy alloy is realized.
Drawings
FIG. 1 is an SEM morphology of the high entropy alloy powder material obtained in example 1;
FIG. 2 is an X-ray diffraction chart of the high entropy alloy powder material obtained in example 1;
FIG. 3 is an X-ray diffraction pattern of the high-strength high-entropy alloy bulk material obtained in examples and comparative examples;
FIG. 4 is a TEM image of the matrix structure and the precipitated phase of the high-strength high-entropy alloy obtained in comparative example 1;
FIG. 5 is a TEM image of the matrix structure and the precipitated phase of the high-strength high-entropy alloy obtained in comparative example 2;
FIG. 6 is a TEM image of the matrix structure and the precipitated phases of the high-strength high-entropy alloy obtained in example 2;
FIG. 7 is a graph showing the tensile engineering stress-strain curve measured at room temperature for the high-strength high-entropy alloy obtained according to the present invention.
Detailed Description
For further explanation of the present invention, the high-strength high-entropy alloy and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention; it will be apparent that the described embodiments are only some, but not all, embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The high-strength high-entropy alloy comprises 25% of Mn, 25% of Fe, 25% of Co and 25% of Ni in terms of atomic percent, wherein the particle size of the high-purity Mn powder is 30 mu m; the grain diameter of the high-purity Fe powder is 25-45 mu m; the grain diameter of the high-purity Co powder is 25-45 mu m; the particle size of the high-purity Ni powder is 25-45 mu m, and the preparation method comprises the following steps:
(1) Respectively weighing high-purity (more than or equal to 99.99%) Mn powder, fe powder, co powder and Ni powder according to atomic ratio, and putting the Mn powder, the Fe powder, the Co powder and the Ni powder into a ball milling tank filled with argon atmosphere; and (3) mechanically alloying the metal powder by adopting a high-energy ball milling method, and adding 1wt% of n-heptane serving as a process control agent into a ball milling tank to finally obtain the high-entropy alloy powder material of the solid solution in order to avoid severe welding of the metal powder during high-energy ball milling. The high-energy ball milling process comprises the following steps: the ball-material ratio is 10:1, the rotating speed is 200rpm, the alloy welding is serious due to the fact that the energy is too high in the ball milling process is avoided, and the high-energy ball milling process is set as follows: and (3) performing forward operation for 20min, stopping for cooling for 10min, performing reverse operation for 20min, and repeatedly and circularly executing the above procedures in sequence until the effective ball milling time is 20h, so as to obtain the high-entropy alloy powder material of the solid solution.
(2) Filling the obtained MnFeCoNi high entropy alloy powder material into a graphite mold with the diameter of 30mm, spraying a high temperature resistant release agent BN between the graphite mold and the high entropy alloy powder (so as to facilitate release), then placing the graphite mold and the high entropy alloy powder into a vacuum hot-pressing sintering furnace, vacuumizing the vacuum hot-pressing sintering furnace to below 10Pa, and applying an axial pressure of 50MPa to the mold; heating to 1050 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, and cooling to room temperature along with a furnace to obtain the initial-state high-strength high-entropy alloy.
(3) Immersing the obtained initial state MnFeCoNi high entropy alloy block material in liquid nitrogen, and performing cryogenic deformation under a hydraulic press after the initial state MnFeCoNi high entropy alloy block material is fully cooled to the liquid nitrogen temperature to obtain the high-strength high entropy alloy with a deformed state, wherein the deformation amount is 10%.
(4) Vacuum packaging the high-strength high-entropy alloy sample with the changed morphology in a quartz tube, placing the quartz tube in a resistance furnace with the temperature of 500 ℃ for heat preservation for 30min for annealing treatment, and then cooling the quartz tube to room temperature by water to obtain the high-strength high-entropy alloy.
The following tests were performed on the high-strength high-entropy alloy obtained in example 1:
fig. 1 is a morphology diagram of a field emission scanning electron microscope of the high-strength high-entropy alloy powder prepared in example 1, and the result shows that the high-entropy alloy powder prepared by high-energy ball milling presents an irregular sphere shape.
The phase of the high-entropy alloy powder material provided by the invention is of an FCC structure, as shown in figure 2, which illustrates that high-energy ball milling can alloy high-purity metal powder; the X-ray diffraction pattern of the high-strength high-entropy alloy block material provided by the invention detects partial precipitated phases besides the matrix with the alloy structure of FCC structure, and the result is shown in figure 3.
FIG. 7 shows the mechanical properties of the high-strength and high-entropy alloy obtained in example 1 of the present invention, and the detection results are: the tensile yield strength is 1359MPa, the ultimate tensile strength is 1461MPa, and the tensile elongation is 3.41%.
Comparative example 1
In contrast, steps (1) and (2) of this example are the same as example 1, but steps (3) and (4) are not performed.
The following tests were performed on the high-strength high-entropy alloy obtained in this example:
the X-ray diffraction pattern of the high-strength high-entropy alloy block material provided by the invention detects partial precipitated phases except for the matrix with an alloy structure of an FCC structure, and the result is shown in figure 3; as can be seen from comparison with example 1, the diffraction peak intensity of the diffraction angle θ=43° in comparative example 1 is much higher than that of example 1, and it can be seen that the crystals of the high-entropy alloy are preferentially oriented in step (3) and step (4).
Fig. 4 is a diagram showing the structure morphology of the high-strength high-entropy alloy block material prepared in comparative example 1 according to the present invention under a transmission electron microscope, and it can be seen that the structure of the high-strength high-entropy alloy consists of a matrix structure and a large number of sub-micron precipitated phases.
FIG. 7 shows the mechanical properties of the high-strength and high-entropy alloy obtained in comparative example 1, and the detection results are: the tensile yield strength is 967MPa, and the ultimate tensile strength is 1132MPa; as can be seen from comparison with example 1, the tensile yield strength of comparative example 1 is reduced by 392MPa compared with example 1, and the ultimate tensile strength is reduced by 329MPa compared with example 1, so that it can be seen that the strength of the high-entropy alloy can be improved in step (3) and step (4), because example 1 can generate twin crystals in advance after the cryogenic deformation treatment to play a role in twin crystal strengthening, exert alloy strengthening potential, and the grain size of the high-entropy alloy after the cryogenic deformation can be reduced to play a role in grain boundary strengthening, thereby enabling the high-entropy alloy to have more excellent strength.
Comparative example 2
In contrast, steps (1), (2) and (3) of this example are the same as example 1, but step (4) is not performed.
The following tests were performed on the high-strength high-entropy alloy obtained in this example:
the X-ray diffraction pattern of the high-strength high-entropy alloy block material provided by the invention detects partial precipitated phases except for the matrix with an alloy structure of an FCC structure, and the result is shown in figure 3; as can be seen from a comparison with example 1, the phase of comparative example 2 still consists of a matrix and a precipitated phase, whereby it can be seen that step (4) has no effect on the phase composition of the high-entropy alloy, since the lower annealing heat treatment temperature does not allow the appearance of new phases or the disappearance of the precipitated phase in the high-entropy alloy system.
Fig. 5 is a diagram showing the structure morphology of the high-strength high-entropy alloy bulk material prepared in comparative example 2 according to the present invention under a transmission electron microscope, and it can be seen that the structure of the high-strength high-entropy alloy is composed of a matrix and a large number of sub-micron precipitated phases, and in addition, the existence of twin crystals is found, because twin crystals are generated in advance after the deep cold deformation treatment in comparative example 2, so that more deformed twin crystals appear in the high-entropy alloy system.
FIG. 7 shows the mechanical properties of the high-strength and high-entropy alloy obtained in comparative example 2, and the detection results are: the tensile yield strength is 1400MPa, and the ultimate tensile strength is 1525MPa; as can be seen by comparing with example 1, the tensile elongation of comparative example 2 is reduced by 0.56% compared to example 1. It can be seen from this that the step (4) can improve the plasticity of the high-entropy alloy because the annealing heat treatment of the step (4) can grow the grains of the high-entropy alloy, and the grain boundary strengthening effect is weakened to some extent, so that the alloy strength is reduced and the plasticity is improved.
Example 2
The high-strength high-entropy alloy comprises 24% of Mn, 26% of Fe, 24% of Co and 26% of Ni in terms of atomic percent, wherein the particle size of the high-purity Mn powder is 45 mu m; the grain diameter of the high-purity Fe powder is 45 mu m; the grain diameter of the high-purity Co powder is 45 mu m; the grain diameter of the high-purity Ni powder is 30 mu m; the preparation method comprises the following steps:
(1) Respectively weighing high-purity (more than or equal to 99.99%) Mn powder, fe powder, co powder and Ni powder according to atomic ratio, and putting the Mn powder, the Fe powder, the Co powder and the Ni powder into a ball milling tank filled with argon atmosphere; and (3) mechanically alloying the metal powder by adopting a high-energy ball milling method, and adding 1wt% of n-heptane serving as a process control agent into a ball milling tank to finally obtain the high-entropy alloy powder material of the solid solution in order to avoid severe welding of the metal powder during high-energy ball milling. The high-energy ball milling process comprises the following steps: the ball-material ratio is 5:1, the rotating speed is 200rpm, the alloy welding is serious due to the fact that the energy is too high in the ball milling process is avoided, and the high-energy ball milling process is set as follows: and (3) performing forward operation for 20min, stopping for cooling for 10min, performing reverse operation for 20min, and repeatedly and circularly executing the above procedures in sequence until the effective ball milling time is 20h, so as to obtain the high-entropy alloy powder material of the solid solution.
(2) Filling the obtained MnFeCoNi high entropy alloy powder material into a graphite mold with the diameter of 30mm, spraying a high temperature resistant release agent BN between the graphite mold and the high entropy alloy powder (so as to facilitate release), then placing the graphite mold and the high entropy alloy powder into a vacuum hot-pressing sintering furnace, vacuumizing the vacuum hot-pressing sintering furnace to below 10Pa, and applying an axial pressure of 50MPa to the mold; heating to 950 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, and cooling to room temperature along with a furnace to obtain the initial state high-strength high-entropy alloy.
(3) Immersing the obtained initial state MnFeCoNi high entropy alloy block material in liquid nitrogen, and performing cryogenic deformation under a four-column hydraulic press after the initial state MnFeCoNi high entropy alloy block material is fully cooled to the liquid nitrogen temperature to obtain the high-strength high entropy alloy with a deformed state, wherein the deformation amount is 3%.
(4) Vacuum packaging the high-strength high-entropy alloy sample with the changed morphology in a quartz tube, placing the quartz tube in a resistance furnace with the temperature of 600 ℃ for heat preservation for 60min for annealing treatment, and then cooling the quartz tube to room temperature by water to obtain the high-strength high-entropy alloy.
The following tests were performed on the high-strength high-entropy alloy obtained in example 2:
the X-ray diffraction pattern of the high-strength high-entropy alloy block material provided by the invention detects partial precipitated phases besides the matrix with the alloy structure of FCC structure, and the result is shown in figure 3.
Fig. 6 is a diagram of the structure morphology of the high-strength high-entropy alloy block material prepared in example 2 of the present invention under a transmission electron microscope, and it can be seen that the structure of the high-strength high-entropy alloy consists of a matrix structure and a large number of submicron precipitated phases, and in addition, a large number of deformed twins are found.
FIG. 7 shows the mechanical properties of the high-strength and high-entropy alloy obtained in example 2 of the present invention, and the detection results are: the tensile yield strength is 1229MPa, the ultimate tensile strength is 1368MPa, and the tensile elongation is 7.11%.
Example 3
The high-strength high-entropy alloy comprises 26% of Mn, 24% of Fe, 26% of Co and 24% of Ni in terms of atomic percent, wherein the particle size of the high-purity Mn powder is 25 mu m; the grain diameter of the high-purity Fe powder is 25 mu m; the grain diameter of the high-purity Co powder is 25 mu m; the grain diameter of the high-purity Ni powder is 25 mu m; the preparation method comprises the following steps:
(1) Respectively weighing high-purity (more than or equal to 99.99%) Mn powder, fe powder, co powder and Ni powder according to atomic ratio, and putting the Mn powder, the Fe powder, the Co powder and the Ni powder into a ball milling tank filled with argon atmosphere; and (3) mechanically alloying the metal powder by adopting a high-energy ball milling method, and adding 1wt% of n-heptane serving as a process control agent into a ball milling tank to finally obtain the high-entropy alloy powder material of the solid solution in order to avoid severe welding of the metal powder during high-energy ball milling. The high-energy ball milling process comprises the following steps: the ball-material ratio is 15:1, the rotating speed is 300rpm, the alloy welding is serious due to the fact that the energy is too high in the ball milling process is avoided, and the high-energy ball milling process is set as follows: and (3) performing forward operation for 20min, stopping for cooling for 10min, performing reverse operation for 20min, and repeatedly and circularly executing the above procedures in sequence until the effective ball milling time is 20h, so as to obtain the high-entropy alloy powder material of the solid solution.
(2) Filling the obtained MnFeCoNi high entropy alloy powder material into a graphite mold with the diameter of 30mm, spraying a high temperature resistant release agent BN between the graphite mold and the high entropy alloy powder (so as to facilitate release), then placing the graphite mold and the high entropy alloy powder into a vacuum hot-pressing sintering furnace, vacuumizing the vacuum hot-pressing sintering furnace to below 10Pa, and applying an axial pressure of 70MPa to the mold; heating to 1050 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, and cooling to room temperature along with a furnace to obtain the initial-state high-strength high-entropy alloy.
(3) Immersing the obtained initial state MnFeCoNi high entropy alloy block material in liquid nitrogen, and performing cryogenic deformation under a four-column hydraulic press after the initial state MnFeCoNi high entropy alloy block material is fully cooled to the liquid nitrogen temperature to obtain the high-strength high entropy alloy with a deformed state, wherein the deformation amount is 20%.
(4) Vacuum packaging the high-strength high-entropy alloy sample with the changed morphology in a quartz tube, placing the quartz tube in a resistance furnace at 700 ℃ for heat preservation for 30min for annealing treatment, and then cooling the quartz tube to room temperature by water to obtain the high-strength high-entropy alloy.
The following tests were performed on the high-strength high-entropy alloy obtained in example 3:
in the X-ray diffraction pattern of the high-strength high-entropy alloy bulk material according to this example, a part of precipitated phases were detected in addition to the matrix having an FCC structure as the alloy structure, and the result is shown in fig. 3.
FIG. 7 shows the mechanical properties of the high-strength and high-entropy alloy obtained in example 3 of the present invention, and the detection results are: the tensile yield strength is 1167MPa, the ultimate tensile strength is 1342MPa, and the tensile elongation is 9.26%.
Example 4
The high-strength high-entropy alloy comprises 25% of Mn, 25% of Fe, 25% of Co and 25% of Ni in terms of atomic percent, wherein the particle size of the high-purity Mn powder is 30 mu m; the grain diameter of the high-purity Fe powder is 25-45 mu m; the grain diameter of the high-purity Co powder is 45 mu m; the particle size of the high-purity Ni powder is 25-45 mu m, and the preparation method comprises the following steps:
(1) Respectively weighing high-purity (more than or equal to 99.99%) Mn powder, fe powder, co powder and Ni powder according to atomic ratio, and putting the Mn powder, the Fe powder, the Co powder and the Ni powder into a ball milling tank filled with argon atmosphere; and (3) mechanically alloying the metal powder by adopting a high-energy ball milling method, and adding 1wt% of n-heptane serving as a process control agent into a ball milling tank to finally obtain the high-entropy alloy powder material of the solid solution in order to avoid severe welding of the metal powder during high-energy ball milling. The high-energy ball milling process comprises the following steps: the ball-material ratio is 8:1, the rotating speed is 100rpm, the alloy welding is serious due to the fact that the energy is too high in the ball milling process is avoided, and the high-energy ball milling process is set as follows: and (3) performing forward operation for 20min, stopping for cooling for 10min, performing reverse operation for 20min, and repeatedly and circularly executing the above procedures in sequence until the effective ball milling time is 20h, so as to obtain the high-entropy alloy powder material of the solid solution.
(2) Filling the obtained MnFeCoNi high entropy alloy powder material into a graphite mold with the diameter of 30mm, spraying a high temperature resistant release agent BN between the graphite mold and the high entropy alloy powder (so as to facilitate release), then placing the graphite mold and the high entropy alloy powder into a vacuum hot-pressing sintering furnace, vacuumizing the vacuum hot-pressing sintering furnace to below 10Pa, and applying an axial pressure of 30MPa to the mold; heating to 1150 ℃ at a heating rate of 20 ℃/min, preserving heat for 1h, and cooling to room temperature along with a furnace to obtain the initial state high-strength high-entropy alloy.
(3) Immersing the obtained initial state MnFeCoNi high entropy alloy block material in liquid nitrogen, and performing cryogenic deformation under a four-column hydraulic press after the initial state MnFeCoNi high entropy alloy block material is fully cooled to the liquid nitrogen temperature to obtain the high-strength high entropy alloy with a deformed state, wherein the deformation amount is 30%.
(4) Vacuum packaging the high-strength high-entropy alloy sample with the changed morphology in a quartz tube, placing the quartz tube in a resistance furnace with the temperature of 800 ℃ for 5min for annealing treatment, and then cooling the quartz tube to room temperature by water to obtain the high-strength high-entropy alloy.
The following tests were performed on the high-strength high-entropy alloy obtained in example 4:
the X-ray diffraction pattern of the high-strength high-entropy alloy block material provided by the invention detects partial precipitated phases besides the matrix with the alloy structure of FCC structure, and the result is shown in figure 3.
FIG. 7 shows the mechanical properties of the high-strength and high-entropy alloy obtained in example 4 of the present invention, and the detection results are: the tensile yield strength is 975MPa, the ultimate tensile strength is 1264MPa, and the tensile elongation is 12.02%.
The above description is only of the preferred embodiments of the present invention, and is only for the purpose of illustrating the present invention, not for limiting the same; any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.

Claims (8)

1. A high strength high entropy alloy, comprising, in atomic percent: 24-26% Mn, 24-26% Fe, 24-26% Co, 24-26% Ni.
2. The method for preparing the high-strength high-entropy alloy according to claim 1, wherein: the particle size of the high-purity Mn powder in the step (1) is 25-45 mu m; the grain diameter of the high-purity Fe powder is 25-45 mu m; the grain diameter of the high-purity Co powder is 25-45 mu m; the grain diameter of the high-purity Ni powder is 25-45 mu m.
3. The method for preparing a high-strength high-entropy alloy according to claim 1 or 2, characterized in that it comprises the following steps:
(1) Respectively weighing high-purity Mn powder, fe powder, co powder and Ni powder according to an equal atomic ratio, and alloying the high-purity simple-substance metal powder by adopting a high-energy ball milling method to obtain a high-entropy alloy powder material;
(2) Carrying out solid-phase sintering on the prepared high-entropy alloy powder material by using a vacuum hot-pressing sintering system to obtain an initial-state high-strength high-entropy alloy;
(3) Soaking the obtained initial state high-strength high-entropy alloy in liquid nitrogen, fully cooling the alloy to the liquid nitrogen temperature, and performing cryogenic deformation treatment to obtain the deformed state high-strength high-entropy alloy;
(4) And carrying out vacuum annealing treatment on the deformed high-strength high-entropy alloy sample, and cooling to room temperature.
4. The method for producing a high-strength high-entropy alloy according to claim 3, wherein: the purity of the high-purity Mn powder in the step (1) is more than or equal to 99.99 percent; the purity of the high-purity Fe powder is more than or equal to 99.99 percent; the purity of the high-purity Co powder is more than or equal to 99.99 percent; the purity of the high-purity Ni powder is more than or equal to 99.99 percent.
5. The method for producing a high-strength high-entropy alloy according to claim 3, wherein: in the step (1), the powder is uniformly mixed and alloyed by adopting a high-energy ball milling method, and the conditions of the high-energy ball milling are as follows: the rotating speed is 100-400 rpm, the ball-material ratio is 5:1-20:1, and the ball milling time is 10-40 h.
6. The method for preparing the high-strength high-entropy alloy according to claim 2, wherein: the sintering temperature in the step (2) is 800-1200 ℃, the sintering pressure is 30-80 MPa, and the vacuum degree is less than or equal to 10Pa.
7. The method for preparing the high-strength high-entropy alloy according to claim 2, wherein: the total deformation in the step (3) is 5-30%.
8. The method for preparing the high-strength high-entropy alloy according to claim 2, wherein: the annealing temperature in the step (4) is 500-800 ℃, the annealing time is 5-60 min, and the cooling mode is water cooling.
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