CN115572881A - Method for regulating and controlling obdurability and failure mode of TiZrHfNbTa system refractory high-entropy alloy - Google Patents
Method for regulating and controlling obdurability and failure mode of TiZrHfNbTa system refractory high-entropy alloy Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
Abstract
The invention particularly relates to a method for regulating and controlling the obdurability and failure mode of a TiZrHfNbTa system refractory high-entropy alloy, belonging to the field of metal materials. The method comprises the steps of taking metal simple substances Ti, zr, hf, nb, ta and M as raw materials, carrying out alloying smelting to form a refractory high-entropy alloy ingot under the protective atmosphere of inert gas, heating the refractory high-entropy alloy ingot to a temperature 50-200 ℃ above the BCC phase transformation temperature, preserving heat for 1-8 h, then cooling to complete solid solution treatment, then heating to 400-700 ℃, preserving heat for 0.5-8 h, then cooling to complete aging treatment, and obtaining Ti with the BCC phase as a main phase structure and a small amount of nano precipitated phase as a second phase a Zr b Hf c Nb d Ta e M x The high-entropy refractory alloy has dynamic compression strength and fracture strain which are correspondingly changed within the ranges of 1000-2000 MPa and 10-40% by regulating and controlling the content of each component and preparation process parameters, and the failure mode is controllable so as to realize uniform crushing under high-speed impact and meet the dual requirements of detonation loading and full crushing after invasion.
Description
Technical Field
The invention particularly relates to a method for regulating and controlling the obdurability and failure mode of a TiZrHfNbTa system refractory high-entropy alloy, belonging to the field of metal materials.
Background
The high-entropy alloy is a novel multi-principal-element alloy designed based on the concept of 'entropy', provides a brand-new idea for designing alloy components, and provides a revolution opportunity for customizing materials meeting different application requirements. The refractory high-entropy alloy is a material widely researched in high-entropy alloys, mainly comprises Ti, zr, hf, ta and other high-melting-point elements, and has good application prospect in the field of warhead structural materials due to the advantages of high density and high strength.
The materials of the components of the warhead are generally required to have good obdurability and be adjustable in a large range so as to meet the service requirements of various detonation/high-speed impact loading. Taking the blast-killing warhead fragment as an example, the fragment material requires that the structure is kept complete after detonation loading, the mass loss is less in the penetration process, the material is required to have high toughness, and the fragment is required to be fully crushed after penetration in order to realize high after-effect damage, which is in contradiction with high toughness.
The refractory high-entropy alloy reported at present, such as TiZrHfTa alloy, has high density and high strength, but has poor plastic deformation capability, is easy to break under detonation loading, and has low effective fragment rate. A Xue Yunfei team of Beijing university of science and engineering designs and prepares a Ti-Zr-Hf-Nb-Ta system high-entropy alloy in an early stage, which has high toughness characteristics and can meet detonation loading, but the localized shear failure is easy to occur under high-speed impact, so that the broken alloy after the impact is insufficient, and the subsequent damage power is limited. In a word, the existing refractory high-entropy alloy has limited regulation and control on obdurability, and the dual requirements of detonation loading and full crushing after invasion are difficult to meet by the failure mode of localized shearing.
Disclosure of Invention
Aiming at the problems, the invention provides a method for regulating and controlling the obdurability and the failure mode of a TiZrHfNbTa system refractory high-entropy alloy, which is characterized in that other elements are added, meanwhile, the process parameters are optimized, the microstructure of the alloy is regulated and controlled, the obtained alloy consists of a BCC matrix phase and a small amount of nanometer precipitated phases, the dynamic compression strength of the system refractory high-entropy alloy is between 1000MPa and 2000MPa, the fracture strain is between 10 percent and 40 percent, the failure mode is controllably changed from localized shear fracture to uniform fracture along crystal under an impact environment, the obdurability of the refractory high-entropy alloy is continuously adjustable in a large range, the failure mode is controllable, and the dual requirements of detonation loading and full fracture after invasion are met.
The purpose of the invention is realized by the following technical scheme.
A method for regulating and controlling the obdurability and failure mode of a TiZrHfNbTa system refractory high-entropy alloy is characterized by taking metal simple substances Ti, zr, hf, nb, ta and M as raw materials, carrying out alloying smelting to form a refractory high-entropy alloy ingot under the protective atmosphere of inert gas, heating the refractory high-entropy alloy ingot to a temperature 50-200 ℃ above the BCC phase transition temperature, preserving heat for 1-8 h, cooling to complete solid solution treatment, then heating to 400-700 ℃, preserving heat for 0.5-8 h, and then cooling to complete aging treatment, thereby obtaining Ti which takes a BCC phase as a main phase structure and contains a small amount of nano precipitated phase as a second phase a Zr b Hf c Nb d Ta e M x The high-entropy refractory alloy has the advantages that the dynamic compression strength and the fracture strain of the high-entropy refractory alloy are correspondingly changed within the ranges of 1000-2000 MPa and 10-40% by regulating and controlling the content of each component and preparation process parameters, and the failure mode is controllable so as to realize uniform crushing under high-speed impact;
the Ti a Zr b Hf c Nb d Ta e M x In the refractory high-entropy alloy, M is one or more of Al, cr, mn, fe, co, ni, cu and Mo, a is more than or equal to 25 and less than or equal to 60,0 and more than or equal to b and less than or equal to 30,0 and more than or equal to 40,0 and more than or equal to d and less than or equal to 30,0 and more than or equal to e and less than or equal to 50,0 and more than or equal to x and less than or equal to 10, and a + b + c + d + e + x =100 and b + c is more than or equal to 15 and less than or equal to 60.
Further, the Ti a Zr b Hf c Nb d Ta e M x In the refractory high-entropy alloy, a is not less than 25 and not more than 50,5 and not more than 20,5 and not more than c and not more than 30,5 and not more than d and not more than 20, e is not less than 15 and not more than 35,0 and not more than x and not more than 5, a + b + c + d + e + x =100, and b + c is not less than 15 and not more than 50.
Further, M is one or more of Al, cr, cu and Mo.
Furthermore, when M is Cu or/and Al, x is more than 0 and less than or equal to 3 and is the optimal addition amount, the optimal aging temperature range is 450-600 ℃, and the optimal aging time is 0.5-3.5 h; when M is Cr or/and Mo, x is more than or equal to 2 and less than 5, and is the optimal addition amount, the optimal aging temperature range is 550-700 ℃, and the optimal aging time is 3-8 h.
Further, alloying melting is performed by using an induction melting furnace, and the number of repeated melting is 4 or more (including 4).
Has the advantages that:
(1) In the regulation and control method, on one hand, the added M element and the TiZrHfNbTa system refractory high-entropy alloy component have relatively negative mixed enthalpy and are easy to form a second phase, and the difference between the atomic radiuses of the M element and the refractory high-entropy alloy component is relatively large, so that a precipitated phase is easy to segregate at a crystal boundary; on the other hand, the optimization of preparation process parameters can regulate and control the content, the form and the precipitation position of a precipitated phase, and the controllable change of the toughness and the failure mode of the TiZrHfNbTa system can be realized based on the regulation and control of the microstructure.
(2) In the regulation and control method, along with the change of the content of the M element, the content and the distribution state (continuous or discontinuous distribution) of the interface precipitated phase also change, so that the plasticity, the failure mode and the like of the refractory high-entropy alloy are changed along with the change; in addition, because the atomic sizes of the M elements are different, the solid solution strengthening of the refractory high-entropy alloy by different M elements has obvious difference, and therefore the regulation range of the obdurability can be further increased through the selection of the types of the M elements and the regulation and control of the content of the M elements.
(3) According to the regulating method, the precipitated phase is completely dissolved back through solid solution treatment, then the content and distribution of the second phase can be effectively controlled through aging treatment, particularly, the content of the second phase at the crystal boundary of the alloy can be increased and distributed densely through optimizing aging temperature and aging time, so that the toughness of the alloy is continuously changed, the failure mode of the alloy gradually tends to uniform fracture along the crystal from crystal-crossing shear fracture, and uniform fracture under high-speed impact is realized.
(4) The regulation and control method provided by the invention is used for carrying out microstructure design on the refractory high-entropy alloy by utilizing the delayed diffusion effect of the refractory high-entropy alloy and combining the solid solution and aging treatment processes, realizes toughness regulation in a large range, is controllable in failure mode in an impact environment, is simple to operate, and is suitable for industrial production.
Drawings
FIG. 1 is a plot of back-scattered electron imaging (BSE) of the refractory high entropy alloy prepared in example 1.
Fig. 2 is a graph comparing the X-ray diffraction (XRD) patterns of the refractory high-entropy alloy prepared in example 2, the refractory high-entropy alloy prepared in example 3, the refractory high-entropy alloy prepared in example 4, and the refractory high-entropy alloy prepared in comparative example 1.
FIG. 3 is a transmission electron microscope open-field (TEM-BF) diagram of the refractory high-entropy alloy prepared in example 1 and the refractory high-entropy alloy prepared in comparative example 1 at the grain boundary.
Fig. 4 is a comparison graph of the dynamic compressive true stress-strain curves of the refractory high entropy alloy prepared in example 1, the refractory high entropy alloy prepared in example 2, and the refractory high entropy alloy prepared in comparative example 1.
Fig. 5 is a Scanning Electron Microscope (SEM) comparison of the refractory high-entropy alloy prepared in example 2, the refractory high-entropy alloy prepared in example 3, and a sample recovered from the refractory high-entropy alloy prepared in comparative example 1 after a dynamic compression test at a corresponding fracture.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification.
1) Reagent and apparatus
The information on the main reagents used in the following examples is shown in Table 1 and the information on the main instruments and equipments is shown in Table 2.
TABLE 1
TABLE 2
2) Performance testing and structural characterization
(1) And (3) density measurement: according to the standard GB-5365-2005, a DT-100 precision balance is adopted to test the density of the refractory high-entropy alloy, and the size of a sample is phi 4 multiplied by 4mm.
(2) Phase analysis: the phase analysis was carried out using a D8 advance X-ray diffractometer from Bruker AXS, germany, operating at 40kV and 40mA, respectively, as well as a CuKa (lambda =0.1542 nm) as the X-ray source, at a scan rate of 0.2sec/step, at a scan step of 0.02 DEG/step, over a scan range of 20 DEG to 110 deg.
(3) And (3) appearance observation: the microstructure characterization is carried out by adopting a HITACHI S4800 type cold field emission scanning electron microscope of Hitachi, japan, and the appearance of a precipitated phase at a crystal boundary is observed by back scattering electron imaging, wherein the working voltage is 15kV. A FEI Talos F200X type Transmission Electron Microscope (TEM) is adopted to observe the microstructure of the refractory high-entropy alloy, a sample is firstly ground and thinned to 50 +/-10 mu m by 400#, 800# and 1500# sandpaper, and then the sample is thinned by ions to be used for TEM observation.
(4) Dynamic compression test: according to the standard GJB-5365-2005, a Separated Hopkins Pressure Bar (SHPB) is adopted to test the room-temperature axial dynamic compression mechanical property of the refractory high-entropy alloy, the size of a test sample is phi 4 multiplied by 4mm, and the strain rate is-10 3 s -1 。
Example 1
Ti 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 The preparation steps of the refractory high-entropy alloy are as follows:
(1) High-purity Ti, high-purity Zr, high-purity Hf, high-purity Nb, high-purity Ta and high-purity Cu are used as raw materials, firstly, an oxide skin on the surface of the raw materials is removed by grinding with a grinding wheel, then, ultrasonic oscillation cleaning is carried out with absolute ethyl alcohol, drying is carried out, and then, the clean raw materials with the total mass of (840 +/-0.1) g are weighed according to the following atomic percentages of Ti;
(2) Weighing clean raw materials in sequence from low melting point to high melting pointPutting the mixture into a water-cooled copper crucible of a vacuum induction melting furnace, and then vacuumizing until the vacuum degree in the furnace reaches 3 multiplied by 10 -3 After Pa, introducing high-purity argon as protective gas until the pressure in the furnace reaches 0.04MPa, turning on a power supply to carry out smelting, keeping the temperature for 20s after the raw materials are completely melted, then turning off the power supply to carry out cooling, turning over the cooled alloy ingot, and then repeatedly smelting to obtain the alloy ingot with the density of 11.61g/cm 3 The refractory high-entropy alloy ingot;
(3) Cutting the energetic high-entropy alloy ingot, polishing the cut surface, sealing the cut surface in a quartz tube filled with high-purity argon, heating the quartz tube to 1300 ℃, preserving the temperature for 2 hours, and then performing water cooling to finish the solid solution treatment; sealing the high-entropy alloy subjected to solution treatment in a quartz tube filled with high-purity argon, heating to 500 ℃, preserving heat for 0.7h, then performing water cooling to finish aging treatment, and correspondingly obtaining the Ti 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 High entropy alloy, abbreviated as alloy 1-500-0.7.
The alloy 1-500-0.7 is subjected to morphology characterization, and as can be seen from figure 1, the alloy 1-500-0.7 is in an equiaxial crystal structure, and the grain size is 230 μm; as can be seen from FIG. 3, fine, continuously distributed Hf-Cu rich nano precipitates appear at the grain boundaries of alloys 1-500-0.7.
The phase analysis of the alloy 1-500-0.7 shows that the alloy 1-500-0.7 is mainly composed of BCC phase, and no obvious second phase peak exists in the XRD spectrogram due to the very small content of the precipitated second phase.
The alloy 1-500-0.7 was tested by dynamic compression test to determine a dynamic yield strength of-1780 MPa and a corresponding strain at break of-28%, as shown in FIG. 4. In addition, after dynamic compression test, the alloy 1-500-0.7 is crushed into 4 parts, and the fracture is mainly characterized by crystal brittle fracture.
Example 2
Based on the example 1, except that the aging treatment time is changed from 0.7h to 0.5h, other steps and conditions are the same as the example 1, and correspondingly Ti is obtained 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 High entropy of refractoryGold, abbreviated as alloy 1-500-0.5.
The shape characterization shows that the alloy 1-500-0.5 is in an isometric crystal structure, and the grain size is 230 mu m; fine and discontinuously distributed Hf-Cu rich nanometer precipitated phases appear at the grain boundary of the alloy 1-500-0.5.
As shown by phase analysis, the alloy 1-500-0.5 is mainly composed of BCC phase, and no obvious second phase peak exists in the XRD spectrum due to the very small content of the precipitated second phase, as shown in FIG. 2.
According to the dynamic compression test results, the dynamic yield strength of the alloy 1-500-0.5 is 1830MPa, and the corresponding fracture strain is 38%, as shown in FIG. 4. In addition, as can be seen from FIG. 5, after the dynamic compression test, the alloy 1-500-0.5 was broken into 3 parts, and the fracture was mainly characterized by mixed crystal brittle fracture.
Example 3
On the basis of example 1, ti was obtained by following the same procedure and conditions as in example 1 except that the aging temperature was changed from 500 ℃ to 600 ℃ and the aging time was changed from 0.7h to 0.5h 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 Refractory high-entropy alloy, which is abbreviated as alloy 1-600-0.5.
The shape characterization shows that the alloy 1-600-0.5 is in an isometric crystal structure, and the grain size is 240 mu m; continuous, coarse and uniformly distributed Hf-Cu rich nano precipitated phase exists at the grain boundary of the alloy 1-600-0.5.
As shown by phase analysis, the alloy 1-600-0.5 is mainly composed of BCC phase, and no obvious second phase peak exists in the XRD spectrum due to the very small content of the precipitated second phase, as shown in FIG. 2.
According to the test result of the dynamic compression test, the dynamic yield strength of the alloy 1-600-0.5 is 1400MPa, and the corresponding fracture strain is 20%. In addition, as can be seen from FIG. 5, after the dynamic compression test, the alloy 1-600-0.5 was broken into 5 parts, and the fracture was mainly characterized by brittle fracture along the crystal.
Example 4
On the basis of example 1, ti was obtained by following the same procedure and conditions as in example 1 except that the aging temperature was changed from 500 ℃ to 700 ℃ and the aging time was changed from 0.7h to 0.5h 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 Refractory high-entropy alloy, which is abbreviated as alloy 1-700-0.5.
The shape characterization shows that the alloy 1-700-0.5 is in an equiaxial crystal structure, and the grain size is 250 mu m; the complete continuous and coarse Hf-Cu rich nano precipitated phase exists at the grain boundary of the alloy 1-700-0.5.
As shown by phase analysis, the alloy 1-700-0.5 is mainly composed of BCC phase, and no obvious second phase peak exists in the XRD spectrum due to the very small content of the precipitated second phase, as shown in FIG. 2.
According to the test result of the dynamic compression test, the dynamic yield strength of the alloy 1-700-0.5 is 1300MPa, and the corresponding fracture strain is 10%. In addition, after dynamic compression test, the alloy 1-700-0.5 is crushed into 5 parts, and the fracture is mainly characterized by crystal brittle fracture.
Example 5
Ti 50 Zr 20 Hf 5 Nb 8 Ta 15 Al 2 The preparation method of the refractory high-entropy alloy fragment comprises the following steps:
(1) High-purity Ti, high-purity Zr, high-purity Hf, high-purity Nb, high-purity Ta and high-purity Al are used as raw materials, firstly, oxide skin on the surfaces of the raw materials is removed by grinding with a grinding wheel, then, ultrasonic oscillation cleaning is carried out by absolute ethyl alcohol, drying is carried out, and then, the clean raw materials with the total mass of (840 +/-0.1) g are weighed according to the following ratio of (2);
(2) Putting the weighed clean raw materials into a water-cooled copper crucible of a high vacuum induction melting furnace in sequence from low melting point to high melting point, then vacuumizing until the vacuum degree in the furnace reaches 3 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas until the pressure in the furnace reaches 0.04MPa, turning on a power supply to smelt, keeping the temperature for 20s after the raw materials are completely melted, then turning off the power supply to cool, and turning over the cooled alloy ingotThen repeatedly smelting to obtain the product with the density of 7.37g/cm 3 The refractory high-entropy alloy ingot;
(3) Cutting the energetic high-entropy alloy ingot, polishing the cut surface, sealing the cut surface in a quartz tube filled with high-purity argon, heating the quartz tube to 1200 ℃, preserving the heat for 1 hour, and then performing water cooling to finish the solid solution treatment; sealing the high-entropy alloy subjected to solution treatment in a quartz tube filled with high-purity argon, heating to 400 ℃, preserving heat for 8 hours, then performing water cooling to finish aging treatment, and accordingly obtaining the Ti 50 Zr 20 Hf 5 Nb 8 Ta 15 Al 2 Refractory high-entropy alloy, which is abbreviated as alloy 2-400-8.
The appearance characterization shows that the alloy 2-400-8 is in an equiaxed crystal structure, the grain size is 200 mu m, and a small amount of dispersed Zr-Al-rich brittle precipitated phase exists in the crystal.
As shown by phase analysis, the alloy 2-400-8 is mainly composed of BCC phase, and no obvious second phase peak exists in an XRD spectrum due to the very small content of the precipitated second phase.
According to the test result of the dynamic compression test, the dynamic yield strength of the alloy 2-400-8 is 1100MPa, and the corresponding fracture strain is 10 percent. In addition, after a dynamic compression test, the alloy 2-400-8 is crushed into 6 parts, and fracture mainly has the characteristic of transgranular brittle fracture.
Example 6
Ti 25 Zr 10 Hf 5 Nb 20 Ta 35 Al 2 Cr 3 The preparation steps of the refractory high-entropy alloy are as follows:
(1) The method comprises the following steps of taking high-purity Ti, high-purity Zr, high-purity Hf, high-purity Nb, high-purity Ta, high-purity Al and high-purity Cr as raw materials, grinding by using a grinding wheel to remove oxide skin on the surface of the raw materials, then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol, and then drying, and then weighing clean raw materials with the total mass of (840 +/-0.1) g according to the following atomic ratio of Ti;
(2) Putting the weighed clean raw materials into a water-cooled copper crucible of a high vacuum induction melting furnace in sequence from low melting point to high melting point, vacuumizing, and waiting for the furnace to be inThe vacuum degree of (2) reaches 3X 10 -3 After Pa, filling high-purity argon as protective gas until the pressure in the furnace reaches 0.04MPa, turning on a power supply to carry out smelting, keeping the temperature for 20s after the raw materials are completely melted, then turning off the power supply to carry out cooling, turning over the cooled alloy ingot, and then repeatedly smelting to obtain the alloy ingot with the density of 10.15g/cm 3 The refractory high-entropy alloy ingot;
(3) Cutting the energy-containing high-entropy alloy ingot, polishing the cut surface, sealing the cut surface in a quartz tube filled with high-purity argon, heating the quartz tube to 1300 ℃, preserving the heat for 4 hours, and then carrying out water cooling to complete solid solution treatment; sealing the high-entropy alloy subjected to solution treatment in a quartz tube filled with high-purity argon, heating to 600 ℃, preserving heat for 2 hours, then performing water cooling to finish aging treatment, and correspondingly obtaining the Ti 25 Zr 10 Hf 5 Nb 20 Ta 35 Al 2 Cr 3 The high-entropy alloy fragment is abbreviated as alloy 3-600-2.
As shown by the appearance characterization, the alloy 3-600-2 is in an equiaxial crystal structure, the grain size of the alloy is 300 mu m, a small amount of dispersed Zr-Al-rich brittle precipitated phase exists in the crystal, and a large amount of Hf-Cr-rich brittle precipitated phase exists in the crystal boundary.
As shown by phase analysis, the alloy 3-600-2 is mainly composed of BCC phase, and no obvious second phase peak exists in an XRD spectrum due to the very small content of the precipitated second phase.
According to the test result of the dynamic compression test, the dynamic yield strength of the alloy 3-600-2 is 1300MPa, and the corresponding fracture strain is 10 percent. In addition, after the dynamic compression test, the alloy 3-600-2 is crushed into 6 parts, and the fracture is mainly characterized by mixed crystal brittle fracture.
Example 7
Ti 25 Zr 9 Hf 30 Nb 5 Ta 30 Cu 1 The refractory high-entropy alloy is prepared by the following steps:
(1) High-purity Ti, high-purity Zr, high-purity Hf, high-purity Nb, high-purity Ta and high-purity Cu are used as raw materials, firstly, oxide skin on the surfaces of the raw materials is removed by grinding with a grinding wheel, then, ultrasonic oscillation cleaning is carried out with absolute ethyl alcohol, drying is carried out, and then, the clean raw materials with the total mass (840 +/-0.1) g are weighed according to the following atomic percentages of Ti;
(2) Putting the weighed clean raw materials into a water-cooled copper crucible of a high vacuum induction melting furnace in sequence from low melting point to high melting point, then vacuumizing until the vacuum degree in the furnace reaches 3 multiplied by 10 -3 After Pa, introducing high-purity argon as protective gas until the pressure in the furnace reaches 0.04MPa, turning on a power supply to carry out smelting, keeping the temperature for 20s after the raw materials are completely melted, then turning off the power supply to carry out cooling, turning over the cooled alloy ingot, and then repeatedly smelting to obtain the alloy ingot with the density of 11.30g/cm 3 The refractory high-entropy alloy ingot;
(3) Cutting the energy-containing high-entropy alloy ingot, polishing the cut surface, sealing the cut surface in a quartz tube filled with high-purity argon, heating the quartz tube to 1300 ℃, preserving the heat for 2 hours, and then carrying out water cooling to complete solid solution treatment; sealing the high-entropy alloy subjected to solution treatment in a quartz tube filled with high-purity argon, heating to 550 ℃, preserving the temperature for 3.5 hours, and then carrying out water cooling to finish aging treatment to obtain the Ti 25 Zr 9 Hf 30 Nb 5 Ta 30 Cu 1 High entropy alloy, abbreviated as alloy 4-550-3.5.
The appearance characterization shows that the alloy 4-550-3.5 is in an equiaxed crystal structure, the grain size is-195 mu m, and a Cu-Hf brittle precipitated phase continuously distributed exists in the grain boundary.
The alloy 4-550-3.5 is tested by a dynamic compression test, and the measured dynamic yield strength is 1400MPa, and the corresponding fracture strain is 36 percent. In addition, after the dynamic compression test, the alloy 4-550-3.5 is crushed into 4 parts, and the fracture is mainly characterized by crystal brittle fracture.
Comparative example 1
In addition to example 1, the Ti after the solution treatment in example 1 was treated 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 Heating the high-entropy alloy to 300 ℃ for aging treatment for 4 hours, and cooling after the aging treatment to obtain Ti 25 Zr 5 Hf 30 Nb 5 Ta 32 Cu 3 High entropy alloys, abbreviated as alloys 1-300-4.
As can be seen from the morphological characterization, the alloy 1-300-4 has an equiaxed crystal structure, the grain size thereof is 200 μm, and no obvious precipitated phase is seen, as shown in FIG. 3, which is mainly caused by the fact that the aging temperature does not reach the transformation temperature. The alloy 1-300-4 is single phase BCC as shown in FIG. 2.
According to the dynamic compression test results, the dynamic yield strength of the alloy 1-300-4 is 1670MPa, and the corresponding fracture strain is 50%, as shown in FIG. 4. In addition, as can be seen from fig. 5, after the dynamic compression test, the fracture of 1-300-4 is 2 parts along the direction of the maximum shear stress, and the fracture mainly has the characteristic of transgranular ductile fracture.
Comparative example 2
Ti 25 Zr 5 Hf 13 Nb 15 Ta 30 Cu 12 The preparation method of the refractory high-entropy alloy fragment comprises the following steps:
(1) High-purity Ti, high-purity Zr, high-purity Hf, high-purity Nb, high-purity Ta and high-purity Cu are used as raw materials, firstly, oxide skin on the surfaces of the raw materials is removed by grinding with a grinding wheel, then, ultrasonic oscillation cleaning is carried out with absolute ethyl alcohol, drying is carried out, and then, the clean raw materials with the total mass of (840 +/-0.1) g are weighed according to the following atomic percentages of Ti;
(2) Putting the weighed clean raw materials into a water-cooled copper crucible of a high vacuum induction melting furnace in sequence from low melting point to high melting point, then vacuumizing until the vacuum degree in the furnace reaches 3 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas until the pressure in the furnace reaches 0.04MPa, turning on a power supply to carry out smelting, keeping the temperature for 20s after the raw materials are completely melted, then turning off the power supply to carry out cooling, turning over the cooled alloy ingot, and then repeatedly smelting to obtain the alloy ingot with the density of 10.69g/cm 3 The refractory high-entropy alloy ingot;
(3) Cutting the energetic high-entropy alloy ingot, polishing the cut surface, sealing the cut surface in a quartz tube filled with high-purity argon, heating the quartz tube to 1300 ℃, preserving the temperature for 2 hours, and then performing water cooling to finish the solid solution treatment; sealing the high-entropy alloy subjected to solution treatment in a quartz tube filled with high-purity argon, heating to 450 ℃, preserving the temperature for 0.5h, and then performing water cooling to finish the processAging treatment to obtain the Ti 25 Zr 5 Hf 13 Nb 15 Ta 30 Cu 12 High entropy alloy, abbreviated as alloy 5-450-0.5.
The morphology characterization shows that the alloy 5-450-0.5 is in an equiaxial crystal structure, the grain size is 240 mu m, and a large amount of Hf-Cu brittle precipitated phases which are continuously distributed exist in the grain boundary.
The alloy 5-450-0.5 is tested by a dynamic compression test, and the measured dynamic yield strength is 950MPa, and the corresponding fracture strain is 0 percent. In addition, after dynamic compression test, alloy 5-450-0.5 is crushed into 10 parts, and fracture is mainly characterized by brittle fracture along the crystal.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A method for regulating and controlling the obdurability and failure mode of TiZrHfNbTa system refractory high-entropy alloy is characterized by comprising the following steps: using metal simple substances Ti, zr, hf, nb, ta and M as raw materials, carrying out alloying smelting to form a refractory high-entropy alloy ingot under the protection of inert gas, then heating the refractory high-entropy alloy ingot to 50-200 ℃ above the BCC phase transformation temperature, preserving heat for 1-8 h, then cooling to complete solid solution treatment, then heating to 400-700 ℃, preserving heat for 0.5-8 h, then cooling to complete aging treatment, and finally obtaining Ti which takes the BCC phase as a main phase structure and contains a small amount of nano precipitated phase as a second phase a Zr b Hf c Nb d Ta e M x The high-entropy refractory alloy has the advantages that the dynamic compressive strength and the fracture strain of the high-entropy refractory alloy are correspondingly changed within the ranges of 1000-2000 MPa and 10-40% by regulating and controlling the content of each component and preparation process parameters, and the failure mode is controllable;
the Ti a Zr b Hf c Nb d Ta e M x In the refractory high-entropy alloy, M is one or more of Al, cr, mn, fe, co, ni, cu and Mo, a is more than or equal to 25 and less than or equal to 60,0b is not less than 30,0 and not less than 40,0 and not less than 30,0 and not less than e is not less than 50,0 and not less than x is not less than 10, a + b + c + d + e + x =100 and 15 is not less than b + c is not less than 60.
2. The method for regulating the obdurability and the failure mode of the TiZrHfNbTa system refractory high-entropy alloy according to claim 1, is characterized in that: the Ti a Zr b Hf c Nb d Ta e M x In the refractory high-entropy alloy, a is not less than 25 and not more than 50,5 and not more than 20,5 and not more than c and not more than 30,5 and not more than d and not more than 20, e is not less than 15 and not more than 35,0 and not more than x and not more than 5, a + b + c + d + e + x =100, and b + c is not less than 15 and not more than 50.
3. The method for regulating and controlling the obdurability and the failure mode of the TiZrHfNbTa system refractory high-entropy alloy as claimed in claim 1 or 2, wherein the method comprises the following steps: m is one or more of Al, cr, cu and Mo.
4. The method for regulating and controlling the obdurability and the failure mode of the TiZrHfNbTa system refractory high-entropy alloy as claimed in claim 1 or 2, wherein the method comprises the following steps: when M is Cu or/and Al, x is more than 0 and less than or equal to 3, the aging temperature range is 450-600 ℃, and the aging time is 0.5-3.5 h.
5. The method for regulating the obdurability and the failure mode of the TiZrHfNbTa system refractory high-entropy alloy as claimed in claim 1 or 2, wherein the method comprises the following steps: when M is Cr or/and Mo, x is more than or equal to 2 and less than 5, the aging temperature range is 550-700 ℃, and the aging time is 3-8 h.
6. The method for regulating the obdurability and the failure mode of the TiZrHfNbTa system refractory high-entropy alloy as claimed in claim 1 or 2, wherein the method comprises the following steps: and alloying smelting is carried out by adopting an induction smelting furnace, and the repeated smelting times are more than 4.
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| CN116815077A (en) * | 2023-08-30 | 2023-09-29 | 北京中辰至刚科技有限公司 | Gas quenching aging heat treatment method based on TaHfNbZrTi refractory high-entropy alloy |
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