CN113088784B - Multi-principal-element alloy containing BCC/B2 dual-phase structure and preparation method thereof - Google Patents

Multi-principal-element alloy containing BCC/B2 dual-phase structure and preparation method thereof Download PDF

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CN113088784B
CN113088784B CN202110325271.4A CN202110325271A CN113088784B CN 113088784 B CN113088784 B CN 113088784B CN 202110325271 A CN202110325271 A CN 202110325271A CN 113088784 B CN113088784 B CN 113088784B
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CN113088784A (en
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靳柯
董亚光
王本鹏
薛云飞
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Zhejiang Institute Of Science And Innovation New Materials
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18High-melting or refractory metals or alloys based thereon

Abstract

The invention relates to a multi-principal-element alloy containing a BCC/B2 dual-phase structure and a preparation method thereof, belonging to the technical field of metal materials. The multi-principal-element alloy is a braided BCC/B2 two-phase structure, and the chemical formula of the multi-principal-element alloy is Ti according to the atomic percentage of each elementaTabNbcZrdAleMfM is at least one of V, Cr, Ni, Cu, Fe, Si, Mg, Y, B, C and O, a is more than 30 and less than or equal to 60, B is more than 0 and less than or equal to 15, C is more than or equal to 5 and less than or equal to 50, d is more than or equal to 5 and less than or equal to 40, e is more than or equal to 5 and less than or equal to 15, f is more than or equal to 0 and less than or equal to 10, B + C + d is more than or equal to 40 and less than or equal to 75, B/d is more than or equal to 0.3 and less than or equal to 0.6, and the multi-principal element alloy has good plasticity and high strength by optimizing the composition elements, the content of each element and the microstructure. In addition, the multi-principal-element alloy can be obtained by alloy smelting and annealing treatment, and the preparation method is simple, safe and reliable and has good application prospect.

Description

Multi-principal-element alloy containing BCC/B2 dual-phase structure and preparation method thereof
Technical Field
The invention relates to a multi-principal-element alloy containing a BCC/B2 dual-phase structure and a preparation method thereof, belonging to the technical field of metal materials.
Background
The multi-principal-element alloy is a novel metal material formed by combining three or more elements according to approximately equal atomic ratio. The appearance of the multi-principal-element alloy breaks through the traditional alloy design concept mainly based on one or two elements, and the degree of freedom of alloy design is increased. The unique high entropy effect, the delayed diffusion effect, the lattice distortion effect and the cocktail effect of the multi-principal-element alloy enable the alloy to have unique structure and excellent performance, thereby gaining wide attention at home and abroad.
In recent years, researchers find that the multi-principal-element alloy with the Body Centered Cubic (BCC) structure shows outstanding high-temperature strength, good wear resistance, good corrosion resistance and excellent radiation resistance, and has good application prospects. On this basis, it was found that by introducing a coherent ordered BCC (B2) phase in BCC solid solution, a significant increase in strength was achieved. The reported multi-principal element alloy with BCC/B2 dual-phase structure has higher strength, but the plasticity of the alloy is generally lower (the compressive fracture strain is lower than 15 percent), which greatly limits the engineering application of the alloy of the system.
Disclosure of Invention
Aiming at the problem that the strength and the plasticity of the existing BCC/B2 dual-phase structure multi-principal-element alloy cannot be compatible, the invention provides the BCC/B2 dual-phase structure multi-principal-element alloy and the preparation method thereof, and the multi-principal-element alloy with good plasticity and higher strength is obtained by optimizing alloy composition elements, the content of each element and the microstructure structure; and the preparation method of the alloy is simple, safe and reliable, and has good application prospect.
The purpose of the invention is realized by the following technical scheme.
A multi-principal-element alloy with BCC/B2 dual-phase structure, the chemical formula of the multi-principal-element alloy is recorded as Ti according to the atomic percentage (at%) of each elementaTabNbcZrdAleMfM is at least one of V, Cr, Ni, Cu, Fe, Si, Mg, Y, B, C and O, a is more than 30 and less than or equal to 60, B is more than 0 and less than or equal to 15, C is more than or equal to 5 and less than or equal to 50, d is more than or equal to 5 and less than or equal to 40, e is more than or equal to 5 and less than 15, f is more than or equal to 0 and less than or equal to 10, B + C + d is more than or equal to 40 and less than or equal to 75, and B/d is more than or equal to 0.3 and less than or equal to 0.6.
Further, the TiaTabNbcZrdAleMfWherein a is more than 30 and less than or equal to 45, b is more than or equal to 5 and less than or equal to 15, c is more than or equal to 15 and less than or equal to 35, d is more than or equal to 15 and less than or equal to 35, e is more than or equal to 5 and less than or equal to 10, f is more than or equal to 0 and less than or equal to 5, b + c + d is more than or equal to 40 and less than or equal to 75, and b/d is more than or equal to 0.3 and less than or equal to 0.6.
Further, the TiaTabNbcZrdAleMfIn the formula, M is at least one of V, Cr, Y and B.
The invention relates to a preparation method of a multi-principal-element alloy with a BCC/B2 dual-phase structure, which comprises the following specific steps:
(1) putting simple substances corresponding to Ti, Ta, Nb, Zr, Al and M elements into a smelting furnace according to atomic percentage, carrying out alloying smelting under the protective atmosphere of nitrogen or inert gas, cooling an alloy liquid formed by smelting to obtain an alloy ingot, turning over the alloy ingot and repeatedly smelting for more than 3 times to obtain an alloy ingot;
(2) in the protective atmosphere of nitrogen or inert gas, the alloy ingot is annealed at the high temperature of 1100-1400 ℃ for 6-24 h, and then is cooled to room temperature in a cooling medium to obtain high-temperature annealing alloy;
(3) directly placing the high-temperature annealing alloy in an argon protective atmosphere, carrying out low-temperature annealing treatment for 0.5-20 h at 400-650 ℃, and then cooling to room temperature in a cooling medium to obtain the multi-principal-element alloy containing the BCC/B2 dual-phase structure.
Further, the purities of the simple substances corresponding to Ti, Ta, Nb, Zr, Al and M in the step (1) are all more than 99.9 wt.%.
Further, the smelting furnace in the step (1) is a non-consumable vacuum arc smelting furnace or a suspension smelting furnace.
Further, the cooling medium in step (2) and step (3) is one of air, room temperature water and brine ice.
Further, the time of the low-temperature annealing treatment at 400 to 650 ℃ is preferably 2 to 12 hours.
Has the advantages that:
(1) according to the invention, the high-temperature mechanical property is ensured by optimizing the content of alloy constituent elements and the content of each element, and selecting high-melting metal elements such as Ti, Ta, Nb and Zr, the high principal component content with good plasticity of Ti, Nb and the like ensures the good plasticity of the alloy, and the woven BCC/B2 dual-phase structure retains the high-strength characteristic of the multi-principal component alloy, so that the BCC/B2 dual-phase structure multi-principal component alloy with good plasticity and high strength is obtained.
(2) In the multi-principal element alloy, the Al element with proper content can promote the order transformation of the multi-principal element alloy, and a braided BCC/B2 dual-phase structure is obtained. If the Al content is too high, a large-sized Al-Zr phase may be formed in the multi-principal alloy during the low-temperature annealing treatment, and the Al-Zr phase may easily aggregate at grain boundaries, resulting in embrittlement of the multi-principal alloy. In addition, Al element can form a layer of compact oxidation film on the surface of the multi-principal-element alloy, which is beneficial to improving the high-temperature oxidation resistance of the multi-principal-element alloy.
(3) In the method, the low-temperature annealing treatment temperature is controlled to be 400-650 ℃, the woven BCC/B2 dual-phase structure is damaged due to overhigh temperature, and Al and Zr are easily enriched at the grain boundary to form an Al-Zr phase, so that the mechanical property of the multi-principal-element alloy is deteriorated; the method has the advantages of simple and easy preparation, safety, reliability, reasonable production process control and great application potential in the fields of aerospace, petrochemical industry and the like.
Drawings
FIG. 1 shows Ti prepared in example 133.25Ta14.25Nb23.75Zr23.75Al5X-ray diffraction pattern of (a).
FIG. 2 shows Ti prepared in example 133.25Ta14.25Nb23.75Zr23.75Al5Low power Scanning Electron Microscope (SEM) images of (a).
FIG. 3 shows Ti prepared in example 133.25Ta14.25Nb23.75Zr23.75Al5High power scanning electron microscopy images of (a).
FIG. 4 shows Ti prepared in example 231.5Ta13.5Nb22.5Zr22.5Al10X-ray diffraction pattern of (a).
FIG. 5 shows Ti prepared in example 231.5Ta13.5Nb22.5Zr22.5Al10Low power scanning electron microscopy images.
FIG. 6 shows Ti prepared in example 231.5Ta13.5Nb22.5Zr22.5Al10High power scanning electron microscopy.
FIG. 7 shows Ti prepared in example 342Ta8Nb15Zr25Al9Cr1Low power scanning electron microscopy images.
FIG. 8 shows Ti prepared in example 342Ta8Nb15Zr25Al9Cr1High power scanning electron microscopy images of (a).
FIG. 9 shows Ti prepared in comparative example 128.5Ta19Nb23.75Zr23.75Al5Low power scanning electron microscopy images.
FIG. 10 shows Ti prepared in comparative example 128.5Ta19Nb23.75Zr23.75Al5High power scanning electron microscopy images.
FIG. 11 shows Ti prepared in comparative example 236Ta9Nb22.5Zr22.5Al10High power scanning electron microscopy images of (a).
FIG. 12 shows Ti prepared in comparative example 335Ta10Nb20Zr20Al20High power scanning electron microscopy images of (a).
Detailed Description
The present invention is further illustrated with reference to specific embodiments, wherein the process is conventional unless otherwise specified, and the starting materials are commercially available from a public source unless otherwise specified.
In the following examples:
phase analysis: the prepared multi-principal-element alloy is subjected to phase analysis by adopting a D8 advanced X-ray diffractometer of Bruker AXS company in Germany, wherein an X-ray source is Cu target Kalpha ray, the working voltage is 40kV, the working current is 110mA, the scanning speed is 5 DEG/min, the scanning angle range is 20-100 DEG, and the step length is 0.02 deg.
And (3) microstructure: the microstructure characterization of the prepared multi-principal-element alloy is carried out by adopting a German Zeiss Supra55 scanning electron microscope, and a back scattering electron signal is used, wherein the emission voltage is 15kV, and the magnification is up to 30000 times. Sample preparation: firstly, polishing by using a silicon dioxide suspension with the granularity of 0.02 mu m, and then performing stress relief polishing by using an OPS + hydrogen peroxide suspension, wherein the volume ratio of OPS to hydrogen peroxide is 7: 3.
Quasi-static compression: the compression mechanical property of the prepared multi-principal-element alloy is tested by adopting an Instron model 5982 electronic universal tester, the size of a compression sample is in a cylinder shape of phi 4mm multiplied by 6mm, and the strain rate is controlled to be 1 multiplied by 10 in the deformation process-3/s。
Example 1
A multi-principal-element alloy with a BCC/B2 dual-phase structure comprises the following constituent elements in percentage by atom: titanium (Ti)33.25 at.%, tantalum (Ta)14.25 at.%, niobium (Nb)23.75 at.%, zirconium (Zr)23.75 at.%, and aluminum (Al)5 at.%. The preparation method of the multi-principal-element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr and Al with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to less than or equal to 5 multiplied by 10- 3Introducing argon after Pa, then carrying out alloying smelting, cooling the alloy liquid formed by smelting to room temperature in a water-cooling copper mold to obtain an alloy ingot, and then overturning the alloy ingot and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon to carry out high-temperature annealing treatment, wherein the annealing treatment temperature is 1300 ℃, the annealing treatment time is 24h, and then placing the alloy ingot in a tank of room temperature water (20-30 ℃, the same below) to cool to room temperature to obtain high-temperature annealed alloy;
(3) placing the high-temperature annealing alloy in a heat treatment furnace filled with argon gas for low-temperature annealing treatment at the temperature of 550 ℃ for 6 hours, and then cooling the high-temperature annealing alloy in the air to room temperature to obtain the Ti with the BCC/B2 dual-phase structure33.25Ta14.25Nb23.75Zr23.75Al5And (3) alloying.
As can be seen from the XRD spectrum of fig. 1, the multi-primary alloy prepared in example 1 contains BCC and B2 phases. As can be seen from the SEM image of FIG. 2, the multi-principal element alloy prepared in example 1 is equiaxed and has a grain size of 318. + -.32 μm. As can be seen from fig. 3, the multi-element alloy prepared in example 1 had a woven structure.
Example 2
A multi-principal-element alloy with a BCC/B2 dual-phase structure comprises the following constituent elements in percentage by atom: titanium (Ti)31.5 at.%, tantalum (Ta)13.5 at.%, niobium (Nb)22.5 at.%, zirconium (Zr)22.5 at.%, and aluminum (Al)10 at.%. The preparation method of the multi-principal element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr and Al with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to be less than or equal to 5 multiplied by 10- 3Introducing argon after Pa, then carrying out alloying smelting, cooling the alloy liquid formed by smelting to room temperature in a water-cooled copper mould to obtain an alloy ingot, and then overturning and repeatedly smelting the alloy ingot for 6 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon gas for high-temperature annealing treatment, wherein the annealing treatment temperature is 1200 ℃, the annealing treatment time is 24 hours, and then placing the alloy ingot in a tank of room-temperature water to cool to room temperature to obtain high-temperature annealed alloy;
(3) placing the high-temperature annealing alloy in a heat treatment furnace filled with argon gas for low-temperature annealing treatment at the temperature of 600 ℃ for 3h, and then cooling the high-temperature annealing alloy in a room-temperature water tank to room temperature to obtain Ti with a BCC/B2 dual-phase structure31.5Ta13.5Nb22.5Zr22.5Al10And (3) alloying.
As can be seen from the XRD spectrum of FIG. 4, the multi-primary alloy prepared in example 2 contains BCC and B2 phases. As can be seen from the SEM image of FIG. 5, the multi-principal element alloy prepared in example 2 is equiaxed and has a grain size of 155. + -. 38 μm. As can be seen from fig. 6, the multi-principal element alloy prepared in example 2 had a woven structure.
Example 3
A multi-principal-element alloy with a BCC/B2 dual-phase structure comprises the following constituent elements in percentage by atom: titanium (Ti)42 at.%, tantalum (Ta)8 at.%, niobium (Nb)15 at.%, zirconium (Zr)25 at.%, aluminum (Al)9 at.%, and chromium (Cr)1 at.%. The preparation method of the multi-principal element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr, Al and Cr with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to be less than or equal to 5 multiplied by 10-3Introducing argon after Pa, then carrying out alloying smelting, cooling the alloy liquid formed by smelting to room temperature in a water-cooling copper mold to obtain an alloy ingot, and then overturning the alloy ingot and repeatedly smelting for 5 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon gas for high-temperature annealing treatment at the temperature of 1200 ℃ for 6h, and then placing the alloy ingot in a trough of ice salt water to cool to room temperature to obtain a high-temperature annealed alloy;
(3) placing the high-temperature annealed alloy in a heat treatment furnace filled with argon gas for low-temperature annealing treatment, wherein the annealing treatment temperature is 500 ℃, the annealing treatment time is 6h, and then cooling the alloy in a room-temperature water tank to room temperature to obtain Ti with a BCC/B2 dual-phase structure42Ta8Nb15Zr25Al9Cr1And (3) alloying.
According to XRD characterization, the multi-element alloy prepared in example 3 contains BCC and B2 phases. As can be seen from the SEM image of FIG. 7, the multi-principal element alloy prepared in example 3 is equiaxed and has a grain size of 495. + -.51 μm. As can be seen from fig. 8, the multi-element alloy prepared in example 3 had a woven structure.
Example 4
A multi-principal-element alloy with a BCC/B2 dual-phase structure comprises the following constituent elements in percentage by atom: titanium (Ti)40 at.%, tantalum (Ta)9 at.%, niobium (Nb)17 at.%, zirconium (Zr)18 at.%, aluminum (Al)8 at.%, vanadium (V)2 at.%, and boron (B)1 at.%. The preparation method of the multi-principal element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr, Al, V and B with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to be less than or equal to 5 multiplied by 10-3Introducing argon after Pa, then carrying out alloying smelting, and carrying out water cooling on the alloy liquid formed by smeltingCooling the copper mold to room temperature to obtain an alloy ingot, and then overturning the alloy ingot and repeatedly smelting for 4 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon gas for high-temperature annealing treatment at 1200 ℃ for 6h, and then placing the alloy ingot in a tank of ice salt water to cool to room temperature to obtain a high-temperature annealed alloy;
(3) placing the high-temperature annealing alloy in a heat treatment furnace filled with argon gas for low-temperature annealing treatment at the temperature of 500 ℃ for 12h, and then cooling the high-temperature annealing alloy in a room-temperature water tank to room temperature to obtain Ti with a BCC/B2 dual-phase structure40Ta9Nb17Zr18Al8V2B1And (3) alloying.
According to XRD characterization, the multi-element alloy prepared in example 4 contains BCC and B2 phases. According to SEM characteristics, the multi-element alloy prepared in example 4 is isometric crystal, the grain size is 448 +/-39 mu m, and the structure is in a braided shape.
Comparative example 1
A multi-principal-element alloy comprises the following constituent elements in atomic percentage: titanium (Ti)28.5 at.%, tantalum (Ta)19 at.%, niobium (Nb)23.75 at.%, zirconium (Zr)23.75 at.%, and aluminum (Al)5 at.%. The preparation method of the multi-principal-element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr and Al with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to be less than or equal to 5 multiplied by 10- 3Introducing argon after Pa, then carrying out alloying smelting, cooling the alloy liquid formed by smelting to room temperature in a water-cooling copper mold to obtain an alloy ingot, and then overturning the alloy ingot and repeatedly smelting for 7 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon gas for high-temperature annealing treatment, wherein the annealing treatment temperature is 1300 ℃, the annealing treatment time is 24 hours, and then placing the alloy ingot in a tank of room-temperature water to cool to room temperature to obtain high-temperature annealed alloy;
(3) will be highThe temperature annealing alloy is placed in a heat treatment furnace filled with argon gas for low temperature annealing treatment, the annealing treatment temperature is 600 ℃, the annealing treatment time is 6 hours, and then the temperature is cooled to room temperature in the air, thus obtaining Ti28.5Ta19Nb23.75Zr23.75Al5And (3) alloying.
According to XRD characterization, the multi-principal element alloy prepared in comparative example 1 contains BCC and B2 dual-phase structures. According to SEM characteristics, the multi-element alloy prepared in comparative example 1 is isometric crystal, the grain size is 298 +/-31 microns, and the structure is in a braided shape, as shown in figures 9 and 10.
Comparative example 2
A multi-principal-element alloy comprises the following constituent elements in atomic percentage: titanium (Ti)36 at.%, tantalum (Ta)9 at.%, niobium (Nb)22.5 at.%, zirconium (Zr)22.5 at.%, and aluminum (Al)10 at.%. The preparation method of the multi-principal-element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr, Al and V with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to be less than or equal to 3 x 10-3Introducing argon after Pa, then carrying out alloying smelting, cooling the alloy liquid formed by smelting to room temperature in a water-cooling copper mold to obtain an alloy ingot, and then overturning the alloy ingot and repeatedly smelting for 5 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon gas for high-temperature annealing treatment, wherein the annealing treatment temperature is 1200 ℃, the annealing treatment time is 8 hours, and then placing the alloy ingot in a tank of room-temperature water to cool to room temperature to obtain high-temperature annealed alloy;
(3) placing the high-temperature annealing alloy in a heat treatment furnace filled with argon gas for low-temperature annealing treatment at 700 ℃ for 12h, and then cooling the high-temperature annealing alloy in a room-temperature water tank to room temperature to obtain Ti36Ta9Nb22.5Zr22.5Al10And (3) alloying.
According to XRD characterization, the multi-principal-element alloy prepared in the comparative example 2 contains a BCC phase and an Al-Zr phase. According to SEM representation, the multi-principal-element alloy prepared in the comparative example 2 is isometric crystal, and the grain size is 441 +/-42 μm. As can be seen from the high-magnification SEM image of fig. 11, a large amount of Al — Zr rich phase appears inside the multi-primary alloy crystal grains, and no braided structure is observed.
Comparative example 3
A multi-principal-element alloy comprises the following constituent elements in atomic percentage: titanium (Ti)35 at.%, tantalum (Ta)10 at.%, niobium (Nb)20 at.%, zirconium (Zr)15 at.%, and aluminum (Al)20 at.%. The preparation method of the multi-principal-element alloy comprises the following steps:
(1) weighing simple substances of Ti, Ta, Nb, Zr, Al and V with the purity of more than 99.9 wt.% according to atomic percentage, sequentially putting the simple substances into a crucible of a non-consumable vacuum arc melting furnace from low to high according to the melting point of the simple substances, and vacuumizing the furnace to be less than or equal to 5 multiplied by 10-3Introducing argon after Pa, then carrying out alloying smelting, cooling the alloy liquid formed by smelting to room temperature in a water-cooling copper mold to obtain an alloy ingot, and then overturning the alloy ingot and repeatedly smelting for 6 times to obtain an alloy ingot;
(2) placing the alloy ingot in a heat treatment furnace filled with argon gas for high-temperature annealing treatment, wherein the annealing treatment temperature is 1200 ℃, the annealing treatment time is 12 hours, and then placing the alloy ingot in a tank of room-temperature water to cool to room temperature to obtain high-temperature annealed alloy;
(3) placing the high-temperature annealing alloy in a heat treatment furnace filled with argon gas for low-temperature annealing treatment at the temperature of 600 ℃ for 12h, and then cooling the high-temperature annealing alloy in a room-temperature water tank to room temperature to obtain Ti36Ta9Nb22.5Zr22.5Al10And (3) alloying.
According to XRD characterization, the multi-element alloy prepared in comparative example 3 contains BCC, B2 and Al-Zr phases. According to SEM characterization, the multi-principal-element alloy prepared in comparative example 3 is isometric crystal, and the grain size is 205 +/-31 microns. As can be seen from the high-power SEM image of FIG. 12, the multi-principal-element alloy crystal grains have a woven texture inside, but a large amount of flaky Al-Zr-rich phases appear at the grain boundaries.
The compressive yield strength, compressive strength and strain at break of the multi-element alloys prepared in examples 1-4 and comparative examples 1-3 are detailed in table 1. The test results in Table 1 show that the multi-principal-element alloy prepared in the embodiments 1-4 has the characteristics that the compressive yield strength is more than 1400MPa, the fracture strain is more than or equal to 35%, and the matching degree of the strength and the plasticity is good.
TABLE 1
Examples Compressive yield strength (MPa) Compressive strength (MPa) Strain at break (%)
Example 1 1437±21 2119±78 37±2
Example 2 1869±40 2906±34 37±2
Example 3 1597±28 -- ≥50
Example 4 1669±17 -- ≥50
Comparative example 1 1509±21 1632±34 17±3
Comparative example 2 1634±19 1715±28 22±5
Comparative example 3 1582±24 1657±35 7±4
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 (8)

1. A multi-primary alloy of BCC/B2 dual phase structure, characterized in that: the chemical formula of the multi-principal element alloy is recorded as Ti according to the atomic percentage content of each elementaTabNbcZrdAleMfM is at least one of V, Cr, Ni, Cu, Fe, Si, Mg, Y, B, C and O, a is more than 30 and less than or equal to 60, B is more than 0 and less than or equal to 15, C is more than or equal to 5 and less than or equal to 50, d is more than or equal to 5 and less than or equal to 35, e is more than or equal to 5 and less than or equal to 15, f is more than or equal to 0 and less than or equal to 10, B + C + d is more than or equal to 40 and less than or equal to 75, and B/d is more than or equal to 0.3 and less than or equal to 0.6; the multi-principal element alloy is a woven BCC/B2 dual-phase structure;
the multi-principal-element alloy is prepared by the following method:
(1) putting simple substances corresponding to Ti, Ta, Nb, Zr, Al and M elements into a smelting furnace according to atomic percentage, carrying out alloying smelting under the protective atmosphere of nitrogen or inert gas, cooling an alloy liquid formed by smelting to obtain an alloy ingot, turning over the alloy ingot and repeatedly smelting for more than 3 times to obtain an alloy ingot;
(2) in the protective atmosphere of nitrogen or inert gas, carrying out high-temperature annealing treatment on the alloy ingot at 1100-1400 ℃ for 6-24 h, and then cooling the alloy ingot to room temperature in a cooling medium to obtain a high-temperature annealed alloy;
(3) directly placing the high-temperature annealing alloy in an argon protective atmosphere, carrying out low-temperature annealing treatment at 400-650 ℃ for 0.5-20 h, and then cooling to room temperature in a cooling medium to obtain the multi-principal-element alloy containing the BCC/B2 dual-phase structure.
2. The multi-host alloy of BCC/B2 dual-phase structure according to claim 1, wherein: the TiaTabNbcZrdAleMfWherein a is more than 30 and less than or equal to 45, b is more than or equal to 5 and less than or equal to 15, c is more than or equal to 15 and less than or equal to 35, d is more than or equal to 15 and less than or equal to 35, e is more than or equal to 5 and less than or equal to 10, f is more than or equal to 0 and less than or equal to 5, b + c + d is more than or equal to 40 and less than or equal to 75, and b/d is more than or equal to 0.3 and less than or equal to 0.6.
3. The multi-host alloy of BCC/B2 dual-phase structure according to claim 1, wherein: the TiaTabNbcZrdAleMfIn the formula, M is at least one of V, Cr, Y and B.
4. A method of preparing a multi-host alloy of BCC/B2 dual phase structure as defined in any of claims 1-3, wherein: the steps of the method are as follows,
(1) putting simple substances corresponding to Ti, Ta, Nb, Zr, Al and M elements into a smelting furnace according to atomic percentage, carrying out alloying smelting under the protective atmosphere of nitrogen or inert gas, cooling an alloy liquid formed by smelting to obtain an alloy ingot, turning over the alloy ingot and repeatedly smelting for more than 3 times to obtain an alloy ingot;
(2) in the protective atmosphere of nitrogen or inert gas, carrying out high-temperature annealing treatment on the alloy ingot at 1100-1400 ℃ for 6-24 h, and then cooling the alloy ingot to room temperature in a cooling medium to obtain a high-temperature annealed alloy;
(3) directly placing the high-temperature annealing alloy in an argon protective atmosphere, carrying out low-temperature annealing treatment at 400-650 ℃ for 0.5-20 h, and then cooling to room temperature in a cooling medium to obtain the multi-principal-element alloy containing the BCC/B2 dual-phase structure.
5. The method of claim 4, wherein the BCC/B2 dual-phase multi-host alloy is prepared by the following steps: in the step (1), the purities of the simple substances corresponding to the Ti, the Ta, the Nb, the Zr, the Al and the M are all more than 99.9 wt.%.
6. The method of claim 4, wherein the BCC/B2 dual-phase multi-principal-element alloy comprises: the smelting furnace in the step (1) is a non-consumable vacuum electric arc smelting furnace or a suspension smelting furnace.
7. The method of claim 4, wherein the BCC/B2 dual-phase multi-principal-element alloy comprises: and (3) the cooling medium in the step (2) and the step (3) is air, room temperature water or brine ice.
8. The method of claim 4, wherein the BCC/B2 dual-phase multi-host alloy is prepared by the following steps: the time of low-temperature annealing treatment at 400-650 ℃ is 2-12 h.
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