CN108220742B - Microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy and preparation method thereof - Google Patents
Microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy and a preparation method thereof, belonging to the technical field of metal materials. The refractory high-entropy alloy has good plasticity and high strength and can adjust the density in a wider range by mainly adjusting the proportion of main components and adding a small amount of microalloying elements; in addition, in the preparation process, the high-melting-point Hf, nb and Ta and micro-alloying elements except Al are pre-alloyed and smelted, and then Ti, zr, V and Al are added for final alloyed smelting, so that the uniform mixing of several components with huge melting point differences is ensured, and the prepared refractory high-entropy alloy is ensured to have excellent comprehensive performance.
Description
Technical Field
The invention particularly relates to a microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy with high strength and good plasticity and a preparation method thereof, belonging to the technical field of metal materials.
Background
The high-entropy alloy is also called multi-principal-element alloy, is a novel alloy developed in recent years, and is defined as an alloy consisting of five or more elements according to equal atomic ratio or nearly equal atoms, and the content of each main component is 5-35 at%; in addition, other alloying elements can be added for alloying, and the addition amount is less than 5at.%. The multi-principal component characteristic of the high-entropy alloy is different from the traditional alloy which has definite matrix elements (such as Fe-based alloy, ti-based alloy, al-based alloy, ni-based alloy and the like), so that the high-entropy alloy has very high mixed entropy in a liquid state or a disordered solid solution state, and the high mixed entropy can stabilize a solid solution phase, so that the alloy has simpler phase composition and microstructure.
Due to the multi-principal-element effect (high entropy effect, delayed diffusion effect, lattice distortion effect and cocktail effect), the metallurgical physical action mechanism of the high-entropy alloy is different from that of the traditional alloy, so that a series of excellent performances such as outstanding high-temperature strength, good low-temperature toughness, wear resistance, corrosion resistance, excellent irradiation resistance and the like are presented. Therefore, the high-entropy alloy has wide application prospects, such as: high-strength and high-hardness cutters and dies; a wear-resistant corrosion-resistant coating; turbine blades, solder for welding, and heat-resistant material for heat exchangers; a high strength structural material; biomedical materials, and the like.
Typical high entropy alloys that have been reported to date can be divided into four types: FCC structure solid solution high entropy alloy with Co, cr, fe, ni, mn and Cu as main constituent elements, typically CoCrFeNi, coCrFeNiMn and CoCrFeNiCu; BCC structure solid solution high entropy alloy formed by adding Al or/and Ti elements on the basis of Co, cr, fe, ni, mn and Cu, typically AlCoCrFeNi and AlCrFeCoNiTi 0.5 (ii) a Refractory high-entropy alloy composed of high-melting-point elements Ti, zr, hf, V, nb, ta, cr, mo and W, generally a solid solution with BCC structure; high-entropy amorphous alloy Zn with disordered structure 20 Ca 20 Sr 20 Yb 20 (Li 0.55 Mg 0.45 ) 20 PdPtCuNiP, tiZrCuNiBe, and the like. Among them, the most widely studied FeCoCrNiMn high entropy alloy has tensile plasticity as high as 60%, but yield strength is less than 300MPa. The refractory high-entropy alloy has the advantages of high yield strength and good high-temperature performance, and has application prospects in the field of high-temperature materials; however, the existing refractory high-entropy alloy has the problems of poor plasticity (almost no tensile plasticity at room temperature), high density and the like (generally more than 8 g/cm) 3 ). This greatly limits the practical application of refractory high-entropy alloys, and therefore, the development of the alloy with good propertiesThe refractory high-entropy alloy with strong plasticity matching has important significance.
Disclosure of Invention
Aiming at the problem of poor plasticity of the existing refractory high-entropy alloy, the invention aims to provide the microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy and the preparation method thereof, wherein the refractory high-entropy alloy has good plasticity and high strength and can adjust the density in a wide range by mainly adjusting the proportion of main components and adding a small amount of microalloying elements; in addition, the alloy is prepared by adopting a mature smelting alloying process, and the operation is simple.
The purpose of the invention is realized by the following technical scheme.
A microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy is composed of Ti, zr, hf, V, nb, ta and microalloyed elements, and the chemical formula of the microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy is marked as Ti a Zr b Hf c V d Nb e Ta f M x ；
Wherein M is more than one of Al, cr, mo, W, mn, fe, co, ni and Si; a = 15-45, b = 5-35, c = 5-35, d = 0-35, e = 0-35, f = 5-40, x = 0.1-15, 15 ≦ b + c ≦ 70, and 5 ≦ d + e + f ≦ 70 when d and e are not 0 at the same time.
The invention discloses a preparation method of a microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy, which comprises the following steps:
(1) Alloying and smelting clean elemental metals Hf, nb, ta and M (except Al) in an argon protective atmosphere, and cooling an alloy liquid I obtained by smelting to obtain an alloy ingot I; then overturning the alloy ingot I, and repeatedly smelting for more than 2 times to obtain a pre-alloyed alloy ingot;
(2) Alloying and smelting clean elemental metals Ti, zr, V and Al and a pre-alloyed alloy ingot under the protection of argon, and cooling an alloy liquid II obtained by smelting to obtain an alloy ingot II; and turning over the alloy ingot II, and repeatedly smelting for more than 4 times to obtain the refractory high-entropy alloy.
Wherein, the alloying smelting adopts vacuum smelting.
In addition, according to the shape and size of a required product, the prepared refractory high-entropy alloy can be heated and remelted under the argon protective atmosphere, and the molten alloy liquid is cast into a corresponding die for molding, so that the microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy with a specific shape is obtained.
Has the beneficial effects that:
(1) The refractory high-entropy alloy disclosed by the invention takes a BCC phase as a main composition phase, the valence electron number of main components is small, the alloy has good plasticity, and the characteristic of high strength of the alloy is retained by adding the microalloying elements, so that the refractory high-entropy alloy has good plasticity and high strength.
(2) The density of the refractory high-entropy alloy is adjustable in a wide range and is between 5.5g/cm 3 ～12g/cm 3 And the requirements of different use conditions can be met.
(3) The preparation of the refractory high-entropy alloy is completed by two steps of pre-alloying smelting and final alloying smelting of high-melting-point components, so that the uniform mixing of several components with great melting point difference is ensured; in addition, the alloy is prepared by adopting a mature alloy smelting process, and the operation is simple.
Drawings
FIG. 1 is Ti as described in example 1 32 Zr 30 Hf 5 V 10 Nb 13 Ta 5 Al 5 XRD (X-ray diffraction) spectrum of the refractory high-entropy alloy.
FIG. 2 is Ti as described in example 1 32 Zr 30 Hf 5 V 10 Nb 13 Ta 5 Al 5 The quasi-static tensile mechanical property curve chart of the refractory high-entropy alloy.
FIG. 3 is Ti of example 2 42 Zr 15 Hf 15 Nb 12 Ta 10 Al 6 XRD spectrogram of refractory high-entropy alloy.
FIG. 4 is Ti as described in example 2 42 Zr 15 Hf 15 Nb 12 Ta 10 Al 6 A quasi-static tensile mechanical property curve chart of the refractory high-entropy alloy.
FIG. 5 is Ti as described in example 3 30 Zr 8 Hf 20 Nb 8 Ta 30 Al 4 XRD spectrogram of refractory high-entropy alloy.
FIG. 6 shows Ti described in example 3 30 Zr 8 Hf 20 Nb 8 Ta 30 Al 4 A quasi-static tensile mechanical property curve chart of the refractory high-entropy alloy.
FIG. 7 is Ti as described in example 4 35 Zr 25 Hf 25 Nb 5 Ta 5 Mo 5 XRD spectrogram of refractory high-entropy alloy.
FIG. 8 is Ti as described in example 4 35 Zr 25 Hf 25 Nb 5 Ta 5 Mo 5 A quasi-static tensile mechanical property curve chart of the refractory high-entropy alloy.
FIG. 9 shows Ti described in example 5 33 Zr 20 Hf 15 Nb 20 Ta 5 Al 5 Mo 2 XRD spectrogram of the refractory high-entropy alloy.
FIG. 10 shows Ti in example 5 33 Zr 20 Hf 15 Nb 20 Ta 5 Al 5 Mo 2 A quasi-static tensile mechanical property curve chart of the refractory high-entropy alloy.
FIG. 11 shows Ti described in example 6 28 Zr 25 Hf 28 Ta 17 Al 2 XRD spectrogram of refractory high-entropy alloy.
FIG. 12 is Ti of example 6 28 Zr 25 Hf 28 Ta 17 Al 2 A quasi-static tensile mechanical property curve chart of the refractory high-entropy alloy.
Detailed Description
The invention is further illustrated by the following figures and detailed description, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public disclosure 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 equipment is shown in Table 2.
TABLE 1
TABLE 2
2) Performance testing and structural characterization
(1) And (3) density measurement: the method adopts an Archimedes drainage method for measurement, and comprises the following specific operation steps: the refractory high-entropy alloy in the embodiment is prepared into 3 pieces
Before measurement, the cylindrical sample is put into a beaker filled with absolute ethyl alcohol, is cleaned for 10min by ultrasonic oscillation, is taken out and dried, and then the dry weight M of each sample is weighed by a DT-100 precision balance (the precision is 0.1 mg) 1 Each sample is weighed 3 times to reduce measurement errors; then, the mass M of each sample in water was reweighed 2 Each sample was weighed 3 times; finally, the density calculation is carried out according to the following formula,
in the formula, ρ 0 The temperature of water is 0.9982g/cm 3 (20℃)；ρ l Air density, 0.0012g/cm 3 。
(2) Phase analysis: the phase analysis is carried out by adopting a D8advance X-ray diffractometer of Bruker AXS company in Germany, the working voltage and the current are respectively 40KV and 40mA, the X-ray source is CuKa (lambda =0.1542 nm) ray, the scanning speed is 0.2sec/step, the scanning step is 0.02 DEG/step, and the scanning range is 20-100 deg.
(3) Quasi-static tensile test: according to the standard GB-T228.1-2010, a CMT4305 type microcomputer electronic universal testing machine is adopted to carry out room-temperature axial quasi-static tensile test, and the strain rate is selected to be 10 -3 s -1 The test sample isThe thickness of a sample is 1.0mm, the width of the sample is 3.14mm, the length of the parallel segment is 10mm, and the length of the gauge length is 5mm.
Example 1
Ti 32 Zr 30 Hf 5 V 10 Nb 13 Ta 5 Al 5 The refractory high-entropy alloy comprises the following specific preparation steps:
(1) The method comprises the following steps of (1) taking simple substances Ti, zr, hf, V, nb, ta and Al with the purity of more than 99.7wt% as raw materials, grinding by using a grinding wheel to remove oxide skin on the surfaces of the raw materials, and then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol to obtain a clean raw material, wherein the clean raw material with the total mass of (80 +/-0.01) g is weighed according to the atomic percent;
(2) Putting the weighed simple substances Hf, nb and Ta into a water-cooled copper crucible in a high-vacuum non-consumable arc melting furnace, then vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot I, overturning the alloy ingot I, and repeatedly smelting for 2 times to obtain a pre-alloyed alloy ingot;
(3) Putting weighed simple substances of Ti, zr, V and Al and the pre-alloyed alloy ingot obtained in the step (2) into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot II, overturning the alloy ingot II, and repeatedly smelting for 4 times to obtain a mother alloy ingot;
(4) Putting the master alloy ingot in a high vacuum arc melting-turnover casting system, vacuumizing a furnace chamber until the vacuum degree reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon; smelting under the protection of argon, and heating with current of 20AIncreasing the step to 500A, after the mother alloy ingot is completely melted, casting the alloy liquid into a copper mould (the size of a cavity is phi 10mm multiplied by 60 mm) for forming to obtain Ti 32 Zr 30 Hf 5 V 10 Nb 13 Ta 5 Al 5 Refractory high-entropy alloy bars.
Fig. 1 is an XRD spectrum of the refractory high-entropy alloy prepared in this example, and according to the lattice diffraction extinction law, five diffraction peaks in the spectrum can be determined to correspond to the (110), (200), (211), (220) and (310) crystal planes of the BCC structural phase, respectively, which indicates that the prepared refractory high-entropy alloy is mainly composed of the BCC phase. According to the graph 2, the yield strength of the prepared refractory high-entropy alloy is 960MPa, the tensile strength is 980MPa, and the elongation rate reaches 37%. The density of the prepared high-entropy alloy is only 6.85g/cm through test calculation 3 The composite material has the advantages of high strength, good plasticity, low density and the like, and has excellent comprehensive performance.
Example 2
Ti 42 Zr 15 Hf 15 Nb 12 Ta 10 Al 6 The refractory high-entropy alloy comprises the following specific preparation steps:
(1) The method comprises the following steps of taking simple substances Ti, zr, hf, nb, ta and Al with the purity of more than 99.7wt% as raw materials, firstly grinding by using a grinding wheel to remove oxide skin on the surfaces of the raw materials, and then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol to obtain a clean raw material, wherein the clean raw material with the total mass of (80 +/-0.01) g is weighed according to the atomic percent;
(2) Putting the weighed simple substances Hf, nb and Ta into a water-cooled copper crucible in a high-vacuum non-consumable arc melting furnace, then vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot I, overturning the alloy ingot I, and repeatedly smelting for 2 times to obtain a pre-alloyed alloy ingot;
(3) Weighing Ti, zr and Al as simple substances and the substances obtained in the step (2)Putting the obtained pre-alloyed alloy ingot into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as a protective gas; before the alloy is smelted, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot II, overturning the alloy ingot II, and repeatedly smelting for 4 times to obtain a mother alloy ingot;
(4) Putting the master alloy ingot in a high vacuum arc melting-turnover casting system, vacuumizing a furnace chamber until the vacuum degree reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon; smelting under the protection of argon, gradually increasing the heating current from 20A to 500A, and after the mother alloy ingot is completely molten, casting the alloy liquid into a copper mold (the size of a cavity is phi 10mm multiplied by 60 mm) for molding to obtain Ti 42 Zr 15 Hf 15 Nb 12 Ta 10 Al 6 Refractory high-entropy alloy bars.
Fig. 3 is an XRD spectrum of the refractory high-entropy alloy prepared in this example, and according to the lattice diffraction extinction law, five diffraction peaks in the spectrum can be determined to correspond to the (110), (200), (211), (220) and (310) crystal planes of the BCC structural phase, respectively, which indicates that the prepared refractory high-entropy alloy is mainly composed of the BCC phase. According to the graph in FIG. 4, the yield strength of the prepared refractory high-entropy alloy is 910MPa, the tensile strength is 930MPa, and the elongation rate is 33%. The density of the prepared high-entropy alloy is 7.42g/cm according to test calculation 3 The composite material has the advantages of high strength, good plasticity, lower density and the like, and has excellent comprehensive performance.
Example 3
Ti 30 Zr 8 Hf 20 Nb 8 Ta 30 Al 4 The refractory high-entropy alloy comprises the following specific preparation steps:
(1) The method comprises the following steps of taking simple substances Ti, zr, hf, nb, ta and Al with the purity of more than 99.7wt% as raw materials, firstly grinding by using a grinding wheel to remove oxide skin on the surfaces of the raw materials, and then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol to obtain a clean raw material, wherein the clean raw material with the total mass of (80 +/-0.01) g is weighed according to the atomic percent;
(2) Putting the weighed simple substances Hf, nb and Ta into a water-cooled copper crucible in a high-vacuum non-consumable arc melting furnace, then vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot I, overturning the alloy ingot I, and repeatedly smelting for 2 times to obtain a pre-alloyed alloy ingot;
(3) Putting weighed simple substances of Ti, zr and Al and the pre-alloyed alloy ingot obtained in the step (2) into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot II, overturning the alloy ingot II, and repeatedly smelting for 4 times to obtain a mother alloy ingot;
(4) Putting the master alloy ingot in a high vacuum arc melting-turnover casting system, vacuumizing a furnace chamber until the vacuum degree reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon; smelting under the protection of argon, gradually increasing the heating current from 20A to 500A, and after the mother alloy ingot is completely molten, casting the alloy liquid into a copper mold (the size of a cavity is phi 10mm multiplied by 60 mm) for molding to obtain Ti 30 Zr 8 Hf 20 Nb 8 Ta 30 Al 4 Refractory high-entropy alloy bars.
Fig. 5 is an XRD spectrum of the refractory high-entropy alloy prepared in this example, and according to the lattice diffraction extinction law, five diffraction peaks in the spectrum can be determined to correspond to the (110), (200), (211), (220) and (310) crystal planes of the BCC structural phase, respectively, which indicates that the prepared refractory high-entropy alloy is mainly composed of the BCC phase. According to FIG. 6, the prepared refractory high-entropy alloyThe yield strength of the steel is 930MPa, the tensile strength is 960MPa, and the elongation reaches 24 percent. The density of the prepared high-entropy alloy is 10.08g/cm according to test calculation 3 The composite material has the advantages of high strength, good plasticity, high density and the like, and has excellent comprehensive performance.
Example 4
Ti 35 Zr 25 Hf 25 Nb 5 Ta 5 Mo 5 The refractory high-entropy alloy comprises the following specific preparation steps:
(1) The method comprises the following steps of taking simple substances Ti, zr, hf, nb, ta and Mo with the purity of more than 99.7wt% as raw materials, firstly grinding by using a grinding wheel to remove oxide skin on the surfaces of the raw materials, and then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol to obtain a clean raw material, wherein the clean raw material with the total mass of (80 +/-0.01) g is weighed according to the atomic percent;
(2) Putting weighed simple substances Hf, nb, ta and Mo into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, then vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before the alloy is smelted, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot I, overturning the alloy ingot I, and repeatedly smelting for 2 times to obtain a pre-alloyed alloy ingot;
(3) Putting weighed simple substances Ti and Zr and the pre-alloyed alloy ingot obtained in the step (2) into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot II, overturning the alloy ingot II, and repeatedly smelting for 4 times to obtain a mother alloy ingot;
(4) Putting the master alloy ingot in a high vacuum arc melting-turnover casting system, vacuumizing a furnace chamber until the vacuum is achievedThe degree reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon; smelting under the protection of argon, gradually increasing the heating current from 20A to 500A, and after the mother alloy ingot is completely molten, casting the alloy liquid into a copper mold (the size of a cavity is phi 10mm multiplied by 60 mm) for molding to obtain Ti 35 Zr 25 Hf 25 Nb 5 Ta 5 Mo 5 Refractory high-entropy alloy bars.
Fig. 7 is an XRD spectrogram of the refractory high-entropy alloy prepared in this example, and according to the lattice diffraction extinction principle, five diffraction peaks in the spectrogram can be determined to correspond to the (110), (200), (211), (220) and (310) crystal planes of the BCC structure phase, respectively, which indicates that the prepared refractory high-entropy alloy mainly consists of the BCC phase. As can be seen from FIG. 8, the yield strength of the prepared refractory high-entropy alloy is 830MPa, the tensile strength is 860MPa, and the elongation is 10%. The density of the prepared high-entropy alloy is 7.96g/cm according to test calculation 3 。
Example 5
Ti 33 Zr 20 Hf 15 Nb 20 Ta 5 Al 5 Mo 2 The refractory high-entropy alloy comprises the following specific preparation steps:
(1) The method comprises the following steps of (1) taking simple substances Ti, zr, hf, nb, ta, al and Mo with the purity of more than 99.7wt% as raw materials, grinding by using a grinding wheel to remove oxide skin on the surfaces of the raw materials, and then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol to obtain a clean raw material, wherein the clean raw material with the total mass of (80 +/-0.01) g is weighed according to the atomic ratio of Ti;
(2) Putting weighed simple substances Hf, nb, ta and Mo into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, then vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot I, overturning the alloy ingot I, and repeatedly smelting for 2 times to obtain a pre-alloyed alloy ingot;
(3) Putting weighed simple substances of Ti, zr and Al and the pre-alloyed alloy ingot obtained in the step (2) into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot II, overturning the alloy ingot II, and repeatedly smelting for 4 times to obtain a mother alloy ingot;
(4) Putting the master alloy ingot in a high vacuum arc melting-turnover casting system, vacuumizing a furnace chamber until the vacuum degree reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon; smelting under the protection of argon, gradually increasing the heating current from 20A to 500A, and after the mother alloy ingot is completely molten, casting the alloy liquid into a copper mold (the size of a cavity is phi 10mm multiplied by 60 mm) for molding to obtain Ti 33 Zr 20 Hf 15 Nb 20 Ta 5 Al 5 Mo 2 Refractory high-entropy alloy bars.
Fig. 9 is an XRD spectrum of the refractory high-entropy alloy prepared in this example, and according to the lattice diffraction extinction law, five diffraction peaks in the spectrum can be determined to correspond to the (110), (200), (211), (220) and (310) crystal planes of the BCC structural phase, respectively, which indicates that the prepared refractory high-entropy alloy is mainly composed of the BCC phase. As can be seen from FIG. 10, the yield strength of the prepared refractory high-entropy alloy is 900MPa, the tensile strength is 917MPa, and the elongation rate is 42%. The density of the prepared high-entropy alloy is 7.72g/cm according to test calculation 3 The composite material has the advantages of high strength, good plasticity, lower density and the like, and has excellent comprehensive performance.
Example 6
Ti 28 Zr 25 Hf 28 Ta 17 Al 2 The refractory high-entropy alloy comprises the following specific preparation steps:
(1) The method comprises the following steps of taking simple substances Ti, zr, hf, ta and Al with the purity of more than 99.7wt% as raw materials, firstly polishing by using a grinding wheel to remove oxide skin on the surfaces of the raw materials, then carrying out ultrasonic oscillation cleaning by using absolute ethyl alcohol to obtain a clean raw material, and weighing the clean raw material with the total mass (80 +/-0.01) g according to the atomic percent of Ti, zr, hf, ta, al = 28;
(2) Putting the weighed simple substances Hf and Ta into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, then vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot I, overturning the alloy ingot I, and repeatedly smelting for 2 times to obtain a pre-alloyed alloy ingot;
(3) Putting weighed simple substances of Ti, zr and Al and the pre-alloyed alloy ingot obtained in the step (2) into a water-cooled copper crucible in a high-vacuum non-consumable electric arc melting furnace, vacuumizing until the vacuum degree in the melting furnace reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon as protective gas; before smelting the alloy, smelting a pure titanium metal ingot to further reduce the oxygen content in a furnace chamber, then carrying out alloying smelting, homogenizing the alloy by utilizing electromagnetic stirring in the smelting process, smelting for 10min, cooling to obtain an alloy ingot II, overturning the alloy ingot II, and repeatedly smelting for 4 times to obtain a mother alloy ingot;
(4) Putting the master alloy ingot in a high vacuum arc melting-turnover casting system, vacuumizing a furnace chamber until the vacuum degree reaches 2.5 multiplied by 10 -3 After Pa, filling high-purity argon; smelting under the protection of argon, gradually increasing the heating current from 20A to 500A, and after the mother alloy ingot is completely molten, casting the alloy liquid into a copper mold (the size of a cavity is phi 10mm multiplied by 60 mm) for molding to obtain Ti 28 Zr 25 Hf 28 Ta 17 Al 2 Refractory high-entropy alloy bars.
Fig. 11 is an XRD spectrogram of the refractory high-entropy alloy prepared in this example, and according to the lattice diffraction extinction law, five diffraction peaks in the spectrogram can be determined to correspond to the (110), (200), (211), (220) and (310) crystal planes of the BCC structural phase, respectively, which indicates that the prepared refractory high-entropy alloy is mainly composed of the BCC phase; in addition, the vicinity of the (110) peakThe three weaker diffraction peaks (indicated by inverted triangles in the figure) of the refractory high-entropy alloy are the diffraction peaks corresponding to HCP, indicating that a small amount of HCP phase exists in the refractory high-entropy alloy. According to the graph 12, the yield strength of the prepared refractory high-entropy alloy is 460MPa, the tensile strength is 800MPa, and the elongation rate reaches 40%. The density of the prepared high-entropy alloy is 9.16g/cm according to test calculation 3 Has the advantages of high strength, good plasticity, high density and the like.
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 (4)
1. A microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy is characterized in that: the chemical formula of the refractory high-entropy alloy is marked as Ti a Zr b Hf c V d Nb e Ta f M x M is more than one of Al, cr, mo, W, mn, fe, co and Ni;
wherein a = 15-45, b = 5-35, c = 5-35, d = 0-10, e = 0-35, f = 5-40, x = 0.1-7, 15 ≦ b + c ≦ 70, and d ≦ d + e + f ≦ 38 when d and e are not 0 at the same time.
2. A method of making a microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high entropy alloy as claimed in claim 1, characterized in that: the method comprises the following steps of,
(1) Alloying and smelting clean elemental metals Hf, nb and Ta and M except Al under the argon protective atmosphere, and cooling an alloy liquid I obtained by smelting to obtain an alloy ingot I; then, turning over the alloy ingot I, and repeatedly smelting for more than 2 times to obtain a pre-alloyed alloy ingot;
(2) Alloying and smelting clean elemental metals Ti, zr and V and a pre-alloyed alloy ingot or alloying and smelting clean elemental metals Ti, zr, V and Al and a pre-alloyed alloy ingot under the protection of argon, and cooling an alloy liquid II obtained by smelting to obtain an alloy ingot II; and turning over the alloy ingot II, and repeatedly smelting for more than 4 times to obtain the refractory high-entropy alloy.
3. The preparation method of the microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy is characterized in that: the alloying smelting adopts vacuum smelting.
4. The preparation method of the microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy according to claim 2, characterized by comprising the following steps of: and heating and remelting the obtained refractory high-entropy alloy in an argon protective atmosphere, and casting the molten alloy liquid into a mold for molding to obtain the microalloyed Ti-Zr-Hf-V-Nb-Ta refractory high-entropy alloy in the required shape.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602872A (en) * | 2013-10-31 | 2014-02-26 | 北京科技大学 | TiZrNbVMo[x] high entropy alloy and preparation method thereof |
| CN104120325A (en) * | 2014-07-04 | 2014-10-29 | 北京科技大学 | Low thermal expansion coefficient NaMxAlySiz high entropy alloy and preparation method thereof |
| CN104451338A (en) * | 2014-12-03 | 2015-03-25 | 北京理工大学 | Cocrfenialcusi high-entropy alloy and preparation method thereof |
| CN105296836A (en) * | 2015-11-17 | 2016-02-03 | 北京科技大学 | NxMy high-entropy alloy with shape memory effect and preparing method thereof |
| WO2016112210A1 (en) * | 2015-01-09 | 2016-07-14 | Scoperta, Inc. | High entropy alloys with non-high entropy second phases |
| KR20170027520A (en) * | 2015-09-02 | 2017-03-10 | 한국과학기술원 | Hight-entropy multioelement alloy with single phase and process for preparing the same |
| CN107619982A (en) * | 2017-11-03 | 2018-01-23 | 北京理工大学 | Hexa-atomic the infusibility high-entropy alloy and its verification method of a kind of high-ductility high intensity |
| CN107686928A (en) * | 2017-10-17 | 2018-02-13 | 中南大学 | A kind of high-performance NiCoCrFeMnTi systems high-entropy alloy and preparation method thereof |
| CN107739956A (en) * | 2017-09-14 | 2018-02-27 | 北京理工大学 | A kind of Nb microalloyings Ni Co Fe Cr Al high-entropy alloys |
-
2018
- 2018-03-14 CN CN201810208569.5A patent/CN108220742B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602872A (en) * | 2013-10-31 | 2014-02-26 | 北京科技大学 | TiZrNbVMo[x] high entropy alloy and preparation method thereof |
| CN104120325A (en) * | 2014-07-04 | 2014-10-29 | 北京科技大学 | Low thermal expansion coefficient NaMxAlySiz high entropy alloy and preparation method thereof |
| CN104451338A (en) * | 2014-12-03 | 2015-03-25 | 北京理工大学 | Cocrfenialcusi high-entropy alloy and preparation method thereof |
| WO2016112210A1 (en) * | 2015-01-09 | 2016-07-14 | Scoperta, Inc. | High entropy alloys with non-high entropy second phases |
| KR20170027520A (en) * | 2015-09-02 | 2017-03-10 | 한국과학기술원 | Hight-entropy multioelement alloy with single phase and process for preparing the same |
| CN105296836A (en) * | 2015-11-17 | 2016-02-03 | 北京科技大学 | NxMy high-entropy alloy with shape memory effect and preparing method thereof |
| CN107739956A (en) * | 2017-09-14 | 2018-02-27 | 北京理工大学 | A kind of Nb microalloyings Ni Co Fe Cr Al high-entropy alloys |
| CN107686928A (en) * | 2017-10-17 | 2018-02-13 | 中南大学 | A kind of high-performance NiCoCrFeMnTi systems high-entropy alloy and preparation method thereof |
| CN107619982A (en) * | 2017-11-03 | 2018-01-23 | 北京理工大学 | Hexa-atomic the infusibility high-entropy alloy and its verification method of a kind of high-ductility high intensity |
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