CN113462929A - High-strength high-toughness alpha + beta type titanium alloy material and preparation method thereof - Google Patents

High-strength high-toughness alpha + beta type titanium alloy material and preparation method thereof Download PDF

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CN113462929A
CN113462929A CN202110745435.9A CN202110745435A CN113462929A CN 113462929 A CN113462929 A CN 113462929A CN 202110745435 A CN202110745435 A CN 202110745435A CN 113462929 A CN113462929 A CN 113462929A
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titanium alloy
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titanium
vanadium
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CN113462929B (en
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徐轶
蒋哲亮
王高见
陈辉
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Southwest Jiaotong University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00Casting ingots, e.g. from ferrous metals
    • B22D7/005Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • 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

Abstract

The invention discloses a high-strength high-toughness alpha + beta type titanium alloy material and a preparation method thereof, wherein the titanium alloy material consists of metal elements of titanium, aluminum and vanadium, wherein the mass percent of each metal element is aluminum x percent, vanadium y percent and the balance of titanium is marked as Ti-xAl-yV, wherein x is 7, and y is 6.2-7.5; the cast Ti-xAl-yV has a crystal structure formed by coexistence of an alpha phase with a close-packed hexagonal structure and a beta phase with a body-centered cubic structure, the tensile strength is more than 1100MPa, and the elongation is not lower than 25%. The preparation method of the titanium alloy material comprises the following steps: s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of the metal elements; s2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, and repeatedly turning and smelting under protective gas to obtain alloy liquid; s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace; and S4, casting the alloy liquid after heat preservation to obtain an alloy ingot, and thus finishing preparation. The titanium alloy has good mechanical property and high temperature resistance.

Description

High-strength high-toughness alpha + beta type titanium alloy material and preparation method thereof
Technical Field
The invention relates to a high-strength high-toughness alpha + beta type titanium alloy material and a preparation method thereof, belonging to the technical field of titanium alloy materials.
Background
The titanium alloy is an important structural metal developed in the 50 s of the 20 th century, and has high strength, good corrosion resistance and high heat resistance. The titanium alloy is mainly used for manufacturing parts of an air compressor of an aircraft engine, and is a structural part of rockets, missiles and high-speed airplanes. Titanium alloys can be subdivided into alpha-type titanium alloys, near-alpha-type titanium alloys, alpha + beta-type titanium alloys, near-beta-type titanium alloys, generally according to the phase composition of the titanium alloy after quenching from a beta-phase single zone and the content of beta-stabilizing elements.
The alpha + beta type titanium alloy has relatively high content of beta stable elements, the structure in an annealing state is composed of alpha phase and beta phase, wherein the content of the beta phase is within the range of 5.0-40.0%, the hardenability is good, and the titanium alloy can be strengthened through heat treatment. The alpha + beta type titanium alloy has good thermal stability, higher strength and shaping, and is usually applied to high-temperature high-strength aviation structural parts. Among them, TC4 titanium alloy (Ti-6Al-4V alloy) is the most widely used alpha + beta type titanium alloy material. In the aviation industry, TC4 titanium alloy is mainly used as a structural part for clapboards, wings, frames, compressor disks, engines, blades, gas cylinders and the like. With the development of high precision and small-size intellectualization of aviation equipment, rigorous requirements are put forward on titanium alloy structural materials for aviation, high strength and good plasticity are required to be met, and the conventional TC4 titanium alloy cannot meet the requirements of some application fields. Therefore, new preparation techniques and means are needed to develop high-strength and high-toughness titanium alloy materials capable of being produced in batches.
Disclosure of Invention
The invention aims to provide a high-strength high-toughness alpha + beta type titanium alloy material and a preparation method thereof, and aims to solve the problem that the comprehensive mechanical property of the traditional titanium alloy needs to be improved urgently.
The invention aims to provide a high-strength high-toughness alpha + beta type titanium alloy material which comprises metal elements of titanium, aluminum and vanadium, and is characterized in that the mass percentages of the metal elements in the titanium alloy material are aluminum (Al) x%, vanadium (V) y% and the balance of titanium, and are marked as Ti-xAl-yV, wherein x is 7, and y is 6.2-7.5; the cast Ti-xAl-yV has a crystal structure formed by two-phase coexistence of an alpha phase with a close-packed hexagonal structure (HCP) and a beta phase with a body-centered cubic structure (BCC), the tensile strength is more than 1100MPa, and the elongation is not less than 25%.
Further, the mass percent y of vanadium in the titanium alloy material is 6.5-7%.
Furthermore, the mass percent y% of vanadium in the titanium alloy material is 7%.
In titanium alloy, alpha phase stabilizing elements are elements capable of stabilizing alpha phase and improving the phase change point of the titanium alloy, Al is the most common alpha phase stabilizing element in various titanium alloys, beta phase stabilizing elements can stabilize beta phase, and V, Mo and Nb are common beta phase stabilizing elements. In the prior art, Mo equivalent is mainly considered in the element design of the titanium alloy, and the performance of the designed titanium alloy cannot meet the requirements of some application fields. The invention mainly considers the synergistic effect of alpha phase and beta phase of titanium alloy in the aspect of titanium alloy component design, on the basis that the content of alpha phase stable element Al is increased to 7%, the content of beta isomorphous element of corresponding component is designed according to the synergistic effect, and the mass fraction of the beta isomorphous element is adjusted to 6.2% -7.5%, so that the titanium alloy has a beta phase dual-phase coexisting crystal structure consisting of alpha phase of a close-packed hexagonal structure (HCP) and a body-centered cubic structure (BCC) in an as-cast state, and the technical effects that the tensile strength is greater than 1100MPa and the elongation is not less than 25% are achieved. The design principle and the beneficial effects of the element proportion of the invention are specifically analyzed as follows:
firstly, the invention changes the content of alpha stabilizing element aluminum element and beta stabilizing element vanadium element on the basis of the traditional Ti6Al4V titanium alloy, adjusts the content of alpha phase and beta phase in the titanium alloy, changes the microstructure and the content of an alloy system, ensures that the titanium alloy has a beta phase dual-phase coexisting crystal structure consisting of alpha phase of a close-packed hexagonal structure (HCP) and beta phase of a body-centered cubic structure (BCC) in an as-cast state, increases the fraction content of the beta phase, gradually refines two phases of the alloy system by increasing the content of the beta phase so as to increase the crossing degree of the two phases, ensures that the two-phase structure is more uniformly distributed, correspondingly reduces the grain size and the residual stress, and is favorable for improving the mechanical property of the alloy material.
Secondly, on the basis of the traditional Ti6Al4V titanium alloy, the content of alpha stabilizing elements (aluminum elements) is increased, the temperature range of an alpha phase is increased, more alpha phases are obtained, and the alpha phase has excellent high-temperature performance, so that the titanium alloy prepared by the method has excellent high-temperature performance stability.
Thirdly, the invention achieves the effect of regulating and controlling phase composition and phase boundary distribution by reasonably optimizing alloy component elements; furthermore, the stacking fault energy of an alloy system is reduced, the number of defects such as stacking faults in the alloy is increased, the local stress of the alloy is reduced, the effects of homogenizing the structure and refining the crystal grains are achieved, and the mechanical property of the alloy material can be obviously improved.
The invention also provides a preparation method of the high-strength high-toughness alpha + beta type titanium alloy material, which comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of each metal element in the Ti-xAl-yV titanium alloy material;
s2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, vacuumizing the vacuum induction furnace, filling protective gas, and repeatedly overturning and smelting under the protective gas to obtain alloy liquid; in the process of repeated turnover smelting, the current of the vacuum induction furnace is kept between 200 and 250A, and the voltage is kept between 14 and 16V;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 15-20 min, and the heat preservation temperature is 1700-1750 ℃;
s4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely, completing the preparation of the high-strength high-toughness alpha + beta type titanium alloy.
Compared with the prior art, the preparation method has the beneficial effects that: the cast titanium alloy prepared by the preparation method in combination with the alloy element proportion has the advantages of stable two-phase coexisting crystal structure in the alloy, uniform and non-segregation tissue, uniform distribution of the two-phase tissue, small grain size and residual stress, low alloy system fault energy and low alloy local stress. The finally prepared cast titanium alloy has tensile strength of more than 1100MPa, elongation of not less than 25%, and good mechanical property and high temperature resistance. The preparation method has the advantages of simple process, low cost, safety and reliability, and can realize large-scale industrial application.
Further, the purity of the titanium particles, the purity of the aluminum particles and the purity of the vanadium particles weighed in the step S1 meet the condition that the mass percentage is more than 99.99%.
Further, in the process of repeatedly turning over and smelting in the step S2 under the protective gas, the turning times are 4-6 times.
Further, in the process of repeatedly turning and smelting in the step S2 under the protective gas, the protective gas is argon with the purity of more than 99.99%.
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
Drawings
FIG. 1 is a light mirror image of a titanium alloy material prepared in a comparative example of the present invention.
FIG. 2 is a light mirror image of the titanium alloy material prepared in example 1 of the present invention.
FIG. 3 is a light mirror image of the titanium alloy material prepared in example 2 of the present invention.
FIG. 4 is an EBSD map of a titanium alloy material prepared according to a comparative example of the present invention.
FIG. 5 is an EBSD map of the titanium alloy material prepared in example 1 of the present invention.
FIG. 6 is an EBSD map of the titanium alloy material prepared in example 2 of the present invention.
FIG. 7 is a bar graph showing the hardness of titanium alloy materials prepared in comparative example, example 1 and example 2 of the present invention.
FIG. 8 is a tensile stress-strain curve of titanium alloy materials prepared in comparative example, example 1 and example 2 of the present invention.
Detailed Description
Comparative example
A titanium alloy material consists of metal elements of titanium, aluminum and vanadium, wherein the mass percentages of the metal elements in the titanium alloy material are 6% of aluminum (Al), 4% of vanadium (V) and the balance of titanium, and are marked as Ti-6 Al-4V;
the preparation method of the Ti-6Al-4V titanium alloy material comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of 90% of titanium, 6% of aluminum and 4% of vanadium, wherein the purity of the weighed titanium particles, aluminum particles and vanadium particles is more than 99.99%.
S2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is 6.58 multiplied by 10-3Pa, then filling argon, and repeatedly turning and smelting under the protection of argon with the purity of more than 99.99 percent to obtain alloy liquid; in the process of repeatedly turning over and smelting, the current of the vacuum induction furnace is kept between 200 and 220A, the voltage is kept at 14V, and the turning times are 6 times, so that the alloy components are uniform;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 15min, and the heat preservation temperature is 1720 ℃;
and S4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely completing the preparation of the titanium alloy.
Example 1
The high-strength high-toughness alpha + beta type titanium alloy material consists of metal elements of titanium, aluminum and vanadium, wherein the mass percentages of the metal elements in the titanium alloy material are 7% of aluminum (Al), 6.5% of vanadium (V) and the balance of titanium, which is marked as Ti-7 Al-6.5V;
the preparation method of the Ti-7Al-6.5V titanium alloy material comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of 86.5% of titanium, 7% of aluminum and 6.5% of vanadium, wherein the purity of the weighed titanium particles, aluminum particles and vanadium particles is more than 99.99%.
S2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is 6.58 multiplied by 10-3Pa, then filling argon, and repeatedly turning and smelting under the protection of argon with the purity of more than 99.99 percent to obtain alloy liquid; in the process of repeatedly overturning and smelting, the current of the vacuum induction furnace is kept between 200 and 220A, the voltage is kept at 14V, and the vacuum induction furnace is overturnedThe number of times of rotation is 6, so that the alloy components are uniform;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 15min, and the heat preservation temperature is 1720 ℃;
s4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely, completing the preparation of the high-strength high-toughness alpha + beta type titanium alloy.
Example 2
The high-strength high-toughness alpha + beta type titanium alloy material consists of metal elements of titanium, aluminum and vanadium, wherein the mass percentages of the metal elements in the titanium alloy material are 7% of aluminum (Al), 7% of vanadium (V) and the balance of titanium, and are marked as Ti-7 Al-7V;
the preparation method of the Ti-7Al-7V titanium alloy material comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of 86% of titanium, 7% of aluminum and 7% of vanadium, wherein the purity of the weighed titanium particles, aluminum particles and vanadium particles is more than 99.99%.
S2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is 6.58 multiplied by 10-3Pa, then filling argon, and repeatedly turning and smelting under the protection of argon with the purity of more than 99.99 percent to obtain alloy liquid; in the process of repeatedly turning over and smelting, the current of the vacuum induction furnace is kept between 200 and 220A, the voltage is kept at 14V, and the turning times are 6 times, so that the alloy components are uniform;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 15min, and the heat preservation temperature is 1720 ℃;
s4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely, completing the preparation of the high-strength high-toughness alpha + beta type titanium alloy.
The titanium alloy materials prepared in the comparative example, the example 1 and the example 2 are cut into corresponding samples according to the test characterization requirements by adopting the wire cut electrical discharge machining technology, and the samples are polished and cleaned for tissue characterization and performance test.
Tissue characterization: the phase composition analysis and the tissue structure characterization of the titanium alloy material are respectively carried out by an X-ray diffractometer (XRD PANalytical), an optical microscope (OM ZEISS) and an electron back scattering diffractometer. The electron back scattering analysis was analyzed by ZEISS aurega type field emission scanning electron microscope in combination with Bruker EBSD probe for phase distribution and phase ratio calculation of the alloy.
And (3) performance testing: the Vickers hardness of the surface of the cut alloy specimen was measured by a hardness tester (HVS-1000B), and the tensile properties of the cut specimen were measured by a universal tensile tester (Instron 5960).
Fig. 1, 2, and 3 are optical mirror images of titanium alloy materials prepared in comparative example, example 1, and example 2, respectively. As can be seen from the light mirror image, compared with the comparative example, in the titanium alloy material of the example 1 and the example 2, the crossing degree of the two phases is increased, the structure distribution of the two phases is more uniform and fine, the massive alpha phase disappears, the structure distribution of the alpha phase is more uniform and fine, and the beta phase is in fine distribution. And as the content of the beta stable element V is increased, the alpha phase structure in the structure is more uniformly and finely distributed.
Fig. 4, 5, and 6 are EBSD graphs of titanium alloy materials prepared in comparative example, example 1, and example 2, respectively, and it can be seen that an α phase having an HCP structure and a β phase having a BCC structure are present in all of the three titanium alloy materials. When the phase distribution and the phase calculation of the titanium alloy materials prepared in the comparative example and the examples 1 and 2 are analyzed by using a ZEISS Auriga type field emission scanning electron microscope and combining a Bruker EBSD probe, the content of alpha phase with HCP structure in the titanium alloy material prepared in the comparative example is 99.8%, the content of beta phase with BCC structure is 0.218%, the content of alpha phase with HCP structure in the titanium alloy material prepared in the example 1 is 98.7%, the content of beta phase with BCC structure is 1.305%, the content of alpha phase with HCP structure in the titanium alloy material prepared in the example 2 is 97.8%, the content of beta phase with BCC structure is 2.24%, the beta phase content fraction tends to increase along with the increase of the content of the beta stabilizing element V, and the increase of the beta phase content is beneficial to the improvement of the strength and the plasticity of the alloy.
Fig. 7 is a bar graph showing the hardness of the titanium alloy materials prepared in comparative example, example 1 and example 2. The hardness of the titanium alloy material of the comparative example is 330HV, the hardness of the titanium alloy material of the example 1 is 372HV, the hardness of the titanium alloy material of the example 2 is 380HV, and the phase structure of the titanium alloy of the example 1 and the titanium alloy of the example 2 is more compact and the hardness is improved due to the increase of beta phase and the grain refinement.
Fig. 8 is a tensile stress-strain graph of the titanium alloy materials prepared in comparative example, example 1 and example 2. The tensile strength value of the titanium alloy material of the comparative example is 975MPa, the elongation is 21%, the tensile strength value of the titanium alloy material of the example 1 is 1150MPa, the elongation is 26%, the tensile strength value of the titanium alloy material of the example 2 is 1118MPa, and the elongation is 27%. The titanium alloy materials of the examples 1 and 2 have higher strength and elongation than the traditional Ti6Al4V titanium alloy (comparative example), and the titanium alloy materials of the examples 1 and 2 have good matching of strength and plasticity and excellent comprehensive performance.
Example 3
The high-strength high-toughness alpha + beta type titanium alloy material consists of metal elements of titanium, aluminum and vanadium, wherein the mass percentages of the metal elements in the titanium alloy material are 7% of aluminum (Al), 7.5% of vanadium (V) and the balance of titanium, which is marked as Ti-7 Al-7.5V;
the preparation method of the Ti-7Al-7.5V titanium alloy material comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of 85.5% of titanium, 7% of aluminum and 7.5% of vanadium, wherein the purity of the weighed titanium particles, aluminum particles and vanadium particles is more than 99.99%.
S2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is 6.58 multiplied by 10-3Pa, then filling argon, and repeatedly turning and smelting under the protection of argon with the purity of more than 99.99 percent to obtain alloy liquid; in the process of repeatedly turning over and smelting, the current of the vacuum induction furnace is kept between 220 and 250A, the voltage is kept at 16V, and the turning times are 4 times, so that the alloy components are uniform;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 20min, and the heat preservation temperature is 1700 ℃;
s4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely, completing the preparation of the high-strength high-toughness alpha + beta type titanium alloy.
Example 4
The high-strength high-toughness alpha + beta type titanium alloy material consists of metal elements of titanium, aluminum and vanadium, wherein the mass percentages of the metal elements in the titanium alloy material are 7% of aluminum (Al), 6.2% of vanadium (V) and the balance of titanium, which is marked as Ti-7 Al-6.2V;
the preparation method of the Ti-7Al-6.2V titanium alloy material comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of 86.8% of titanium, 7% of aluminum and 6.2% of vanadium, wherein the purity of the weighed titanium particles, aluminum particles and vanadium particles is more than 99.99%.
S2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, and vacuumizing the vacuum induction furnace until the vacuum degree is 6.58 multiplied by 10-3Pa, then filling argon, and repeatedly turning and smelting under the protection of argon with the purity of more than 99.99 percent to obtain alloy liquid; in the process of repeatedly turning over and smelting, the current of the vacuum induction furnace is kept between 220 and 240A, the voltage is kept at 15V, and the turning times are 5 times, so that the alloy components are uniform;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 16min, and the heat preservation temperature is 1750 ℃;
s4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely, completing the preparation of the high-strength high-toughness alpha + beta type titanium alloy.

Claims (7)

1. The alpha + beta type titanium alloy material with high strength and high toughness consists of metal elements of titanium, aluminum and vanadium, and is characterized in that the mass percentages of the metal elements in the titanium alloy material are aluminum x%, vanadium y% and the balance of titanium are marked as Ti-xAl-yV, wherein x is 7, and y is 6.2-7.5; the cast Ti-xAl-yV has a crystal structure formed by coexistence of an alpha phase with a close-packed hexagonal structure and a beta phase with a body-centered cubic structure, the tensile strength is more than 1100MPa, and the elongation is not lower than 25%.
2. The high-strength high-toughness alpha + beta type titanium alloy material according to claim 1, wherein: the mass percent y percent of vanadium in the titanium alloy material is 6.5-7%.
3. The high-strength high-toughness alpha + beta type titanium alloy material according to claim 2, wherein: the mass percent y percent of the titanium alloy material is 7 percent.
4. A method for preparing the high-strength high-toughness alpha + beta type titanium alloy material according to any one of claims 1 to 3, which comprises the following steps:
s1, weighing titanium particles, aluminum particles and vanadium particles according to the mass percentage of each metal element in the Ti-xAl-yV titanium alloy material;
s2, putting the weighed titanium particles, aluminum particles and vanadium particles into a vacuum induction furnace, vacuumizing the vacuum induction furnace, filling protective gas, and repeatedly overturning and smelting under the protective gas to obtain alloy liquid; in the process of repeated turnover smelting, the current of the vacuum induction furnace is kept between 200 and 250A, and the voltage is kept between 14 and 16V;
s3, carrying out heat preservation treatment on the obtained alloy liquid in a vacuum induction furnace, wherein the heat preservation time is 15-20 min, and the heat preservation temperature is 1700-1750 ℃;
s4, casting the alloy liquid after heat preservation to obtain an alloy ingot, namely, completing the preparation of the high-strength high-toughness alpha + beta type titanium alloy.
5. The method for preparing the high-strength high-toughness alpha + beta type titanium alloy material according to claim 3, wherein the method comprises the following steps: the purities of the titanium particles, the aluminum particles and the vanadium particles weighed in the step S1 all meet the requirement that the mass percentage is more than 99.99%.
6. The method for preparing the high-strength high-toughness alpha + beta type titanium alloy material according to claim 4, wherein the method comprises the following steps: and in the step S2, in the process of repeatedly overturning and smelting under the protective gas, the overturning times are 4-6 times.
7. The method for preparing the high-strength high-toughness alpha + beta type titanium alloy material according to claim 4, wherein the method comprises the following steps: in the step S2, in the process of repeatedly turning over and smelting under the protective gas, the protective gas is argon with the purity of more than 99.99 percent.
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