CN115725888B - Nanophase reinforced TiNiCuHfZr high-entropy shape memory alloy and preparation method thereof - Google Patents
Nanophase reinforced TiNiCuHfZr high-entropy shape memory alloy and preparation method thereof Download PDFInfo
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application relates to the technical field of shape memory alloys, in particular to a nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy and a preparation method thereof. The TiNiCuHfZr high-entropy high-strength shape memory alloy provided by the application comprises the following chemical components in percentage by atom: 30% -39% of Ti, 44% of Ni, 10% of Hf, 6% of Cu and 1% -10% of Zr. The alloy is prepared by the following method: the Ti, ni, hf, cu, zr raw materials with the composition ratio are placed in a vacuum arc melting furnace, and are repeatedly melted to obtain alloy ingots, and the as-cast TiNiCuHfZr high-entropy memory alloy is subjected to solution treatment and aging treatment, so that the nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy can be obtained. Compared with the prior art, the high-entropy shape memory alloy prepared by the application has obviously improved yield strength, output stress and output work. In addition, the preparation process is convenient, only needs arc melting and low-temperature short-time heat treatment, does not need long-time homogenization heat treatment and plastic deformation processing, is easy to operate, and has very good application prospect.
Description
Technical Field
The application belongs to the technical field of alloy materials and preparation thereof, and particularly relates to a nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy and a preparation method thereof. Compared with similar materials, the application has the advantages of obviously improved yield strength, output stress and output work, excellent memory performance, uniform and fine reinforcing phase and nanometer grade.
Background
A shape memory alloy is a material that has a thermoelastic or stress-induced martensitic transformation that, after a certain degree of deformation, is able to fully or partially revert to its pre-deformed shape and volume by heating or stress unloading. Important indexes for measuring the performance of the shape memory alloy are mechanical performance (yield strength, breaking strength, plasticity and the like), memory performance (recoverable strain, super-elastic strain and the like), stability performance and the like. When the shape memory alloy has high strength and large recoverable strain, the shape memory alloy has higher output work (product of output stress and recoverable strain), and has important application value in the fields of medical instruments, shock resistance and damping structures, mechanical connection, driving devices and the like.
In 2014, the first time the Ukraut scholars first proposed high-entropy memory alloy, which has higher work output compared with the common memory alloy due to the effect of improving the alloy strength of 'lattice distortion'. To further improve the properties of as-cast high-entropy memory alloys, various processes have been performed on them. Such as: chen et al homogenizing TiZrHfCoNiCu-series as-cast high-entropy memory alloy firstly proposed by Firstov at 900 ℃ for 24 hours, then homogenizing heat treatment at 950 ℃ for 12 hours, then carrying out solution treatment at 1000 ℃ for 2 hours, and finally raising the maximum recoverable strain of the as-cast high-entropy memory alloy from 1.63% to 4.8%, raising the loading stress from 500MPa to 650MPa and outputting work from 8.15J/cm 3 Increased to 31.2J/cm 3 (C.H.Chen, Y.J.Chen, et al, scripta Materialia,2019, 162:185-189); piorunek et al annealed a TiZrHfNiCuPd et al atomic ratio as-cast high-entropy memory alloy at 900 ℃ for 100 hours to obtain a high-entropy memory alloy with a transformation temperature of 100-200 ℃ (D.Piorunek, J.Frenzel, et al, intermetallics,2020, 122:106792);yaacoub et al will be as-cast (TiZrHf) 50 Ni 25 Co 10 Cu 15 After the high-entropy memory alloy is subjected to solution treatment at 1050 ℃ for 2-6 hours and then is subjected to aging treatment at 400-450 ℃ for 1.5 hours, the maximum recoverable strain of the obtained high-entropy memory alloy is 5%, the output stress is 1000-1200MPa, and the yield strength is about 400-600MPa (J.Yaacoub, W.Abuzaid, scripta Materialia,2020, 186:43-47); the TiZrHfAlNb high-entropy memory alloy reported by Wang et al is beta titanium alloy, and is prepared by cold-rolling 40% of the as-cast alloy, and then annealing at 800-900 ℃ for 30 minutes to obtain an alloy with a yield strength of about 350-480MPa, a breaking strength of about 900MPa, a maximum recoverable strain of 5.2% and a complete recoverable strain of 4% (Lu Wang, chao Fu, et al, scripta Materialia,2019, 162:112-117); the TiZrHfNbTaSn high-entropy memory alloy beta titanium alloy reported by Gao et al is prepared by cold rolling and then recrystallization annealing at 750 ℃ for 30 minutes. The maximum recoverable strain of the alloy can reach 3.8% with corresponding yield and break strengths of about 500MPa and 800MPa (J.J.Gao, P.Castany, et al Scripta Materialia,2021, 198:113824).
As is clear from the above prior art, the following problems still remain in further improving the overall properties of the high-entropy shape memory alloy: (1) As-cast high-entropy shape memory alloys are reported, the mechanical properties and memory properties of the high-entropy shape memory alloys are required to be further improved. However, the current technical process for improving the performance of the high-entropy shape memory alloy is complex, part of the alloy needs plastic deformation processes such as cold rolling, hot rolling and the like, the heat treatment temperature of part of the alloy is high (900-1000 ℃) and the time is too long (as the heat treatment time of the TiZrHfCoNiCu alloy is 12-24 hours, the TiZrHfNiCuPd even exceeds 100 hours), the preparation process is complex and a large amount of energy sources are consumed; (2) Reported as-cast high entropy shape memory alloys have limited performance improvement after heat treatment. The main reasons are as follows: the main principle of the performance improvement of the alloys after heat treatment is that the compound phase is dissolved into the matrix to strengthen the lattice distortion of the high-entropy alloy, thereby playing the role of solid solution strengthening. While the precipitation of the nano-reinforced phase of the high-entropy memory alloy by the heat treatment process has not been reported yet; (3) The high-entropy shape memory alloy reported at present cannot have both high yield strength and large recoverable strain, so that the output stress, output work and the like of the existing alloy are required to be further improved. In particular, during low strain loading, the prior alloy cannot continuously provide higher output stress and output work, so the yield strength of the as-cast high-entropy memory alloy needs to be further improved.
In summary, in the field of improving the performance of the high-entropy shape memory alloy, various problems still exist to be solved, and further optimization of alloy components and simplification of the preparation process are required, so that the comprehensive performance of the as-cast high-entropy memory alloy is further improved, and the application range of the alloy is widened.
Disclosure of Invention
In view of the problems existing in the prior art, the application provides a nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy and a preparation method thereof, the preparation process is simple, the alloy structure has uniform and fine nano-grade reinforced phases, and the alloy structure has remarkably improved yield strength, output stress and output work and has excellent memory performance.
In order to achieve the purpose, the application adopts the following technical scheme:
a nanophase reinforced TiNiCuHfZr high entropy shape memory alloy, the raw materials of the alloy comprising the following chemical components in atomic percent: 30% -39% of Ti, 44% of Ni, 10% of Hf, 6% of Cu and 1% -10% of Zr.
Preferably, the alloy has a structure composition comprising a B2 austenitic matrix, nano-scale Ti 2 Ni-based reinforcement phase in which nano-scale Ti 2 The size of the Ni-based reinforcing phase is 40-150 nm, and the number is 5-50 per square micron.
A method for manufacturing a nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy, the alloy preparation method comprises the following steps:
1) Batching and smelting: raw material Ti, ni, hf, cu, zr is prepared according to atomic percent, the raw material Ti, ni, hf, cu, zr is placed into a vacuum arc melting furnace, argon is filled after vacuumizing to prevent oxidation in the alloy melting process, and the alloy is repeatedly melted in a molten state to uniformly mix alloy components, so that the as-cast TiNiCuHfZr high-entropy shape memory alloy is obtained;
2) Solution treatment: placing the cast TiNiCuHfZr high-entropy shape memory alloy obtained in the step 1) into a resistance furnace, performing solution treatment, and quenching and cooling in water;
3) Primary aging treatment: placing the TiNiCuHfZr high-entropy shape memory alloy subjected to solution treatment obtained in the step 2) into a resistance furnace, performing primary aging treatment, and then performing air cooling to obtain the nano-phase reinforced high-entropy shape memory alloy subjected to primary aging treatment;
4) And (3) secondary aging treatment: and (3) placing the nano-phase reinforced high-entropy shape memory alloy obtained in the step (3) after the primary aging treatment into a resistance furnace, performing secondary aging treatment, and then air-cooling to obtain the nano-phase reinforced high-entropy shape memory alloy after the secondary aging treatment.
Preferably, in the step 1), the vacuum degree of the vacuum arc melting furnace is less than 10 -3 Pa, the pressure in the smelting furnace after argon is filled is-0.06-0.08 MPa, and the smelting current is 200-340A; the repeated re-smelting times are more than 5 times, and each time the melting state is kept for 1-2 minutes.
Preferably, in the step 2), the solution treatment temperature is 800-900 ℃ and the heat preservation time is 30-50 minutes.
Preferably, in the step 3), the temperature of the primary aging treatment is 300-350 ℃ and the heat preservation time is 120-180 minutes.
Further preferably, in the step 3), the alloy is heated up along with the furnace during the primary aging treatment, and the heating rate is 10-15 ℃/min.
Preferably, in the step 4), the temperature of the secondary aging treatment is 400-450 ℃ and the heat preservation time is 120-180 minutes.
Further preferably, in the step 4), the alloy is heated up along with the furnace during the secondary aging treatment, and the heating rate is 10-15 ℃/min.
Further preferably, the temperature of the solution treatment in the step 2) is 800 ℃, the heat preservation time is 30 minutes, the temperature of the alloy is increased along with the furnace, and the temperature rising rate is 10-15 ℃/min.
Further preferably, the temperature of the aging treatment in the step 3) is 300 ℃, the heat preservation time is 120 minutes, the temperature of the alloy is increased along with the furnace, and the temperature rising rate is 10-15 ℃/min.
Further preferably, the temperature of the aging treatment in the step 4) is 400 ℃, the heat preservation time is 120 minutes, the temperature of the alloy is increased along with the furnace, and the temperature rising rate is 10-15 ℃/min.
After the primary aging treatment in the step 3), a small amount of nano reinforcing phases are precipitated in the alloy, the number is 5-10 per square micrometer, and the size is 40-80 nanometers. The properties are significantly improved compared to the as-cast structure of step 1). When the loading strain is 2% -15%, the output stress can be maximally increased by 14% -72%, the output work can be maximally increased by 32% -62%, the critical yield strength can be maximally increased by 113MPa (17.4%), the yield strength can be maximally increased by 265MPa (14.2%), and the output work can be maximally increased by 24.9J/cm 3 (15.2％)。
After the secondary aging treatment in the step 4), a large amount of nanoscale reinforcing phases are precipitated in the alloy, the number of the nanoscale reinforcing phases is 40-50 per square micrometer, and the size of the nanoscale reinforcing phases is 80-150 nanometers. Compared with the cast high-entropy memory alloy in the step 1), the performance is obviously improved. When the loading strain is 2% -15%, the output stress can be increased by 33% -105% at maximum, the output work can be increased by 32% -136% at maximum, the critical yield strength can be increased by 350MPa (54%) at maximum, the yield strength can be increased by 205MPa (13.6%) at maximum, the output stress can be increased by 294MPa (20.1%) at maximum, and the output work can be increased by 16J/cm at maximum 3 (11.3％)。
The application has the following beneficial effects:
(1) The high entropy shape memory alloy of the present application has a high yield strength. Compared with the prior art, the reason for improving the yield strength of the alloy is as follows: (1) the aging treatment process separates out a nanoscale reinforcing phase, which is a main factor for improving the yield strength of the alloy; (2) the lattice distortion effect of the high-entropy alloy enhances the solid solution strengthening effect, ti, hf and Zr are in the same period with the main group, ni and Cu can replace the mutual solid solution, and the alloy yield strength can be further improved; (3) the higher Ni content (44%) and the lower Cu content (6%) ensure that the alloy has high strength and good plasticity;
(2) The high-entropy shape memory alloy has excellent memory performance. Compared with the prior art, the alloy has excellent memory performance due to the following reasons: (1) the Ti element (Ti, hf, zr) and the Ni element (Ni, cu) are 50% each, so that the good memory performance of the alloy is ensured, and the alloy has large recoverable strain. (2) The Zr element changes within the range of 1-10 percent, and has positive effects on improving the plasticity and toughness of the alloy and adjusting the phase transition temperature of the alloy;
(3) The high-entropy shape memory alloy has high output work in the whole strain loading interval. Compared with the prior art, the alloy has high yield strength and large recoverable strain, can uniformly and continuously have high output stress and high output work in the whole strain loading process (including a low strain zone), and greatly expands the application range of the high-entropy memory alloy.
(4) The preparation process is convenient. The application is based on the as-cast TiNiCuHfZr high-entropy shape memory alloy, optimizes the performance of the as-cast high-entropy shape memory alloy by adjusting the content of Zr element, does not need plastic deformation such as cold rolling, hot rolling and the like, and can further improve the comprehensive performance of the high-entropy shape memory alloy only through simple solid solution treatment and low-temperature short-time aging treatment. Because the ageing temperature is low and the time is short, the vacuumizing or sealing anti-oxidation treatment is not needed, the preparation convenience of the alloy can be further improved, and the cost is reduced.
Drawings
FIG. 1 shows the microstructure of the alloys prepared in example 1, example 2 and comparative example 1;
FIG. 2 shows the microstructure of the alloys prepared in example 3, example 4 and comparative example 2;
FIG. 3 shows the microstructure of the alloys prepared in example 5, example 6, and comparative example 3;
FIG. 4 is a graph showing the comparison of the output stress and the output work of the alloys prepared in example 1, example 2 and comparative example 1;
FIG. 5 is a graph showing the comparison of the output stress and the output work of the alloys prepared in example 3, example 4 and comparative example 2;
FIG. 6 is a graph showing the output stress versus output work of the alloys prepared in example 5, example 6, and comparative example 3;
FIG. 7 is a graph showing the memory performance test of examples 1-6 and comparative examples 1-3
FIG. 8 is a graph showing the microstructure and memory properties of the alloys prepared in comparative examples 4-6.
The specific embodiment is as follows:
the application will be further described with reference to the accompanying drawings and tables.
Example 1
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking the alloy 1 as an alloy with the atomic ratio of 39% Ti, 44% Ni, 10% Hf, 6% Cu and 1% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 And (3) charging argon to below Pa, striking an arc after charging the argon to-0.06 MPa, controlling the smelting current to be 200-300A, and continuously heating the alloy for more than 2 minutes in an alloy molten state to ensure that all metals are completely melted together, overturning the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy. The cast high-entropy memory alloy is put into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. Finally, the alloy 1 subjected to solution treatment is put into a resistance furnace again, heated to 300 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, and the high-entropy shape memory alloy 1:Ti subjected to primary aging treatment is obtained 39 Ni 44 Hf 10 Cu 6 Zr 1 。
The microstructure of alloy 1 is shown in fig. 1 (b), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 4, and the cyclic loading stress-strain curve is shown in fig. 7. In comparison to the as-cast structure of comparative example 1 in FIG. 1 (a), a small amount of nanoscale reinforcing phase is precipitated in alloy 1, about 10 per square micron, and about 45-83 nanometers in size. As is clear from the statistics of Table 1, the maximum output stress of alloy 1 was increased by 238MPa (16.1%) as compared with the as-cast alloy of comparative example 1, and the critical yield strength and yield strength were also increased, and the maximum recoverable strain, maximum output work and other parameters were equivalent to those of the as-cast alloy of comparative example 1. When the loading strain is 2% -15%, the output stress is improved by 16% -72% (fig. 4 (a)), and the output work is improved by 4% -62% (fig. 4 (b)).
Example 2
With high-purity metal Ti, ni, hf, cu, zr asThe raw materials are cleaned by alcohol and then are prepared into alloy 2 according to the atomic ratio of 39 percent Ti, 44 percent Ni, 10 percent Hf, 6 percent Cu and 1 percent Zr, the raw materials are placed into a vacuum arc furnace, and the vacuum is pumped to 10 percent -3 And (3) charging argon to below Pa, striking an arc after charging the argon to-0.06 MPa, controlling the smelting current to be 200-300A, and continuously heating the alloy for more than 2 minutes in an alloy molten state to ensure that all metals are completely melted together, overturning the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy. The cast high-entropy memory alloy is put into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. And (3) putting the alloy 2 subjected to solution treatment into a resistance furnace again, heating to 300 ℃ along with the furnace, preserving heat for 120 minutes, and then cooling in air to obtain the alloy 2 subjected to primary aging treatment. Finally, the alloy 2 subjected to primary aging treatment is put into a resistance furnace again, heated to 400 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, and the high-entropy shape memory alloy 2:Ti subjected to secondary aging treatment is obtained 39 Ni 44 Hf 10 Cu 6 Zr 1 。
The microstructure of alloy 2 is shown in fig. 1 (c) and fig. 1 (d), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 4, and the cyclic loading stress-strain curve is shown in fig. 7. In comparison to the as-cast structure of comparative example 1 in FIG. 1 (a), a significant amount of nanoscale reinforcing phase is precipitated in alloy 2, about 55 per square micron, and about 75-140 nanometers in size. As can be seen from the statistics in Table 1, the critical yield strength of alloy 2 was increased by 43MPa (11.5%), the yield strength was increased by 205MPa (13.6%), the maximum output stress was increased by 294MPa (20.1%), and the maximum output work was increased by 12.4J/cm as compared with the as-cast alloy of comparative example 1 3 (11.3%). When the loading strain is 2% -15%, the output stress is increased by 20% -105% (fig. 4 (a)), and the output work is increased by 12% -136% (fig. 4 (b)).
Example 3
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking alloy 3 as an alloy 3 according to an atomic ratio of 35% Ti, 44% Ni, 10% Hf, 6% Cu and 5% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 Charging argon gas below Pa to-0.06 MPa, striking arc, controlling smelting current at 230-300A, and alloyingAnd (3) continuing for more than 2 minutes in a molten state, ensuring that after all metals are completely melted together, overturning the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy. The cast high-entropy memory alloy is put into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. Finally, the alloy 3 subjected to solution treatment is put into a resistance furnace again, heated to 300 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, and the high-entropy shape memory alloy 3:Ti subjected to primary aging treatment is obtained 35 Ni 44 Hf 10 Cu 6 Zr 5 。
The microstructure of alloy 3 is shown in fig. 2 (b), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 5, and the cyclic loading stress-strain curve is shown in fig. 7. In comparison to the as-cast structure of comparative example 2 in FIG. 2 (a), a small amount of nanoscale reinforcing phase is precipitated in alloy 3, about 5 per square micron, and about 40-80 nanometers in size. As can be seen from the statistics in Table 1, the critical yield strength of alloy 3 is increased by 60MPa (10.5%), the yield strength is increased by 110MPa (6.3%), the maximum output stress is increased by 76MPa (4.1%), the maximum recoverable strain is increased by 1.0 (11.5%), and the maximum output work is increased by 24.9J/cm as compared with the as-cast alloy of comparative example 2 3 (15.2%). When the strain is loaded by 2% -15%, the output stress is improved by 6% -14% (fig. 5 (a)), and the output work is improved by 10% -32% (fig. 5 (b)).
Example 4
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking alloy 4 as an alloy according to an atomic ratio of 35% Ti, 44% Ni, 10% Hf, 6% Cu and 5% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 And (3) charging argon to below Pa, striking an arc after the argon is charged to-0.06 MPa, controlling the smelting current to be 230-300A, and keeping for more than 2 minutes in an alloy melting state to ensure that all metals are completely melted together. And turning over the obtained alloy ingot by using a mechanical arm, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy. The cast high-entropy memory alloy is put into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. The alloy 4 subjected to solution treatment is put into a resistance furnace againAnd (3) heating to 300 ℃ along with a furnace, preserving heat for 120 minutes, and then air-cooling to obtain the high-entropy shape memory alloy 4 subjected to primary aging treatment. Finally, the alloy 4 subjected to primary aging treatment is placed into a resistance furnace again, heated to 400 ℃ along with the furnace, kept for 120 minutes and then air-cooled to obtain the high-entropy shape memory alloy 4 subjected to secondary aging treatment: ti (Ti) 35 Ni 44 Hf 10 Cu 6 Zr 5 。
The microstructure of alloy 4 is shown in fig. 2 (c) and fig. 1 (d), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 5, and the cyclic loading stress-strain curve is shown in fig. 7. In comparison to the as-cast structure of comparative example 2 in FIG. 2 (a), a significant amount of nanoscale reinforcing phase is precipitated in alloy 4, about 50 per square micron, and about 80-150 nanometers in size. As can be seen from the statistics of Table 1, the critical yield strength of the alloy is increased by 310MPa (54.4%), the yield strength is increased by 180MPa (10.5%), the maximum output stress is increased by 110MPa (5.9%), the maximum recoverable strain is increased by 0.4 (4.6%), and the maximum output work is increased by 16.0J/cm, as compared with the as-cast alloy of comparative example 2 3 (9.8%). When the strain is loaded by 4% -15%, the output stress is increased by 24% -45% (fig. 5 (a)), and the output work is increased by 10% -32% (fig. 5 (b)).
Example 5
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking alloy 5 as an alloy according to an atomic ratio of 30% Ti, 44% Ni, 10% Hf, 6% Cu and 10% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 And (3) charging argon to below Pa, striking an arc after charging the argon to-0.06 MPa, controlling the smelting current to be 250-310A, and continuously maintaining the smelting current for more than 2 minutes in an alloy melting state, ensuring that all metals are completely melted together, overturning the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy. The cast high-entropy memory alloy is put into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. Finally, the alloy 5 subjected to solution treatment is put into a resistance furnace again, heated to 300 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, and the high-entropy shape memory alloy 5:Ti subjected to primary aging treatment is obtained 30 Ni 44 Hf 10 Cu 6 Zr 10 。
The microstructure of alloy 5 is shown in fig. 3 (b), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 6, and the cyclic loading stress-strain curve is shown in fig. 7. In comparison to the as-cast structure of comparative example 2 in FIG. 2 (a), a small amount of nanoscale reinforcing phase is precipitated in alloy 5, about 6 per square micron, and about 40-75 nanometers in size. As can be seen from the statistics of Table 1, the critical yield strength of alloy 5 is increased by 113MPa (17.4%) and the yield strength is increased by 265MPa (14.2%) as compared to the as-cast alloy of comparative example 3. When the strain is loaded by 2% -15%, the output stress can be improved by 8% -18% (fig. 6 (a)), and the output work can be improved by 32% -58% (fig. 6 (b)).
Example 6
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking alloy 6 as an alloy according to an atomic ratio of 30% Ti, 44% Ni, 10% Hf, 6% Cu and 10% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 And (3) charging argon to below Pa, striking an arc after charging the argon to-0.06 MPa, controlling the smelting current to be 250-310A, and continuously maintaining the smelting current for more than 2 minutes in an alloy melting state, ensuring that all metals are completely melted together, overturning the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy. The cast high-entropy memory alloy is put into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. And (3) putting the alloy 6 subjected to solution treatment into a resistance furnace again, heating to 300 ℃ along with the furnace, preserving heat for 120 minutes, and then cooling in air to obtain the high-entropy shape memory alloy 6 subjected to primary aging treatment. Finally, the alloy 6 subjected to primary aging treatment is placed into a resistance furnace again, heated to 400 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, so that the high-entropy shape memory alloy 6 subjected to secondary aging treatment is obtained: ti (Ti) 30 Ni 44 Hf 10 Cu 6 Zr 10 。
The microstructure of alloy 6 is shown in fig. 3 (c) and fig. 3 (d), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 6, and the cyclic loading stress-strain curve is shown in fig. 7. In comparison to the as-cast structure of comparative example 2 in FIG. 3 (a), a significant amount of nanoscale reinforcing phase is precipitated in alloy 6, about 45 per square micron, and about 70-145 nanometers in size. As can be seen from the statistics of Table 1, the critical yield strength of alloy 6 is increased by 350MPa (54%) as compared to the as-cast alloy of comparative example 3. When the strain is loaded by 2% -15%, the output stress can be improved by 13% -33% (fig. 6 (a)), and the output work can be improved by 26% -58% (fig. 6 (b)).
Comparative example 1
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking the alloy 7 as an alloy with the atomic ratio of 39% Ti, 44% Ni, 10% Hf, 6% Cu and 1% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 Charging argon to below Pa, striking an arc after reaching minus 0.06MPa, controlling the smelting current to be 200-300A, and keeping for more than 2 minutes in an alloy melting state, ensuring that after all metals are completely melted together, overturning the obtained alloy ingot by a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy 7:Ti 39 Ni 44 Hf 10 Cu 6 Zr 1 。
The microstructure of alloy 7 is shown in fig. 1 (a), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 4, and the cyclic loading stress-strain curve is shown in fig. 7.
Comparative example 2
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking alloy 8 as alloy according to the atomic ratio of 35% Ti, 44% Ni, 10% Hf, 6% Cu and 5% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 And (3) charging argon to below Pa, striking an arc after the argon is charged to-0.06 MPa, controlling the smelting current to be 230-300A, and keeping for more than 2 minutes in an alloy melting state to ensure that all metals are completely melted together. Turning over the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thus obtaining the as-cast high-entropy shape memory alloy 8:Ti 35 Ni 44 Hf 10 Cu 6 Zr 5 。
The microstructure of alloy 8 is shown in fig. 2 (a), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 5, and the cyclic loading stress-strain curve is shown in fig. 7.
Comparative example 3
The method comprises the steps of taking high-purity metal Ti, ni, hf, cu, zr as a raw material, cleaning the raw material by alcohol, taking the alloy 9 as an alloy according to the atomic ratio of 30% Ti, 44% Ni, 10% Hf, 6% Cu and 10% Zr, placing the raw material into a vacuum arc furnace, and vacuumizing to 10% -3 And (3) charging argon to below Pa, striking an arc after the argon is charged to-0.06 MPa, controlling the smelting current to be 250-310A, and keeping the smelting current in an alloy melting state for more than 2 minutes to ensure that all metals are completely melted together. Turning over the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast high-entropy shape memory alloy 9:Ti 30 Ni 44 Hf 10 Cu 6 Zr 10 。
The microstructure of alloy 9 is shown in fig. 3 (a), the performance parameters in the cyclic loading process are shown in table 1, the output stress and output work are shown in fig. 6, and the cyclic loading stress-strain curve is shown in fig. 7.
Comparative example 4
Taking high-purity metals Ti, ni and Cu as raw materials, cleaning the raw materials by alcohol, taking the alloy 10 as alloy with the atomic ratio of 50 percent of Ti, 44 percent of Ni and 6 percent of Cu, placing the raw materials into a vacuum arc furnace, and vacuumizing to 10 percent -3 And (3) charging argon to below Pa, striking an arc after the argon is charged to-0.06 MPa, controlling the smelting current to be 250-300A, and keeping for more than 2 minutes in an alloy melting state to ensure that all metals are completely melted together. Turning over the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast shape memory alloy 10:Ti 50 Ni 44 Cu 6 . The microstructure of alloy 10 is shown in FIG. 8 (a), the performance parameters during cyclic loading are shown in Table 1, and the cyclic loading stress-strain curve is shown in FIG. 8 (b).
Comparative example 5
Taking high-purity metals Ti, ni and Cu as raw materials, cleaning the raw materials by alcohol, taking the alloy 11 as alloy with the atomic ratio of 50 percent of Ti, 44 percent of Ni and 6 percent of Cu, placing the raw materials into a vacuum arc furnace, and vacuumizing to 10 percent -3 Charging argon gas to below Pa, striking an arc after-0.06 MPa, controlling the smelting current to be 250-300A, and keeping for more than 2 minutes in the alloy melting state, ensuring that all metals are completely melted together, overturning the obtained alloy ingot by a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the alloy ingotObtaining the as-cast shape memory alloy. The as-cast memory alloy is placed into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. Finally, the alloy 11 after solution treatment is put into a resistance furnace again, heated to 300 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, and the shape memory alloy 11:Ti of primary aging treatment is obtained 50 Ni 44 Cu 6 . The microstructure of alloy 11 is shown in FIG. 8 (c), the performance parameters during cyclic loading are shown in Table 1, and the cyclic loading stress-strain curve is shown in FIG. 8 (d).
Comparative example 6
Taking high-purity metals Ti, ni and Cu as raw materials, cleaning the raw materials by alcohol, taking the alloy 12 as alloy materials according to the atomic ratio of 50 percent of Ti, 44 percent of Ni and 6 percent of Cu, placing the raw materials into a vacuum arc furnace, and vacuumizing to 10 percent -3 And (3) charging argon to below Pa, striking an arc after charging the argon to-0.08 MPa, controlling the smelting current to be 250-300A, and continuously heating the alloy for more than 2 minutes in the molten state of the alloy, so that after all metals are completely melted together, turning over the obtained alloy ingot by using a manipulator, and repeatedly smelting for 6 times to ensure that the raw material components are uniform, thereby obtaining the as-cast shape memory alloy. The as-cast memory alloy is placed into a resistance furnace, heated to 800 ℃ along with the furnace, kept for 30 minutes, and then quenched and cooled in water. The alloy 12 after solution treatment is put into a resistance furnace again, heated to 300 ℃ along with the furnace, kept warm for 120 minutes and then air-cooled, and the shape memory alloy 12 after primary aging treatment is obtained. Finally, putting the alloy 12 subjected to primary aging treatment into a resistance furnace again, heating to 400 ℃ along with the furnace, preserving heat for 120 minutes, and then air-cooling to obtain the shape memory alloy 12 subjected to secondary aging treatment: ti (Ti) 50 Ni 44 Cu 6 . The microstructure of alloy 12 is shown in FIG. 8 (e), the performance parameters during cyclic loading are shown in Table 1, and the cyclic loading stress-strain curve is shown in FIG. 8 (f).
Table 1 performance parameters of the memory alloys of examples 1-6 and comparative examples 1-6 during cyclic loading
As can be seen from the data in Table 1 and FIGS. 4-6, the nanophase enhanced high entropy shape memory alloy prepared in accordance with the present application has significantly improved yield strength, output stress, output work, etc., and also has excellent memory properties, as compared with the as-cast alloy of comparative examples 1-3 and the non-high entropy alloy of comparative examples 4-6.
After the primary aging treatment, a small amount of nano phase is separated out, about 5-10 nano phases are separated out per square micron, and the size is about 40-80 nanometers. Under the action of a small amount of nano reinforcing phase, the performance parameters of the alloy are obviously improved. Compared with the cast structure with the same components in the comparative example, when the loading strain is 2% -15% after the primary aging treatment, the output stress of the alloy 1, 3 and 5 is respectively improved by 16% -72%, 6% -14%, 8% -18%, and the output work is respectively improved by 4% -62%, 10% -32% and 32% -58%. The critical yield strength of alloy 3 and alloy 5 is respectively increased by 60MPa (10.5%) and 113MPa (17.4%), the yield strength is respectively increased by 110MPa (6.3%) and 265MPa (14.2%), the maximum output stress of alloy 3 is increased by 76MPa (4.1%), the maximum recoverable strain is increased by 1.0 (11.5%), and the maximum output work is increased by 24.9J/cm 3 (15.2％)。
After the secondary aging treatment, a large amount of nano phase is separated out, about 40-50 nano phases are separated out per square micron, and the size is about 80-150 nanometers. Under the action of a large number of nano reinforcing phases, the performance parameters of the alloy are obviously improved. Compared with the cast structure of the comparative example, when the loading strain is 2% -15% after the secondary aging treatment, the output stress of the alloys 1, 3 and 5 is respectively increased by 20% -105%, 24% -45% and 13% -33%, and the output work is respectively increased by 12% -136%, 10% -32% and 26% -58%. The critical yield strengths of alloys 2, 4, and 6 were increased by 43MPa (11.5%), 310MPa (54.4%), and 350MPa (54%). The yield strength of the alloy 2 and the alloy 4 are respectively increased by 205MPa (13.6 percent), 180MPa (10.5 percent), the maximum output stress is respectively increased by 294MPa (20.1 percent), 110MPa (5.9 percent), and the maximum output work is respectively increased by 12.4J/cm 3 (11.3％)、16.0J/cm 3 (9.8％)。
In addition, compared with the prior art, the preparation process is convenient, only needs arc melting, solution treatment and low-temperature short-time aging heat treatment, does not need long-time homogenization heat treatment and plastic deformation processing, is easy to operate, and has very good application prospect.
The above embodiments are merely preferred embodiments of the present application, and should not be construed as limiting the present application, and the embodiments and features of the embodiments of the present application may be arbitrarily combined with each other without collision. The protection scope of the present application is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this application are also within the scope of the application.
Claims (7)
1. The nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy is characterized in that the raw materials of the alloy comprise the following chemical components in percentage by atom: the structural composition of the alloy comprises 30% -39% of Ti, 44% of Ni, 10% of Hf, 6% of Cu and 1% -10% of Zr, wherein the structural composition comprises a B2 austenitic matrix and nanoscale Ti 2 Ni-based reinforcement phase in which nano-scale Ti 2 The size of the Ni reinforcing phase is 40-150 nanometers, and the number is 5-50 per square micrometer;
the preparation method of the alloy comprises the following steps:
1) Batching and smelting: raw material Ti, ni, hf, cu, zr is prepared according to atomic percent, the raw material Ti, ni, hf, cu, zr is placed into a vacuum arc melting furnace, argon is filled after vacuumizing to prevent oxidation in the alloy melting process, and the alloy is repeatedly melted in a molten state to uniformly mix alloy components, so that the as-cast TiNiCuHfZr high-entropy shape memory alloy is obtained;
2) Solution treatment: placing the cast TiNiCuHfZr high-entropy shape memory alloy obtained in the step 1) into a resistance furnace, performing solution treatment, and quenching and cooling in water;
3) Primary aging treatment: placing the TiNiCuHfZr high-entropy shape memory alloy subjected to solution treatment obtained in the step 2) into a resistance furnace, performing primary aging treatment, and then performing air cooling to obtain the nano-phase reinforced high-entropy shape memory alloy subjected to primary aging treatment;
4) And (3) secondary aging treatment: placing the nano-phase reinforced high-entropy shape memory alloy obtained in the step 3) into a resistance furnace, performing secondary aging treatment, and then air-cooling to obtain the nano-phase reinforced high-entropy shape memory alloy subjected to secondary aging treatment;
after the primary aging treatment in the step 3), nano reinforcing phases are precipitated in the alloy, wherein the number of the nano reinforcing phases is 5-10 per square micron, and the size of the nano reinforcing phases is 40-80 nanometers; after the secondary aging treatment in the step 4), the number of the nano-scale reinforcing phases precipitated in the alloy is 40-50 per square micrometer, and the size is 80-150 nanometers.
2. The nanophase reinforced TiNiCuHfZr high entropy shape memory alloy of claim 1, wherein in step 1), the vacuum degree of the vacuum arc melting furnace is less than 10 -3 Pa, the pressure in the smelting furnace after argon is filled is-0.06-0.08 MPa, and the smelting current is 200-340A; the repeated re-smelting times are more than 5 times, and each time the melting state is kept for 1-2 minutes.
3. The nanophase reinforced TiNiCuHfZr high entropy shape memory alloy of claim 1, wherein in step 2), the solution treatment temperature is 800-900 ℃ and the holding time is 30-50 minutes.
4. The nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy according to claim 1, wherein in said step 3), the temperature of the primary aging treatment is 300-350 ℃, and the holding time is 120-180 minutes.
5. The nano-phase reinforced TiNiCuHfZr high-entropy shape memory alloy according to claim 4, wherein in step 3), the alloy is heated up with the furnace during the primary aging treatment and the heating rate is 10-15 ℃/min.
6. The nanophase reinforced TiNiCuHfZr high entropy shape memory alloy of claim 1, wherein in step 4), the secondary aging is performed at a temperature of 400-450 ℃ for a holding time of 120-180 minutes.
7. The nanophase reinforced TiNiCuHfZr high entropy shape memory alloy of claim 6, wherein in step 4), the alloy is heated with the furnace and at a heating rate of 10-15 ℃/min during the secondary aging treatment.
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