CN114150205B - High-temperature-resistant high-entropy alloy with high room-temperature plasticity and preparation method thereof - Google Patents
High-temperature-resistant high-entropy alloy with high room-temperature plasticity and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-temperature-resistant high-entropy alloy with high room-temperature plasticity and a preparation method thereof, wherein the high-entropy alloy comprises Ni as a component 3 Co 2 CrFeAlTi 0.25 Nb a Mo b Wherein a and b respectively represent the molar ratio of corresponding elements, a is more than or equal to 0.15 and less than or equal to 0.3, and b is more than or equal to 0.4 and less than or equal to 0.8. Removing oxide skin from a pure alloy raw material, cleaning, accurately weighing and proportioning according to alloy components and a molar ratio, putting the weighed raw material into a non-consumable vacuum arc furnace for smelting, and finally overturning an alloy ingot to repeatedly smelt for more than 6 times to obtain the high-entropy alloy consisting of an FCC solid solution and a small amount of Laves phases. The high-entropy alloy prepared by the invention has low density, high room temperature plasticity, good strength and high temperature plasticity, and can be widely applied as a high-temperature resistant material with higher service temperature in the fields of aerospace, energy, ships and the like in the future.
Description
Technical Field
The invention relates to a high-temperature-resistant high-entropy alloy with high room-temperature plasticity and a preparation method thereof, belonging to the field of metal materials.
Background
With the continuous improvement of the service temperature of key hot end components in the fields of aerospace, energy, ships and the like, the requirement on the temperature bearing capacity of high-temperature materials is higher and higher. At present, the nickel-based high-temperature alloy is a main material, but the nickel-based high-temperature alloy is difficult to have greater breakthrough in alloy design and manufacturing technology and meet the high-temperature application requirements under increasingly severe higher service temperatures.
The high-entropy alloy is a novel subversive alloy system, and all main elements are mixed in equal atomic ratio or near equal atomic ratio. Compared with the traditional alloy, the high-entropy alloy is more prone to form a stable simple solid solution phase and has excellent comprehensive properties such as excellent high-temperature strength and thermal stability, high-temperature oxidation resistance, high corrosion resistance and the like. Therefore, the high-entropy alloy has wide application prospect.
At present, the refractory high-entropy alloy has extremely high melting point and excellent high-temperature performance, and has great advantages in the high-temperature field. However, refractory high-entropy alloys that meet the requirements of high-temperature-resistant alloy density and strength, such as HfMoTaTiZr, CrHfNbTiZr, Al 0.4 Hf 0.6 NbTaTiZr and AlNbTiZrMo 0.5 Ta 0.5 The alloy generally has the technical problem of low room temperature plasticity, and cannot meet the performance requirement that the room temperature tensile plasticity of the high temperature resistant alloy is more than 15 percent.
Although the Chinese patent CN110777273A mentions that the liquid hydrogen placement method is adopted to improve the room temperature plasticity of the TiZrNbHf0.5Mo0.5 high entropy alloy, the method is not all applicable to other refractory high entropy alloys, and the alloy strength after hydrogen placement can not meet the performance index requirement. Moreover, the refractory high-entropy alloy belongs to a typical BCC (body centered cubic) structural alloy, and compared with an FCC (face centered cubic) structural alloy, the high-entropy alloy has the defects of smaller dislocation width, higher Pi-Na force, complex dislocation core and the like, so that the BCC structural alloy has poorer plastic deformation capability. Therefore, the material structure characteristics and the plastic processing status quo of the refractory high-entropy alloy influence the application prospect of the refractory high-temperature resistant alloy as a high-temperature resistant substitute material at higher service temperature to a certain extent.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant high-entropy alloy with high room-temperature plasticity and a preparation method thereof aiming at the defect of low room-temperature plasticity of the existing candidate material refractory high-entropy alloy for high service temperature, and aims to provide a second-phase precipitation-strengthened high-temperature-resistant high-entropy alloy material with an FCC structure, effectively improve the room-temperature deformability of the high-temperature-resistant high-entropy alloy, and simultaneously ensure that the alloy obtains good strength and high-temperature plasticity so as to meet the performance requirement at higher service temperature.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
the molar ratio expression of the components of the high-temperature-resistant high-entropy alloy material with high room-temperature plasticity provided by the technical scheme of the invention is Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b Wherein a is more than or equal to 0.15 and less than or equal to 0.3, and b is more than or equal to 0.4 and less than or equal to 0.8.
In practice, the molar ratio of the components of the high-entropy alloy material is expressed as Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b ，a＝0.25，b＝0.5。
In practice, the molar ratio table of the components of the high-entropy alloy materialIs expressed as Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b ，a＝0.2，b＝0.7。
In practice, the molar ratio of the components of the high-entropy alloy material is expressed as Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b ，a＝0.3，b＝0.4。
The high-entropy alloy material composition can enable Ni to be contained 3 Co 2 CrFeAlTi 0.25 Nb a Mo b The high-entropy alloy has an FCC structure, and compared with a BCC structure, the high-entropy alloy is fundamentally ensured to have good room temperature and high temperature plasticity. The Nb and Mo elements have larger atomic radius and strong lattice distortion effect, and the solid solution strengthening effect of the high-entropy alloy can be effectively enhanced by adding the Nb and Mo elements in the high-entropy alloy component design. Moreover, the bonding force of the Nb element and the Cr element is strong, and then the content of Nb is adjusted to form a 10-30% lumpy dispersed discontinuously distributed Laves strengthened second phase. The Laves phase can effectively block dislocation movement, plays a role in further improving the room temperature and high temperature strength of the alloy, and meanwhile, the distribution state and the content of the Laves phase enable dislocation movement to be still transferred and expanded to the alloy solid solution when being blocked, so that the influence on the alloy deformation coordination is small, and the alloy can be guaranteed to have good room temperature plasticity.
In addition, Nb has strong binding capacity with Cr and Fe, can form a Laves phase, and plays a role in strengthening a second phase in the high-entropy alloy. In the earlier research process, however, the Laves phase content is controlled to be 10% -30% when the Nb content in the high-entropy alloy system is 0.15-0.3, and the Laves phase is in a block-shaped dispersion distribution state, so that the alloy has high strength while good room-temperature and high-temperature plasticity is ensured; when the Nb content is more than 0.3, the Laves phase content is more than 30%, and the Laves phase is easy to aggregate into sheets, so that the deformation coordination with the matrix is poor, and the room temperature plasticity of the alloy is lower than 8%; when the Nb content is less than 0.15 and the Laves phase content is less than 10%, the ability to inhibit dislocations becomes poor, resulting in insufficient strength of the alloy.
Mo effectively enhances the solid solution strengthening effect of the alloy, thereby improving the room temperature strength and the high temperature strength of the alloy. Earlier researches show that when the content of the Mo element is lower than 0.4, the lattice distortion strengthening effect of the Mo element is not obvious, so that the room-temperature and high-temperature strength of the alloy is insufficient, and when the content of the Mo element is higher than 0.8, the lattice distortion strengthening effect of the Mo element is too large, so that the continuous deformation capability of a high-entropy alloy matrix at room temperature is damaged, and the room-temperature plasticity of the alloy is reduced to be below 10 percent, therefore, the content of the Mo element is determined to be 0.4-0.8.
Therefore, the high-entropy alloy composition design can ensure that the alloy has high strength while having good room temperature and high temperature plasticity so as to meet the performance requirement of a high-temperature-resistant high-entropy alloy material with higher service temperature.
The method for preparing the high-temperature-resistant high-entropy alloy material with high room-temperature plasticity provided by the technical scheme of the invention comprises the following steps:
firstly, selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, removing oxide skin on the surface of the raw materials by a mechanical method, and exposing a bright metal surface for later use;
step two, the Ni, Co, Cr, Fe, Al, Ti, Nb and Mo metal raw materials treated in the step one are subjected to high-entropy alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b Converting into mass percent, proportioning, weighing, and cleaning the weighed metal raw materials in an ultrasonic cleaning instrument;
step three, putting the processed metal raw materials into a non-consumable vacuum melting furnace copper crucible from high to low according to the melting point, closing a furnace door, and opening cooling water;
step four, vacuumizing the sample chamber, wherein when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa is needed, stopping vacuumizing, and introducing high-purity argon as protective gas to enable the pressure in the furnace to reach 0.05 Pa;
step five, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb a Mo b Smelting the alloy, keeping the time of the alloy in a liquid state for 4-8 minutes, and cooling the alloy quicklyThe alloy is turned over, the process is repeated for more than 6 times, and the high-temperature-resistant high-entropy alloy with high room-temperature plasticity is obtained after the alloy is cooled after being smelted.
In the implementation, the adopted Ni, Co, Cr, Fe, Al, Ti, Nb and Mo metal materials have the purity of not less than 99.5wt percent.
In the implementation, when the step four is carried out, the operation is repeated for 2 to 3 times to clean the vacuum chamber.
In practice, the number of flipping times in step five is 6.
The preparation method of the high-entropy alloy material provided by the technical scheme of the invention adopts a vacuum non-consumable arc melting method to prepare the alloy ingot, and can ensure that the ingot structure is uniform through repeated melting for many times.
The high-temperature-resistant high-entropy alloy material with high room temperature plasticity, provided by the technical scheme of the invention, has an FCC (fluid catalytic cracking) crystal grain structure, can be enabled to have high room temperature and high temperature plasticity, and meanwhile, a Laves strengthening phase is precipitated in an FCC matrix, so that the good strength of the material is ensured, and the application requirements of the material in the aspects of high-temperature-resistant materials or structural members in the fields of aerospace, energy, ships and the like are met, and the characteristics and the beneficial effects of the material are explained as follows:
ni prepared by the method of the present invention 3 Co 2 CrFeAlTi 0.25 Nb a Mo b The high-entropy alloy has an FCC structure, and the high-entropy alloy prepared by the invention has higher plasticity performance from the alloy crystal structure;
secondly, in order to meet the performance requirements of higher service temperature and high strength, the solid solution strengthening effect of the high-entropy alloy is enhanced by adding Nb and Mo elements with high lattice distortion;
thirdly, by separating out blocky dispersed discontinuously distributed Laves phase, the room temperature and high temperature strength of the alloy is further improved while the good room temperature plasticity of the alloy is ensured;
fourthly, the alloy is mixed with refractory high-entropy alloy (such as HfMoTaTiZr and AlMo 0.5 NbTa 0.5 TiZr and other alloy systems), the invention has lower cost, lower alloy melting point, relatively simple smelting process and easy realizationAnd (4) industrialization.
Drawings
FIG. 1 shows Ni in example 1 of the present invention 3 Co 2 CrFeAlTi 0.25 Nb 0.25 Mo 0.5 An X-ray diffraction pattern of the high entropy alloy;
FIG. 2 shows Ni in example 2 of the present invention 3 Co 2 CrFeAlTi 0.25 Nb 0.2 Mo 0.7 An X-ray diffraction pattern of the high entropy alloy;
FIG. 3 shows Ni in example 3 of the present invention 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 An as-cast microstructure of the high entropy alloy;
FIG. 4 shows Ni in example 4 of the present invention 3 Co 2 CrFeAlTi 0.25 Nb 0.15 Mo 0.8 An as-cast microstructure of the high entropy alloy;
FIG. 5 shows Ni in example 5 of the present invention 3 Co 2 CrFeAlTi 0.25 Nb 0.18 Mo 0.6 An as-cast microstructure of the high entropy alloy;
FIG. 6 shows Ni in example 6 of the present invention 3 Co 2 CrFeAlTi 0.25 Nb 0.28 Mo 0.55 The as-cast microstructure of the high entropy alloy.
Detailed Description
Example one
The high-temperature-resistant high-entropy alloy material with high room-temperature plasticity described in this embodiment includes the following metal elements in mole percentage: ni 34.39%; 23.02% of Co; 10.91 percent of Cr; 10.16 percent of Fe; 5.27 percent of Al; 2.34 percent of Ti2; 4.54 percent of Nb; mo 9.37%, the mol ratio expression of the high-entropy alloy is Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.25 Mo 0.5 。
The Ni, Co, Cr, Fe, Al, Ti, Nb and Mo are solid pure raw materials with the purity of not less than 99.5 wt%.
The Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.25 Mo 0.5 The preparation method of the high-entropy alloy comprises the following steps:
selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, mechanically removing oxide skin on the surfaces of the raw materials to expose bright metal surfaces, ultrasonically cleaning the raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo by using absolute ethyl alcohol, taking out and drying for later use;
step two, according to an alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.25 Mo 0.5 1719.69g of Ni, 1151.15g of Co, 545.49g of Fe, 507.89g of Cr, 263.52g of Al, 116.89g of Ti, 226.86g of Nb and 468.53g of Mo metal raw materials which are obtained in the first step are weighed according to the molar ratio of the elements;
putting the weighed raw materials into a copper crucible of a non-consumable vacuum smelting furnace according to the melting point; closing the furnace door, opening cooling water, and vacuumizing the sample chamber; when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa, stopping vacuumizing, and introducing high-purity argon as protective gas; when the pressure in the furnace reaches 0.05Pa, the step is repeated for 2 times to clean the vacuum chamber;
step four, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb 0.25 Mo 0.5 And (3) smelting the alloy, keeping the time of the alloy in a liquid state for 4 minutes, turning the alloy after the alloy is cooled quickly, repeating the process for 10 times, and cooling the alloy after the alloy is smelted to obtain the alloy material.
Ni obtained in the example 3 Co 2 CrFeAlTi 0.25 Nb 0.25 Mo 0.5 The high-entropy alloy consists of FCC and Laves phases, and the X-ray diffraction pattern of the high-entropy alloy is shown in figure 1. The alloy has a density of 7.91g/cm 3 The yield strength at room temperature is 802.7MPa, the tensile strength is 2365.2MPa, and the elongation is 21.59 percent; the yield strength at 850 ℃ is 750.6MPa, the tensile strength is 1558.2MPa, and the elongation is 38.82%; the yield strength at 950 ℃ is 724.6MPa, the tensile strength is 985.6MPa, and the elongation is 52.54%. The alloy has good room temperature and high temperature performance, and especially has high room temperature plasticity.
Example two
The implement of this embodimentThe high-temperature-resistant high-entropy alloy material with high room-temperature plasticity comprises the following metal elements in percentage by mole: ni 33.44%; 22.39% of Co; 10.61 percent of Cr; 9.88 percent of Fe; 5.12 percent of Al; 2.27 percent of Ti; nb 3.53 percent; 12.76 percent of Mo. The expression of the molar ratio of the high-entropy alloy is Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.2 Mo 0.7 。
The Ni, Co, Cr, Fe, Al, Ti, Nb and Mo are solid pure raw materials with the purity of not less than 99.5 wt%.
The Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.2 Mo 0.7 The preparation method of the high-entropy alloy comprises the following steps:
selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, mechanically removing oxide skin on the surfaces of the raw materials to expose bright metal surfaces, ultrasonically cleaning the raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo by using absolute ethyl alcohol, taking out and drying for later use;
step two, according to an alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.2 Mo 0.7 1672.18g of Ni, 1119.35g of Co, 530.42g of Fe, 493.86g of Cr, 256.24g of Al, 113.66g of Ti, 176.48g of Nb and 637.82g of Mo metal raw materials are weighed according to the molar ratio of the elements in the alloy;
putting the weighed raw materials into a copper crucible of a non-consumable vacuum smelting furnace according to the melting point; closing the furnace door, opening cooling water and vacuumizing the sample chamber; when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa, stopping vacuumizing, and introducing high-purity argon as protective gas; when the pressure in the furnace reaches 0.05Pa, the step is repeated for 2 times to clean the vacuum chamber;
step four, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb 0.2 Mo 0.7 Smelting the alloy, keeping the alloy in a liquid state for 6 minutes, turning the alloy after the alloy is cooled quickly, repeating the process for 8 times, and cooling the alloy after the alloy is smelted to obtain the alloyThe alloy material of the invention is obtained.
Ni obtained in this example 3 Co 2 CrFeAlTi 0.25 Nb 0.2 Mo 0.7 The X-ray diffraction pattern of the high-entropy alloy consisting of FCC and Laves phases is shown in figure 2. The alloy has a density of 7.97g/cm 3 Room temperature yield strength of 813.7MPa, tensile strength of 2453.8MPa, and elongation of 22.85%; the yield strength at 850 ℃ is 759.3MPa, the tensile strength is 1624.5MPa, and the elongation is 31.67%; the yield strength at 950 ℃ is 718.6MPa, the tensile strength is 991.5MPa, and the elongation is 53.39%. The alloy has good room temperature and high temperature performance, and especially has high room temperature plasticity.
EXAMPLE III
The high-temperature-resistant high-entropy alloy material with high room-temperature plasticity described in this embodiment includes the following metal elements in mole percentage: ni 34.73%; 23.25 percent of Co; 11.02 percent of Cr; 10.27 percent of Fe; 5.32 percent of Al; 2.36 percent of Ti; 5.50 percent of Nb; 7.57 percent of Mo. The expression of the molar ratio of the high-entropy alloy is Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 。
The Ni, Co, Cr, Fe, Al, Ti, Nb and Mo are solid pure raw materials with the purity of not less than 99.5 wt%.
Said Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 The preparation method of the high-entropy alloy comprises the following steps:
selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, mechanically removing oxide skin on the surfaces of the raw materials to expose bright metal surfaces, ultrasonically cleaning the raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo by using absolute ethyl alcohol, taking out and drying for later use;
step two, according to an alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 1736.47g of Ni, 1162.38g of Co, 550.81g of Fe, 512.84g of Cr, 266.09g of Al, 118.03g of Ti, 274.89g of Nb and 378.48g of Mo metal raw materials which are obtained in the first step are weighed according to the molar ratio of the elements;
step three, mixingWeighing raw materials, and putting the raw materials into a copper crucible of a non-consumable vacuum smelting furnace according to the melting point; closing the furnace door, opening cooling water and vacuumizing the sample chamber; when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa, stopping vacuumizing, and introducing high-purity argon as protective gas; when the pressure in the furnace reaches 0.05Pa, the step is repeated for 3 times to clean the vacuum chamber;
step four, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 And (3) smelting the alloy, keeping the alloy in a liquid state for 5 minutes, turning the alloy after the alloy is cooled quickly, repeating the process for 9 times, and cooling the alloy after the alloy is smelted to obtain the alloy material.
Ni obtained in the example 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 The high-entropy alloy consists of FCC and Laves phases, and the microstructure of the high-entropy alloy is shown in figure 3. The alloy has a density of 7.87g/cm 3 Room temperature yield strength of 796.8MPa, tensile strength of 2402.3MPa, and elongation of 23.72%; the yield strength at 850 ℃ is 762.6MPa, the tensile strength is 1673.1MPa, and the elongation is 33.96 percent; the yield strength at 950 ℃ is 721.7MPa, the tensile strength is 1001.9MPa, and the elongation is 50.19%. The alloy has good room temperature and high temperature performance, and especially has very high room temperature plasticity.
Example four
The high-temperature-resistant high-entropy alloy material with high room-temperature plasticity described in this embodiment includes the following metal elements in mole percentage: ni 33.13%; 22.18 percent of Co; 10.51 percent of Cr; 9.79 percent of Fe; 5.08 percent of Al; 2.25 percent of Ti; 2.62 percent of Nb; and Mo 14.44%. The expression of the molar ratio of the high-entropy alloy is Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.15 Mo 0.8 。
The Ni, Co, Cr, Fe, Al, Ti, Nb and Mo are solid pure raw materials with the purity of not less than 99.5 wt%.
Said Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.15 Mo 0.8 Of high-entropy alloysThe preparation method comprises the following steps:
selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, mechanically removing oxide skin on the surfaces of the raw materials to expose bright metal surfaces, ultrasonically cleaning the raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo by using absolute ethyl alcohol, taking out and drying for later use;
step two, according to an alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.3 Mo 0.4 1656.61g of Ni, 1108.92g of Co, 525.48g of Fe, 489.26g of Cr, 253.85g of Al, 112.60g of Ti, 131.13g of Nb and 722.15g of Mo metal raw materials which are obtained in the first step are weighed according to the molar ratio of the elements;
putting the weighed raw materials into a copper crucible of a non-consumable vacuum smelting furnace according to the melting point; closing the furnace door, opening cooling water and vacuumizing the sample chamber; when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa, stopping vacuumizing, and introducing high-purity argon as protective gas; when the pressure in the furnace reaches 0.05Pa, the step is repeated for 3 times to clean the vacuum chamber;
step four, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb 0.15 Mo 0.8 And (3) smelting the alloy, keeping the alloy in a liquid state for 6 minutes, turning the alloy after the alloy is cooled quickly, repeating the process for 7 times, and cooling the alloy after the alloy is smelted to obtain the alloy material.
Ni obtained in the example 3 Co 2 CrFeAlTi 0.25 Nb 0.15 Mo 0.8 The high-entropy alloy consists of FCC and Laves phases, and the microstructure of the high-entropy alloy is shown in figure 4. The alloy has a density of 7.99g/cm 3 Room temperature yield strength of 792.4MPa, tensile strength of 2469.5MPa and elongation of 20.02 percent; the yield strength at 850 ℃ is 749.1MPa, the tensile strength is 1653.6MPa, and the elongation is 39.06%; the yield strength at 950 ℃ is 716.4MPa, the tensile strength is 998.1MPa, and the elongation is 54.71 percent. The alloy has good room temperature and high temperature performance, and especially has very high performanceAnd (4) plasticity at room temperature.
EXAMPLE five
The high-temperature-resistant high-entropy alloy material with high room-temperature plasticity described in this embodiment includes the following metal elements in mole percentage: 34.19 percent of Ni; 22.88 percent of Co; 10.84 percent of Cr; 10.10 percent of Fe; 5.24 percent of Al; 2.32 percent of Ti; 3.25 percent of Nb; 11.18 percent of Mo. The expression of the molar ratio of the high-entropy alloy is Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.18 Mo 0.6 。
The Ni, Co, Cr, Fe, Al, Ti, Nb and Mo are solid pure raw materials with the purity of not less than 99.5 wt%.
The Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.18 Mo 0.6 The preparation method of the high-entropy alloy comprises the following steps:
selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, mechanically removing oxide skin on the surfaces of the raw materials to expose bright metal surfaces, ultrasonically cleaning the raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo by using absolute ethyl alcohol, taking out and drying for later use;
step two, according to an alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.18 Mo 0.6 1709.37g of Ni, 1144.24g of Co, 542.22g of Fe, 504.84g of Cr, 261.93g of Al, 116.19g of Ti, 162.36g of Nb and 558.86g of Mo metal raw materials which are obtained in the first step are weighed according to the molar ratio of the elements;
step three, putting the weighed raw materials into a non-consumable vacuum smelting furnace copper crucible according to the melting point; closing the furnace door, opening cooling water and vacuumizing the sample chamber; when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa, stopping vacuumizing, and introducing high-purity argon as a protective gas; when the pressure in the furnace reaches 0.05Pa, the step is repeated for 3 times to clean the vacuum chamber;
step four, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb 0.18 Mo 0.6 Alloy is smeltedThe time for keeping the alloy in the liquid state is 5 minutes, the alloy is turned over after being cooled quickly, the process is repeated for 8 times, and the alloy material is obtained after the alloy is melted and cooled.
Ni obtained in the example 3 Co 2 CrFeAlTi 0.25 Nb 0.18 Mo 0.6 The high-entropy alloy consists of FCC and Laves phases, and the microstructure of the high-entropy alloy is shown in figure 5. The alloy has a density of 7.93g/cm 3 Room temperature yield strength of 806.9MPa, tensile strength of 2472.3MPa, and elongation of 24.04%; the yield strength at 850 ℃ is 768.6MPa, the tensile strength is 1583.6MPa, and the elongation is 32.56 percent; the yield strength at 950 ℃ is 728.6MPa, the tensile strength is 989.9MPa, and the elongation is 55.14%. The alloy has good room temperature and high temperature performance, and especially has high room temperature plasticity.
EXAMPLE six
The high-temperature-resistant high-entropy alloy material with high room-temperature plasticity described in this embodiment includes the following metal elements in mole percentage: ni 33.89%; 22.69% of Co; 10.75 percent of Cr; 10.01 percent of Fe; 5.19 percent of Al; 2.30 percent of Ti; 5.01 percent of Nb; 10.16 percent of Mo. The expression of the molar ratio of the high-entropy alloy is Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.28 Mo 0.55 。
The Ni, Co, Cr, Fe, Al, Ti, Nb and Mo are solid pure raw materials with the purity of not less than 99.5 wt%.
The Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.28 Mo 0.55 The preparation method of the high-entropy alloy comprises the following steps:
selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, mechanically removing oxide skin on the surfaces of the raw materials to expose bright metal surfaces, ultrasonically cleaning the raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo by using absolute ethyl alcohol, taking out and drying for later use;
step two, according to an alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb 0.28 Mo 0.55 1694.58g of Ni, 1134.34g of Co, 537.53g of Fe and 500.47g of Ni, 1134.34g of Co, obtained in the first step, were weighed out in terms of the molar ratio of the elementsCr, 259.67g of Al, 115.18g of Ti, 250.38g of Nb and 507.85g of Mo metal raw materials;
putting the weighed raw materials into a copper crucible of a non-consumable vacuum smelting furnace according to the melting point; closing the furnace door, opening cooling water, and vacuumizing the sample chamber; when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa, stopping vacuumizing, and introducing high-purity argon as protective gas; when the pressure in the furnace reaches 0.05Pa, the step is repeated for 3 times to clean the vacuum chamber;
step four, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then Ni in the crucible 3 Co 2 CrFeAlTi 0.25 Nb 0.28 Mo 0.55 And (3) smelting the alloy, keeping the alloy in a liquid state for 6 minutes, turning the alloy after the alloy is cooled quickly, repeating the process for 9 times, and cooling the alloy after the alloy is smelted to obtain the alloy material.
Ni obtained in the example 3 Co 2 CrFeAlTi 0.25 Nb 0.28 Mo 0.55 The high-entropy alloy consists of FCC and Laves phases, and the microstructure of the high-entropy alloy is shown in figure 6. The alloy has a density of 7.92g/cm 3 The yield strength at room temperature is 798.1MPa, the tensile strength is 2394.3MPa, and the elongation is 23.09%; the yield strength at 850 ℃ is 755.8MPa, the tensile strength is 1612.4MPa, and the elongation is 34.13%; the yield strength at 950 ℃ is 722.9MPa, the tensile strength is 996.2MPa, and the elongation is 51.52 percent. The alloy has good room temperature and high temperature performance, and especially has very high room temperature plasticity.
The high-entropy alloy prepared by the invention has good room temperature and high temperature plasticity, higher room temperature and high temperature strength than the existing nickel-based high-temperature alloy, and lower density than the existing nickel-based high-temperature alloy, and lays a theoretical foundation for the feasibility of the design and application of high-temperature resistant materials for higher service temperature.
Claims (7)
1. A high-temperature-resistant high-entropy alloy with high room-temperature plasticity is characterized in that: the molar ratio expression of the components of the high-entropy alloy material is Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b Wherein a is more than or equal to 0.15 and less than or equal to 0.3, and b is more than or equal to 0.4 and less than or equal to 0.8, and the preparation method comprises the following steps:
firstly, selecting metallurgical raw materials of Ni, Co, Cr, Fe, Al, Ti, Nb and Mo, removing oxide skin on the surface of the raw materials by a mechanical method, and exposing a bright metal surface for later use;
step two, the Ni, Co, Cr, Fe, Al, Ti, Nb and Mo metal raw materials treated in the step one are subjected to high-entropy alloy expression Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b Converting into mass percent, proportioning, weighing, and cleaning the weighed metal raw materials in an ultrasonic cleaning instrument;
step three, putting the processed metal raw materials into a non-consumable vacuum melting furnace copper crucible from high to low according to the melting point, closing a furnace door, and opening cooling water;
step four, vacuumizing the sample chamber, wherein when the vacuum degree of the cavity is 2.5 multiplied by 10 -3 When Pa is needed, stopping vacuumizing, and introducing high-purity argon as protective gas to enable the pressure in the furnace to reach 0.05 Pa;
step five, during smelting, firstly smelting the pure titanium particles in the smelting pool once to absorb residual gas in the sample chamber; then the Ni in the crucible is treated 3 Co 2 CrFeAlTi 0.25 Nb a Mo b And smelting the alloy, keeping the alloy in a liquid state for 4-8 minutes, turning the alloy after the alloy is cooled quickly, repeating the process for more than 6 times, and cooling the alloy after the alloy is smelted to obtain the high-temperature-resistant high-entropy alloy with high room-temperature plasticity.
2. High temperature resistant high entropy alloy with high room temperature plasticity according to claim 1, characterized in that: the molar ratio expression of the components of the high-entropy alloy material is Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b ，a=0.25，b=0.5。
3. The high temperature-resistant high entropy alloy with high room temperature plasticity as claimed in claim 1, wherein: the molar ratio table of the components of the high-entropy alloy materialIs expressed as Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b ，a=0.2，b=0.7。
4. High temperature resistant high entropy alloy with high room temperature plasticity according to claim 1, characterized in that: the molar ratio expression of the components of the high-entropy alloy material is Ni 3 Co 2 CrFeAlTi 0.25 Nb a Mo b ，a=0.3，b=0.4。
5. High temperature resistant high entropy alloy with high room temperature plasticity according to claim 1, characterized in that: the purity of the adopted Ni, Co, Cr, Fe, Al, Ti, Nb and Mo metal solid raw materials is not less than 99.5 wt%.
6. High temperature resistant high entropy alloy with high room temperature plasticity according to claim 1, characterized in that: and repeating the operation for 2-3 times to clean the vacuum chamber in the fourth step.
7. High temperature resistant high entropy alloy with high room temperature plasticity according to claim 1, characterized in that: and the turnover frequency in the step five is 6 times.
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