Preparation method of micro low-oxygen spherical Ti-based high-entropy alloy powder

Abstract

The invention provides a preparation method of fine low-oxygen spherical Ti-based high-entropy alloy powder, and relates to the technical field of spherical titanium-based alloy powder. The preparation method comprises the steps of raw material selection and treatment of the wire, preparation of the pre-alloyed wire, preparation of the titanium-based high-entropy alloy wire, treatment of the titanium-based high-entropy alloy wire, establishment of a gas system, high-frequency induction preheating, radio frequency plasma smelting and atomization pulverization which are carried out in sequence. Through multiple wire twisting, multiple continuous hot drawing, diffusion homogenization annealing, high-frequency induction preheating, radio frequency plasma smelting and atomization powder preparation, the Ti-based high-entropy alloy wire with uniform component distribution can be directly prepared at a low temperature, then the Ti-based high-entropy alloy fine powder with low oxygen content and uniform component distribution is prepared, and the Ti-based high-entropy alloy fine powder is suitable for additive manufacturing and has good application prospects. The method is high in flexibility, simple to operate, wide in application, low in cost and very suitable for large-scale industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of spherical titanium-based alloy powder, in particular to a method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder. Background Art

[0002] High entropy alloy is a new type of alloy composed of five or more main components, mixed in equal atomic ratio or approximately equal atomic ratio, with the characteristics of high strength, high hardness, good thermal stability, excellent corrosion resistance, etc. Adding Ti element (atomic ratio of 5-35%) to high entropy alloy to form titanium-based high entropy alloy can effectively reduce the density of the alloy and improve the hardness and strength of the alloy, which is of great significance for the development of high-temperature structural materials for a new generation of high thrust-to-weight ratio and high power-to-weight ratio aircraft engines. In recent years, with the continuous development of large aircraft, aero engines, and new generation launch vehicles, aerospace parts tend to be integrated and complex, and their preparation methods have also been gradually replaced by traditional casting, forging combined with machining to powder near-net forming technologies such as injection molding and additive manufacturing.

[0003] For injection molding (powder 0~25μm) and additive manufacturing (powder 15~53μm), the performance of the finished product depends largely on the powder raw material. Generally speaking, the powder raw material for manufacturing high-performance finished products should have high sphericity, fluidity, purity, low hollow rate and fine powder particle size. Due to the room temperature brittleness of titanium-based high-entropy alloys, there are still technical bottlenecks in the preparation of titanium-based high-entropy alloy wires. Due to the presence of active elements such as Ti, it is easy to react with other substances at high temperatures. Therefore, the preparation of spherical titanium-based high-entropy alloy powders mainly uses rods as raw materials and adopts non-contact melting, such as plasma rotating electrode (PREP) method, electrode induction melting gas atomization (EIGA) method, etc.

[0004] Among them, the PREP method is to prepare titanium-based high-entropy alloy into a rod-type consumable electrode. One end of the consumable electrode melts into droplets under the action of plasma heating, and then is thrown out under the action of high-speed rotating centrifugal force to form fine droplets. The small droplets are quickly cooled and solidified into spherical powders under the action of surface tension. However, titanium-based high-entropy alloys have poor plasticity, so it is very easy for the rods to crack during the powder making process. In addition, the rotation speed of the titanium-based high-entropy alloy rod in this technology is lower than 20,000 r / min, which makes the centrifugal force of the molten droplet dispersion atomization smaller, and the viscosity of the molten droplet is larger, so the spherical powder obtained is coarse in particle size, with a powder particle size of 40-400μm.

[0005] The EIGA method uses titanium-based high-entropy alloy rods as raw materials, and uses high-frequency induction current to melt the surface of the rods and form a molten liquid flow that falls into the atomizing nozzle. Under the action of high-speed airflow, dispersed molten droplets are formed and quickly cooled and solidified into fine particles. Compared with the PREP method, the powder particle size produced by the EIGA method is finer, but the fine powder yield that meets the requirements of injection molding and additive manufacturing is low, less than 40%. In addition, the titanium-based high-entropy alloy droplets after induction melting will leave the high-temperature zone too quickly, resulting in insufficient temperature and time during the gas atomization condensation process to ensure that the droplets shrink into balls under the action of surface tension. The sphericity of the powder produced is low, and hollow balls are easily produced.

[0006] Chinese patent CN117758123A discloses a single-phase TiZrMo-based spherical refractory high-entropy alloy powder and a preparation method thereof, which requires first crushing and screening to obtain single-element powders of each element, then mixing them in proportion, and then wet grinding + high-energy ball milling + drying and grinding, and finally spheroidization treatment to obtain spherical refractory high-entropy alloy powder; wherein the wet grinding + high-energy ball milling will mix in impurity elements, and the grinding time is long, the cost is high, and the efficiency is low.

[0007] Chinese patent CN113579246A discloses a method for preparing nano high entropy alloy powder, which comprises dissolving five or more transition metal salt precursors in the same solvent, ultrasonically dispersing to obtain a blended solution, then adding a strong alkali solution for co-precipitation, followed by aging, separation, water washing, alcohol washing, drying, and finally calcining and reducing. Obviously, the solution chemical reaction time of this method is relatively long. Although nano powder can be obtained, in order to remove impurities in the nano powder and allow the reduction to proceed fully, the cost required is relatively high and the process is relatively long.

[0008] Chinese patent CN118256762A discloses a Cu micro-alloyed low-oxygen NbMoTaW ultrafine-grained high-entropy alloy and a preparation method thereof, wherein micron-sized Nb powder, Mo powder, Ta powder, W powder and Cu powder are used as raw materials, and mechanical alloying is performed under argon conditions to obtain Cu micro-alloyed NbMoTaW high-entropy alloy powder; obviously, the high-entropy alloy component selection is not a titanium-based high-entropy alloy, and the preparation method adopted is mechanical alloying, the mixing uniformity is poor, impurities are easily doped, and the time consumption is long; and the powder needs to be scraped every 6 hours during the ball milling process to avoid cold welding.

[0009] In addition to the above problems, the PREP and EIGA methods also have limitations in the preparation of titanium-based high-entropy alloy spherical powders, such as complex raw material bar preparation, slow melting rate, low powder yield, and electrode pollution. Therefore, it is urgent to invent a method for preparing high-quality and high-yield fine titanium-based high-entropy alloy spherical powders to meet the high-performance complex shape near-net forming requirements of existing titanium-based high-entropy alloys. Summary of the invention

[0010] In order to solve the problem that Ti-based high entropy alloys for injection molding and additive manufacturing in the prior art have poor room temperature plasticity and are difficult to be drawn, most of the current powder making technologies can only use titanium-based high entropy alloy rods as raw materials. However, due to the lack of a crucible for holding titanium liquid, the existing powder making technology has a low superheat of the titanium-based high entropy alloy liquid, resulting in high viscosity of the titanium-based high entropy alloy droplets, which in turn leads to poor atomization or rotational dispersion effects. The powder particle size after cooling is relatively coarse, and the fine powder yield rate suitable for injection molding, additive manufacturing, etc. does not exceed 40%. In addition, the prepared powder also has problems such as low sphericity, wide particle size distribution, high impurity content, and hollow powder. At the same time, the complex preparation of raw material rods and the slow melting rate of rods also lead to low powder yield and high production costs. Therefore, the embodiment of the present invention provides a method for preparing a fine low-oxygen spherical Ti-based high-entropy alloy powder with a small particle size (0-60 μm), a smooth surface, high sphericity, good fluidity, no hollow powder, low impurity content (oxygen content ≤ 1000 ppm), and high production efficiency. The technical solution is as follows:

[0011] A method for preparing a fine low-oxygen spherical Ti-based high-entropy alloy powder, the method for preparing the fine low-oxygen spherical Ti-based high-entropy alloy powder comprises the following steps:

[0012] S1. Selection and processing of raw materials for wire: according to the mass ratio of the components of the target Ti-based high-entropy alloy wire, select a corresponding plurality of Ti wires and a plurality of wires of other components in a corresponding proportion as wire raw materials; and use commercially available cleaning agents to ultrasonically clean the wire raw materials to obtain wire raw materials with clean surfaces;

[0013] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and hot-drawn continuously for multiple times. After the first round of hot-drawing, the obtained wire is divided into multiple equal parts along the cross section, twisted by a twisting machine, and then hot-drawn for the second time, and then the process of dividing into multiple equal parts-twisting-drawing is repeated until a uniform pre-alloyed wire is obtained;

[0014] S3, preparation of titanium-based high-entropy alloy wire: the pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine, and the entire process is automatically transmitted until the target pass is stopped. The extrusion target pass is related to the diameter of the titanium-based high-entropy alloy wire, the diameter of the extrusion die, and the amount of diameter reduction per pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation to obtain a titanium-based high-entropy alloy wire;

[0015] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0016] S5. Establishment of gas system: adopt radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated, and then filled with inert gas to establish the gas system and adjust the system pressure.

[0017] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5 to obtain the preheated titanium-based high-entropy alloy wire;

[0018] S7, radio frequency plasma melting: sending the titanium-based high entropy alloy wire preheated in S6 to the radio frequency plasma high temperature area for radio frequency plasma melting treatment to obtain titanium-based high entropy alloy droplets with low viscosity;

[0019] S8, atomization powder making: sending the low viscosity titanium-based high entropy alloy droplets in S7 into the atomization reaction chamber for atomization reaction treatment, and obtaining fine low-oxygen spherical Ti-based high entropy alloy powder after cooling and solidification.

[0020] Optionally, the target titanium-based high entropy alloy wire in S1 is mainly composed of Ti a M b X c Y d Z e (M=Cr, Ni, Zr; X=Al, Fe, Mo; Y=Nb, Cu, W, Co; Z=V, Hf, Ta, Mn), where a: 20-80at.%, b, c, d, e: 3-40at.%, a≥b, c, d, e, and a+b+c+d+e=100%, diameter is 1-5mm; the frequency of ultrasonic cleaning is 20-60kHz, and the power is 240-720W.

[0021] Optionally, the speed of the stranding machine in S2 is greater than 500rmp, and the length of the stranded wire after stranding is 70-90% of the wire raw material; the continuous multi-pass hot drawing is specifically as follows: the drawing temperature is 250-500°C, the drawing rate is 5-30m / min, and according to the uniformity of the pre-alloyed wire, the total number of drawing passes is 2-10 rounds, and the total deformation of the multi-pass drawing is 20-90%; the yield strength of the uniform pre-alloyed wire is 50-600MPa, and the elongation is 6-30%.

[0022] Optionally, the extrusion rate of the continuous drawing extrusion in S3 is 1-20 m / min, the temperature of the wire drawing machine is 600-1200° C., and the vacuum degree of the vacuum furnace is 10 -1 ~10 -3Pa, the diameter of the prepared titanium-based high-entropy alloy wire is 0.8-5mm, and the diameter decreases by 0.2-1mm gradually until the target pass stops; the heating and insulation are heated to 800-1300°C and kept warm for 60-120min; the yield strength of the titanium-based high-entropy alloy wire is 800-2600MPa, and the elongation is 4-12%.

[0023] Optionally, the vacuum degree of S5 is 10 -1 ~10 -3 Pa, adjust the system pressure to -55kPa~+55kPa, the gas system has its own oxygen detection device, and the oxygen content of the whole system is ≤20ppm.

[0024] Optionally, the preheating temperature of the preheating treatment in S6 is 500-1000° C., the wire feeding speed is 1-20 m / min, the high-frequency induction heating power is 10-75 kW, and the oscillation frequency is 30-380 kHz.

[0025] Optionally, the RF plasma power of the RF plasma melting treatment in S7 is 30-150kW, the oscillation frequency is 2-230MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 10-50L / min, and the side gas flow rate is 100-300L / min; the viscosity of the titanium-based high entropy alloy droplets is 10-100mPa·s.

[0026] Optionally, the high-pressure gas flow for the atomization reaction treatment in S8 is an argon gas flow or a helium gas flow, the gas purity is ≥99.999%, the pressure is 5-20 MPa, and the gas flow rate is 4-20 m 3 / min.

[0027] Optionally, the oxygen content of the fine low-oxygen spherical Ti-based high-entropy alloy powder in S8 is ≤1000ppm, the powder particle size is 0-60μm, the sphericity is ≥95%, the spheroidization rate is about 100%, and the 0-50μm fine powder recovery rate is ≥90%.

[0028] Optionally, the preparation method described in S1-S8 is not only applicable to the preparation of fine low-oxygen spherical Ti-based high entropy alloy powder, but also to the preparation of other spherical high entropy alloy powders.

[0029] Compared with the prior art, the above technical solution has at least the following beneficial effects:

[0030] The above scheme, the present invention proposes a method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder, which can solve the problems of the existing powder making technology using titanium-based high-entropy alloy rods as raw materials, without a crucible for holding titanium liquid, resulting in large droplet viscosity and coarse powder particle size during the preparation process, as well as other quality problems such as poor sphericity of the prepared powder, wide particle size distribution, high impurity content, hollow powder, etc.; at the same time, it also solves the problem of low preparation efficiency caused by complex raw material rod preparation and slow rod melting rate in the existing powder making technology.

[0031] The present invention is not limited to the preparation of spherical Ti-based high entropy alloy powders, the preparation of spherical titanium-based high entropy alloy powders, and is also applicable to the preparation of other spherical high entropy alloy powders, and has no special restrictions on the raw material grades and components, and can be freely adjusted according to the target composition, with a wide range of raw materials, high design flexibility, and strong industrial applicability. Injection molding and additive manufacturing can prepare a large number of complex shapes with different components containing titanium alloys, which is conducive to industrial large-scale production and commercial promotion and application.

[0032] The present invention utilizes the good room temperature plasticity of a single metal wire, adopts a single metal wire of the alloy to be compounded, and forms a tight spiral structure with two or more of the aforementioned single metal wires through a twisting method. Combined with a multi-pass continuous warm drawing process, the pre-alloying of the single metal alloy to be compounded can be achieved at a relatively low temperature, breaking the technical bottleneck of the raw materials limited by the titanium-based high-entropy alloy powder making technology. Compared with the titanium-based high-entropy alloy rods used in the existing powder preparation method, the invention is convenient to operate and low in cost, and can be applied to alloy injection molding and additive manufacturing of complex shapes with different performance requirements; in particular, thinner wire raw materials are easier to melt during the powder making process, the formed molten droplets have low viscosity, the atomization and dispersion effect is good, and the powder obtained has a fine particle size.

[0033] The present invention combines high-frequency induction heating with radio frequency plasma to achieve segmented continuous heating of titanium-based high-entropy alloy wire. Compared with single induction heating or plasma heating, the present invention can effectively accelerate the melting rate of raw materials, reduce the viscosity of molten droplets, and increase the wire feeding speed and powder yield. The high-temperature plasma can ensure that the molten droplets have high superheat and low viscosity, and use high-pressure gas atomization to atomize low-viscosity titanium-based high-entropy alloy droplets into fine droplets, which are condensed and spheroidized under the action of surface tension. The obtained spherical Ti-based high-entropy alloy powder has fine particle size, good sphericity, high spheroidization rate, no hollow powder, and high yield.

[0034] The present invention uses specially prepared titanium-based high-entropy alloy wire with uniform component distribution as raw material, replacing the traditional radio frequency plasma with powder as raw material. This replacement can effectively reduce the oxidation of the raw material and the adsorption of impurities, and reduce the oxygen content and impurity content of the powder product, thereby obtaining low-oxygen and high-purity spherical Ti-based high-entropy alloy powder with uniform component distribution.

[0035] The entire powder making process of the present invention is carried out under the protection of inert gas, the oxygen content of the entire gas system is ≤20ppm, and the radio frequency plasma equipment used does not have electrode pollution, ensuring that the prepared spherical Ti-based high entropy alloy powder is pollution-free and free of inclusions.

[0036] The invention further disperses the molten droplets after radio frequency plasma atomization by the high-pressure airflow of the atomizing nozzle, thereby avoiding the generation of coarse particle ball powder, ensuring that the fine powder recovery rate of the spherical Ti-based high entropy alloy powder is high, the sphericity is high, the particle size distribution is narrow, and the generation of a large number of hollow balls is avoided.

[0037] The fine low-oxygen spherical titanium-based high-entropy alloy powder prepared by the present invention has a small particle size (0-60 μm), a smooth surface, a high sphericity, good fluidity, no hollow powder, a low impurity content (oxygen content ≤ 1000 ppm), and a high production efficiency. It can effectively improve the performance of titanium-based high-entropy alloy finished products by injection molding and additive manufacturing while reducing the raw material cost.

[0038] In summary, compared with other traditional methods, the method of the present invention can directly prepare Ti-based high-entropy alloy wires with uniform composition distribution at a lower temperature through multiple wire twisting, multiple continuous hot drawing, diffusion homogenization annealing, high-frequency induction preheating, radio frequency plasma melting and atomization powder making, and then prepare Ti-based high-entropy alloy fine powder with low oxygen content and uniform composition distribution. It is suitable for injection molding and additive manufacturing, has high flexibility, simple operation, wide applicability, low cost, and is very suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0040] Figure 1 The present invention is a process flow chart of a method for preparing a fine low-oxygen spherical Ti-based high-entropy alloy powder. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is described below in conjunction with the accompanying drawings.

[0042] In the embodiments of the present invention, words such as "exemplarily" and "for example" are used to indicate examples, illustrations or explanations. Any embodiment or design described as "example" in the present invention should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of the word "example" is intended to present the concept in a specific way. In addition, in the embodiments of the present invention, the meaning expressed by "and / or" can be both, or it can be either of the two.

[0043] In the embodiments of the present invention, "image" and "picture" can sometimes be used interchangeably. It should be noted that when the difference between them is not emphasized, the meanings they want to express are the same. "of", "corresponding" and "corresponding" can sometimes be used interchangeably. It should be noted that when the difference between them is not emphasized, the meanings they want to express are the same.

[0044] In the embodiments of the present invention, sometimes a subscript such as W1 may be written as a non-subscript such as W1. When the difference is not emphasized, the meanings to be expressed are the same.

[0045] In order to make the technical problems, technical solutions and advantages to be solved by the present invention more clear, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

[0046] A method for preparing fine low-oxygen spherical Ti-based high entropy alloy powder, such as Figure 1 As shown, the preparation method of the fine low-oxygen spherical Ti-based high entropy alloy powder comprises the following steps:

[0047] S1. Selection and processing of raw materials for wire: according to the mass ratio of the components of the target Ti-based high-entropy alloy wire, select a corresponding plurality of Ti wires and a plurality of wires of other components in a corresponding proportion as wire raw materials; and use commercially available cleaning agents to ultrasonically clean the wire raw materials to obtain wire raw materials with clean surfaces;

[0048] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and hot-drawn continuously for multiple times. After the first round of hot-drawing, the obtained wire is divided into multiple equal parts along the cross section, twisted by a twisting machine, and then hot-drawn for the second time, and then the process of dividing into multiple equal parts-twisting-drawing is repeated until a uniform pre-alloyed wire is obtained;

[0049] S3, preparation of titanium-based high-entropy alloy wire: the pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine, and the entire process is automatically transmitted until the target pass is stopped. The extrusion target pass is related to the diameter of the titanium-based high-entropy alloy wire, the diameter of the extrusion die, and the amount of diameter reduction per pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation to obtain a titanium-based high-entropy alloy wire;

[0050] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0051] S5. Establishment of gas system: adopt radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated, and then filled with inert gas to establish the gas system and adjust the system pressure.

[0052] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5 to obtain the preheated titanium-based high-entropy alloy wire;

[0053] S7, radio frequency plasma melting: sending the titanium-based high entropy alloy wire preheated in S6 to the radio frequency plasma high temperature area for radio frequency plasma melting treatment to obtain titanium-based high entropy alloy droplets with low viscosity;

[0054] S8, atomization powder making: sending the low viscosity titanium-based high entropy alloy droplets in S7 into the atomization reaction chamber for atomization reaction treatment, and obtaining fine low-oxygen spherical Ti-based high entropy alloy powder after cooling and solidification.

[0055] In particular, the target titanium-based high entropy alloy wire in S1 is mainly composed of Ti a M b X c Y d Z e (M=Cr, Ni, Zr; X=Al, Fe, Mo; Y=Nb, Cu, W, Co; Z=V, Hf, Ta, Mn), where a: 20-80at.%, b, c, d, e: 3-40at.%, a≥b, c, d, e, and a+b+c+d+e=100%, diameter is 1-5mm; the frequency of ultrasonic cleaning is 20-60kHz, and the power is 240-720W.

[0056] In particular, the speed of the stranding machine in S2 is greater than 500rmp, and the length of the stranded wire after stranding is 70-90% of the wire raw material; the continuous multi-pass hot drawing is specifically as follows: the drawing temperature is 250-500°C, the drawing rate is 5-30m / min, and according to the uniformity of the pre-alloyed wire, the total number of drawing passes is 2-10 rounds, and the total deformation of the multi-pass drawing is 20-90%; the yield strength of the uniform pre-alloyed wire is 50-600MPa, and the elongation is 6-30%.

[0057] In particular, the extrusion rate of the continuous drawing extrusion in S3 is 1-20 m / min, the drawing machine temperature is 600-1200°C, and the vacuum degree of the vacuum furnace is 10 -1 ~10 -3 Pa, the diameter of the prepared titanium-based high-entropy alloy wire is 0.8-5mm, and the diameter decreases by 0.2-1mm gradually until the target pass stops; the heating and insulation are heated to 800-1300°C and kept warm for 60-120min; the yield strength of the titanium-based high-entropy alloy wire is 800-2600MPa, and the elongation is 4-12%.

[0058] In particular, the vacuum degree of S5 after evacuation is 10 -1 ~10-3 Pa, adjust the system pressure to -55kPa~+55kPa, the gas system has its own oxygen detection device, and the oxygen content of the whole system is ≤20ppm.

[0059] In particular, the preheating temperature of the preheating treatment in S6 is 500-1000° C., the wire feeding speed is 1-20 m / min, the high-frequency induction heating power is 10-75 kW, and the oscillation frequency is 30-380 kHz.

[0060] In particular, the RF plasma power of the RF plasma melting treatment in S7 is 30-150kW, the oscillation frequency is 2-230MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 10-50L / min, and the side gas flow rate is 100-300L / min; the viscosity of the titanium-based high-entropy alloy droplets is 10-100mPa·s.

[0061] In particular, the high-pressure gas flow for the atomization reaction treatment in S8 is an argon gas flow or a helium gas flow, the gas purity is ≥99.999%, the pressure is 5-20MPa, and the gas flow rate is 4-20m 3 / min.

[0062] In particular, the oxygen content of the fine low-oxygen spherical Ti-based high entropy alloy powder in S8 is ≤1000ppm, the powder particle size is 0-60μm, the sphericity is ≥95%, the spheroidization rate is about 100%, and the 0-50μm fine powder recovery rate is ≥90%.

[0063] In particular, the preparation method described in S1-S8 is not only applicable to the preparation of fine low-oxygen spherical Ti-based high entropy alloy powder, but also to the preparation of other spherical high entropy alloy powders.

[0064] Example 1

[0065] A method for preparing a fine low-oxygen spherical Ti-based high-entropy alloy powder, the composition mass ratio of the titanium-based high-entropy alloy wire is: Ti 35 Ni 25 Fe 10 Hf 10 Nb 20 The preparation method of the fine low-oxygen spherical Ti-based high entropy alloy powder is as follows:

[0066] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target TiAl alloy wire, select two Ti wires with a diameter of 2 mm and other wires of corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 40 kHz and the power being 360 W to obtain the raw wire materials with clean surfaces;

[0067] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing, the total number of drawing rounds is determined to be 2 according to the uniformity of the pre-alloyed wire, the obtained wire is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed, and then the multiple division-twisting-drawing process is repeated until a uniform pre-alloyed wire is obtained; wherein: the two-round drawing temperature is 470-500°C, the drawing rate is 12-16m / min, and the total deformation after two rounds of drawing is 75%; the yield strength of the uniform pre-alloyed wire is 430MPa, and the elongation is 11%;

[0068] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 850°C, the extrusion rate is 8m / min, the extrusion die diameter is 4mm and the diameter decreases by 0.5mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the diameter of the titanium-based high-entropy alloy wire, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and insulation. The vacuum degree is 10 -1 Pa, heating and heat preservation is heating to 800℃ and heat preservation for 80min, and a titanium-based high entropy alloy wire with a diameter of 1mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 1028MPa, and the elongation is 5%;

[0069] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0070] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -1 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -15kPa~+15kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0071] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 700°C, the wire feeding speed is 6m / min, the high-frequency induction heating power is 18kW, and the oscillation frequency is 80kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0072] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 90kW, the oscillation frequency is 30MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 13L / min, the side gas flow rate is 110L / min, and titanium-based high entropy alloy droplets with a viscosity of 12mPa·s are obtained;

[0073] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 7MPa, and the gas flow rate is 9m 3 / min, and after cooling and solidification, fine, low-oxygen spherical Ti-based high entropy alloy powder is obtained.

[0074] The fine low-oxygen spherical Ti-based high-entropy alloy powder prepared in this embodiment has an oxygen content of 647ppm, a powder particle size of 0-60μm, a sphericity ≥95%, a spheroidization rate of about 100%, and a 0-50μm fine powder yield ≥90%.

[0075] Example 2

[0076] A method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder, the mass ratio of the components of the titanium-based high-entropy alloy wire is: TiAlFeMgZn; the method for preparing the fine low-oxygen spherical Ti-based high-entropy alloy powder comprises the following steps:

[0077] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, select 3 Ti wires with a diameter of 3 mm and other component wires in corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 60 kHz and the power being 720 W to obtain the raw wire materials with clean surfaces;

[0078] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing, the total number of drawing rounds is determined to be 3 according to the uniformity of the pre-alloyed wire. The obtained wire is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed. Then, the wire obtained by the second round is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then three rounds of drawing are performed until a uniform pre-alloyed wire is obtained; wherein: the three-round drawing temperature is 380-430°C, the drawing rate is 20-25m / min, and the total deformation after three rounds of drawing is 75%; the yield strength of the uniform pre-alloyed wire is 410MPa, and the elongation is 7%;

[0079] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 1000°C, the extrusion rate is 15m / min, the extrusion die diameter is 5mm and the diameter decreases by 0.2mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the diameter of the titanium-based high-entropy alloy wire, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and insulation. The vacuum degree is 10 -2 Pa, heating and heat preservation is heating to 900℃ and heat preservation for 80min, and a titanium-based high entropy alloy wire with a diameter of 2mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 1000MPa, and the elongation is 5.8%;

[0080] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0081] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -2 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -30kPa~+30kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0082] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 850°C, the wire feeding speed is 10m / min, the high-frequency induction heating power is 30kW, and the oscillation frequency is 150kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0083] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 100kW, the oscillation frequency is 50MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 25L / min, the side gas flow rate is 200L / min, and a titanium-based high entropy alloy droplet with a viscosity of 60mPa·s is obtained;

[0084] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 13MPa, and the gas flow rate is 15m 3 / min, and after cooling and solidification, fine, low-oxygen spherical Ti-based high entropy alloy powder is obtained.

[0085] The fine low-oxygen spherical Ti-based high-entropy alloy powder prepared in this embodiment has an oxygen content of 449 ppm, a powder particle size of 0-60 μm, a sphericity ≥ 95%, a spheroidization rate of about 100%, and a 0-50 μm fine powder yield ≥ 90%.

[0086] Comparative Example 1

[0087] A method for preparing a fine low-oxygen spherical titanium-based high-entropy alloy powder, the composition mass ratio of the titanium-based high-entropy alloy wire is: Ti 35 Ni 25 Fe 10 Hf 10 Nb 20 The preparation method of the fine low-oxygen spherical titanium-based high entropy alloy powder is as follows:

[0088] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, select two Ti wires with a diameter of 2 mm and other wires of corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 40 kHz and the power being 360 W to obtain the raw wire materials with clean surfaces;

[0089] S2. Preparation of pre-alloyed wire: The wire materials in S1 are tightly twisted together by a stranding machine, and a round of continuous multi-pass hot drawing is performed, wherein: the drawing temperature is 470°C, the drawing rate is 12m / min, and the total deformation after drawing is 65%; the yield strength of the pre-alloyed wire is 320MPa, and the elongation is 15%;

[0090] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 850°C, the extrusion rate is 8m / min, the extrusion die diameter is 4mm and the diameter decreases by 0.5mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the titanium-based high-entropy alloy wire diameter, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation. The vacuum degree is 10 -1 Pa, heating and heat preservation is heating to 800℃ and heat preservation for 80min, and a titanium-based high entropy alloy wire with a diameter of 1mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 933MPa, and the elongation is 4.3%;

[0091] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0092] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -1 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -15kPa~+15kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the whole system is >20ppm;

[0093] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 700°C, the wire feeding speed is 6m / min, the high-frequency induction heating power is 18kW, and the oscillation frequency is 80kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0094] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 90kW, the oscillation frequency is 30MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 13L / min, the side gas flow rate is 110L / min, and titanium-based high entropy alloy droplets with a viscosity of 12 mPa·s are obtained;

[0095] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 7MPa, and the gas flow rate is 9m 3 / min, and after cooling and solidification, fine, low-oxygen, spherical titanium-based high-entropy alloy powder is obtained.

[0096] The fine spherical titanium-based high entropy alloy powder obtained in this comparative example has a smooth surface, high sphericity, good fluidity, no hollow powder, small particle size and a narrow distribution range (0-60μm), but due to insufficient continuous warm drawing passes in the preparation process of the titanium-based high entropy alloy wire, the fine spherical titanium-based high entropy alloy powder has component segregation, and since the oxygen content of the entire system is greater than 20ppm, the impurity content of the fine spherical titanium-based high entropy alloy powder is relatively high (the oxygen content is 1984ppm).

[0097] Comparative Example 2

[0098] A method for preparing a fine low-oxygen spherical titanium-based high-entropy alloy powder, wherein the mass ratio of the components of the titanium-based high-entropy alloy wire is: TiAlFeMgZn; the method for preparing the fine low-oxygen spherical titanium-based high-entropy alloy powder comprises the following steps:

[0099] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, select 3 Ti wires with a diameter of 3 mm and other component wires in corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 60 kHz and the power being 720 W to obtain the raw wire materials with clean surfaces;

[0100] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing, the total number of drawing rounds is determined to be 3 according to the uniformity of the pre-alloyed wire. The obtained wire is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed. Then, the wire obtained by the second round is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then three rounds of drawing are performed until a uniform pre-alloyed wire is obtained; wherein: the three-round drawing temperature is 380-430°C, the drawing rate is 20-25m / min, and the total deformation after three rounds of drawing is 75%; the yield strength of the uniform pre-alloyed wire is 410MPa, and the elongation is 7%;

[0101] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 1000°C, the extrusion rate is 15m / min, the extrusion die diameter is 5mm and the diameter decreases by 0.2mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the titanium-based high-entropy alloy wire diameter, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation. The vacuum degree is 10 -2 Pa, heating and heat preservation is heating to 900℃ and heat preservation for 80min, and a titanium-based high entropy alloy wire with a diameter of 2mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 1000MPa, and the elongation is 2.8%;

[0102] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0103] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -2 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -30kPa~+30kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0104] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 400°C, the wire feeding speed is 5m / min, the high-frequency induction heating power is 10kW, and the oscillation frequency is 50kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0105] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 25kW, the oscillation frequency is 12MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 25L / min, the side gas flow rate is 200L / min, and the titanium-based high entropy alloy droplets with a viscosity of 60 mPa·s are obtained;

[0106] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 17MPa, and the gas flow rate is 19m 3 / min, and after cooling and solidification, fine, low-oxygen, spherical titanium-based high-entropy alloy powder is obtained.

[0107] The spherical titanium-based high-entropy alloy powder obtained in this comparative example has a low impurity content (oxygen content is 239ppm), but due to the low high-frequency induction pretreatment temperature and radio frequency melting power, the superheat of the titanium-based high-entropy alloy droplets is insufficient, the viscosity of the molten droplets is too large, the particle size of the obtained titanium-based high-entropy alloy powder is relatively coarse (~350μm), and the sphericity is low (<95%), and the yield of 0-50μm fine powder is <90%.

[0108] In summary, by comparing the embodiments with the comparative examples, it can be found that the uniformity of the titanium-based high-entropy alloy wire determines whether there will be composition segregation in the fine low-oxygen spherical titanium-based high-entropy alloy powder; the control of the impurity content of the system directly affects the impurity content of the final spherical titanium-based high-entropy alloy powder; high-frequency induction preheating temperature, radio frequency plasma melting power, gas flow rate, etc. are important parameters for controlling the particle size and morphology of the titanium-based high-entropy alloy powder.

[0109] Example 3

[0110] A method for preparing a fine low-oxygen spherical Ti-based high-entropy alloy powder, the composition mass ratio of the titanium-based high-entropy alloy wire is: TiAlNbVZr 0.5 The preparation method of the fine low-oxygen spherical Ti-based high entropy alloy powder is as follows:

[0111] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target Ti-based high-entropy alloy wire, select 4 Ti wires with a diameter of 1 mm and other wires of corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 20 kHz and the power being 240 W to obtain the raw wire materials with clean surfaces;

[0112] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing, the total number of drawing rounds is determined to be 6 according to the uniformity of the pre-alloyed wire, and the obtained wire is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed. Then, the wire obtained in the second round is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then three rounds of drawing are performed, and four, five and six rounds of drawing are performed in this way until a uniform pre-alloyed wire is obtained; wherein: the 6-round drawing temperature is 300-480°C, the drawing rate is 7-9m / min, and the total deformation after two rounds of drawing is 87%; the yield strength of the uniform pre-alloyed wire is 567MPa, and the elongation is 6.3%;

[0113] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 750°C, the extrusion rate is 6 m / min, the extrusion die diameter is 3 mm and the diameter decreases by 0.2 mm each time. The whole process is automatically transmitted until the target pass is stopped. The extrusion target pass is related to the diameter of the titanium-based high-entropy alloy wire, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation. The vacuum degree is 10 -3 Pa, heating and heat preservation is heating to 960℃ and heat preservation for 110min, and a titanium-based high entropy alloy wire with a diameter of 0.8mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 1070MPa, and the elongation is 5%;

[0114] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0115] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -3 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -50kPa~+50kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0116] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 900°C, the wire feeding speed is 18m / min, the high-frequency induction heating power is 50kW, and the oscillation frequency is 220kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0117] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 50kW, the oscillation frequency is 8MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 10L / min, the side gas flow rate is 150L / min, and titanium-based high entropy alloy droplets with a viscosity of 32mPa·s are obtained;

[0118] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 17MPa, and the gas flow rate is 19m 3 / min, and after cooling and solidification, fine, low-oxygen spherical Ti-based high entropy alloy powder is obtained.

[0119] The fine low-oxygen spherical Ti-based high-entropy alloy powder prepared in this embodiment has an oxygen content of 205ppm, a powder particle size of 0-60μm, a sphericity ≥95%, a spheroidization rate of about 100%, and a 0-50μm fine powder yield ≥90%.

[0120] Example 4

[0121] A method for preparing a fine low-oxygen spherical titanium-based high-entropy alloy powder, wherein the mass ratio of the components of the titanium-based high-entropy alloy wire is: TiAlFeMgZn; the method for preparing the fine low-oxygen spherical titanium-based high-entropy alloy powder comprises the following steps:

[0122] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, select two Ti wires with a diameter of 2 mm and other wires of corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 40 kHz and the power being 360 W to obtain the raw wire materials with clean surfaces;

[0123] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing, the total number of drawing rounds is determined to be 2 according to the uniformity of the pre-alloyed wire, the obtained wire is divided into two equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed, and then the multiple division-twisting-drawing process is repeated until a uniform pre-alloyed wire is obtained; wherein: the drawing temperature of the two rounds is 480°C, the drawing rate is 14-16m / min, and the total deformation after the two rounds of drawing is 75%; the yield strength of the uniform pre-alloyed wire is 417MPa, and the elongation is 6.8%;

[0124] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 850°C, the extrusion rate is 8m / min, the extrusion die diameter is 4mm and the diameter decreases by 0.5mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the titanium-based high-entropy alloy wire diameter, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation. The vacuum degree is 10 -1 Pa, heating and heat preservation is heating to 800℃ and heat preservation for 80min, and a titanium-based high entropy alloy wire with a diameter of 1mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 936MPa, and the elongation is 6.5%;

[0125] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0126] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -1 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -17kPa~+17kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0127] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 720°C, the wire feeding speed is 6m / min, the high-frequency induction heating power is 20kW, and the oscillation frequency is 87kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0128] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 85kW, the oscillation frequency is 20MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 15L / min, the side gas flow rate is 130L / min, and titanium-based high entropy alloy droplets with a viscosity of 18 mPa·s are obtained;

[0129] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 9MPa, and the gas flow rate is 12m 3 / min, and after cooling and solidification, fine, low-oxygen, spherical titanium-based high-entropy alloy powder is obtained.

[0130] The fine low-oxygen spherical titanium-based high-entropy alloy powder prepared in this embodiment has an oxygen content of 605ppm, a powder particle size of 0-60μm, a sphericity ≥95%, a spheroidization rate of about 100%, and a 0-50μm fine powder yield ≥90%.

[0131] Example 5

[0132] A method for preparing a fine low-oxygen spherical titanium-based high-entropy alloy powder, the composition mass ratio of the titanium-based high-entropy alloy wire is: Ti 35 Ni 25 Fe 10 Hf 10 Nb 20 The preparation method of the fine low-oxygen spherical titanium-based high entropy alloy powder is as follows:

[0133] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, select 4 Ti wires with a diameter of 1 mm and other component wires in corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 20 kHz and the power being 240 W to obtain the raw wire materials with clean surfaces;

[0134] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing is completed, the total number of drawing rounds is determined to be 4 according to the uniformity of the pre-alloyed wire, the obtained wire is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed, and then the wire obtained by the second round is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then three rounds of drawing are performed until the four rounds of hot drawing are completed to obtain uniform pre-alloyed wire; wherein: the drawing temperature of the four rounds is 300-480°C, the drawing rate is 8-10m / min, and the total deformation after two rounds of drawing is 85%; the yield strength of the uniform pre-alloyed wire is 557MPa, and the elongation is 7.1%;

[0135] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 750°C, the extrusion rate is 6m / min, the extrusion die diameter is 3mm and the diameter decreases by 0.2mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the titanium-based high-entropy alloy wire diameter, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation. The vacuum degree is 10 -3 Pa, heating and heat preservation is heating to 960℃ and heat preservation for 110min, and a titanium-based high entropy alloy wire with a diameter of 0.8mm and uniform composition is obtained; the yield strength of the titanium-based high entropy alloy wire is 1053MPa, and the elongation is 6.6%;

[0136] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0137] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -3 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -40kPa~+40kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0138] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 880°C, the wire feeding speed is 16m / min, the high-frequency induction heating power is 45kW, and the oscillation frequency is 200kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0139] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 45kW, the oscillation frequency is 6MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 13L / min, the side gas flow rate is 140L / min, and titanium-based high entropy alloy droplets with a viscosity of 67 mPa·s are obtained;

[0140] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 16MPa, and the gas flow rate is 19m 3 / min, and after cooling and solidification, fine, low-oxygen, spherical titanium-based high-entropy alloy powder is obtained.

[0141] The fine low-oxygen spherical titanium-based high-entropy alloy powder prepared in this embodiment has an oxygen content of 248ppm, a powder particle size of 0-60μm, a sphericity of ≥95%, a spheroidization rate of about 100%, and a 0-50μm fine powder yield of ≥90%.

[0142] Example 6

[0143] A method for preparing a fine low-oxygen spherical titanium-based high-entropy alloy powder, the composition mass ratio of the titanium-based high-entropy alloy wire is: TiAlNbVZr 0.5 The preparation method of the fine low-oxygen spherical titanium-based high entropy alloy powder is as follows:

[0144] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, select 3 Ti wires with a diameter of 3 mm and other component wires in corresponding proportions; and use commercially available cleaning agents to ultrasonically clean the raw wire materials, with the frequency of ultrasonic cleaning being 60 kHz and the power being 720 W to obtain the raw wire materials with clean surfaces;

[0145] S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and continuous multiple hot drawing is performed. After the first round of hot drawing, the total number of drawing rounds is determined to be 3 according to the uniformity of the pre-alloyed wire. The obtained wire is divided into two equal parts along the cross section, and then twisted by a twisting machine, and then two rounds of hot drawing are performed. Then, the wire obtained by the two rounds is divided into four equal parts along the cross section, and then twisted by a twisting machine, and then three rounds of drawing are performed until a uniform pre-alloyed wire is obtained; wherein: the three-round drawing temperature is 380-420°C, the drawing rate is 20-25m / min, and the total deformation after three rounds of drawing is 75%; the yield strength of the uniform pre-alloyed wire is 468MPa, and the elongation is 8.3%;

[0146] S3. Preparation of titanium-based high-entropy alloy wire: The pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine. The temperature of the wire drawing machine is 1000°C, the extrusion rate is 16m / min, the extrusion die diameter is 5mm and the diameter decreases by 0.2mm each time. The whole process is automatically transmitted until the target pass stops. The extrusion target pass is related to the titanium-based high-entropy alloy wire diameter, the extrusion die diameter and the diameter reduction of each pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation. The vacuum degree is 10 -2 Pa, heating and heat preservation is heating to 900℃ and heat preservation for 80min, and a titanium-based high entropy alloy wire with uniform composition and a diameter of 3mm is obtained; the yield strength of the titanium-based high entropy alloy wire is 1068MPa, and the elongation is 4.4%;

[0147] S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface;

[0148] S5. Establishment of gas system: Use radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated to a vacuum degree of 10 -2 Pa, then fill in inert gas to establish a gas system, adjust the system pressure to -25kPa~+25kPa, the gas system is equipped with an oxygen detection device, and the oxygen content of the entire system is ≤20ppm;

[0149] S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5, the preheating temperature is 800°C, the wire feeding speed is 8m / min, the high-frequency induction heating power is 28kW, and the oscillation frequency is 140kHz, to obtain the preheated titanium-based high-entropy alloy wire;

[0150] S7, radio frequency plasma melting: the titanium-based high entropy alloy wire preheated in S6 is sent to the radio frequency plasma high temperature area for radio frequency plasma melting treatment, the radio frequency plasma power is 90kW, the oscillation frequency is 30MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 20L / min, the side gas flow rate is 170L / min, and titanium-based high entropy alloy droplets with a viscosity of 76 mPa·s are obtained;

[0151] S8, atomization powder making: send the titanium-based high entropy alloy droplets with low viscosity S7 into the atomization reaction chamber for atomization reaction treatment, wherein the high-pressure gas flow is argon gas flow or helium gas flow, the gas purity is ≥99.999%, the pressure is 15MPa, and the gas flow rate is 18m 3 / min, and after cooling and solidification, fine, low-oxygen, spherical titanium-based high-entropy alloy powder is obtained.

[0152] The fine low-oxygen spherical titanium-based high-entropy alloy powder prepared in this embodiment has an oxygen content of 376 ppm, a powder particle size of 0-60 μm, a sphericity ≥ 95%, a spheroidization rate of about 100%, and a 0-50 μm fine powder yield ≥ 90%.

[0153] The above scheme, the present invention proposes a method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder, which can solve the problems of the existing powder making technology using titanium-based high-entropy alloy rods as raw materials, without a crucible for holding titanium liquid, resulting in large droplet viscosity and coarse powder particle size during the preparation process, as well as other quality problems such as poor sphericity of the prepared powder, wide particle size distribution, high impurity content, hollow powder, etc.; at the same time, it also solves the problem of low preparation efficiency caused by complex raw material rod preparation and slow rod melting rate in the existing powder making technology.

[0154] The present invention is not limited to the preparation of spherical Ti-based high entropy alloy powders, the preparation of spherical titanium-based high entropy alloy powders, and is also applicable to the preparation of other spherical high entropy alloy powders, and has no special restrictions on the raw material grades and components, and can be freely adjusted according to the target composition, with a wide range of raw materials, high design flexibility, and strong industrial applicability. Injection molding and additive manufacturing can prepare a large number of complex shapes with different components containing titanium alloys, which is conducive to industrial large-scale production and commercial promotion and application.

[0155] The present invention utilizes the good room temperature plasticity of a single metal wire, adopts a single metal wire of the alloy to be compounded, and forms a tight spiral structure with two or more of the aforementioned single metal wires through a twisting method. Combined with a multi-pass continuous warm drawing process, the pre-alloying of the single metal alloy to be compounded can be achieved at a relatively low temperature, breaking the technical bottleneck of the raw materials limited by the titanium-based high-entropy alloy powder making technology. Compared with the titanium-based high-entropy alloy rods used in the existing powder preparation method, the invention is convenient to operate and low in cost, and can be applied to alloy injection molding and additive manufacturing of complex shapes with different performance requirements; in particular, thinner wire raw materials are easier to melt during the powder making process, the formed molten droplets have low viscosity, the atomization and dispersion effect is good, and the powder obtained has a fine particle size.

[0156] The present invention combines high-frequency induction heating with radio frequency plasma to achieve segmented continuous heating of titanium-based high-entropy alloy wire. Compared with single induction heating or plasma heating, the present invention can effectively accelerate the melting rate of raw materials, reduce the viscosity of molten droplets, and increase the wire feeding speed and powder yield. The high-temperature plasma can ensure that the molten droplets have high superheat and low viscosity, and use high-pressure gas atomization to atomize low-viscosity titanium-based high-entropy alloy droplets into fine droplets, which are condensed and spheroidized under the action of surface tension. The obtained spherical Ti-based high-entropy alloy powder has fine particle size, good sphericity, high spheroidization rate, no hollow powder, and high yield.

[0157] The present invention uses specially prepared titanium-based high-entropy alloy wire with uniform component distribution as raw material, replacing the traditional radio frequency plasma with powder as raw material. This replacement can effectively reduce the oxidation of the raw material and the adsorption of impurities, and reduce the oxygen content and impurity content of the powder product, thereby obtaining low-oxygen and high-purity spherical Ti-based high-entropy alloy powder with uniform component distribution.

[0158] The entire powder making process of the present invention is carried out under the protection of inert gas, the oxygen content of the entire gas system is ≤20ppm, and the radio frequency plasma equipment used does not have electrode pollution, ensuring that the prepared spherical Ti-based high entropy alloy powder is pollution-free and free of inclusions.

[0159] The invention further disperses the molten droplets after radio frequency plasma atomization by the high-pressure airflow of the atomizing nozzle, thereby avoiding the generation of coarse particle ball powder, ensuring that the fine powder recovery rate of the spherical Ti-based high entropy alloy powder is high, the sphericity is high, the particle size distribution is narrow, and the generation of a large number of hollow balls is avoided.

[0160] The fine low-oxygen spherical titanium-based high-entropy alloy powder prepared by the present invention has a small particle size (0-60 μm), a smooth surface, a high sphericity, good fluidity, no hollow powder, a low impurity content (oxygen content ≤ 1000 ppm), and a high production efficiency. It can effectively improve the performance of titanium-based high-entropy alloy finished products by injection molding and additive manufacturing while reducing the raw material cost.

[0161] In summary, compared with other traditional methods, the method of the present invention can directly prepare Ti-based high-entropy alloy wires with uniform composition distribution at a lower temperature through multiple wire twisting, multiple continuous hot drawing, diffusion homogenization annealing, high-frequency induction preheating, radio frequency plasma melting and atomization powder making, and then prepare Ti-based high-entropy alloy fine powder with low oxygen content and uniform composition distribution. It is suitable for injection molding and additive manufacturing, has high flexibility, simple operation, wide applicability, low cost, and is very suitable for large-scale industrial production.

[0162] It should be understood that the term "and / or" in this article is only a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship, but it may also indicate an "and / or" relationship. Please refer to the context for specific understanding.

[0163] In the present invention, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, at least one of a, b, or c can be represented by: a, b, c, ab, ac, bc, or abc, where a, b, and c can be single or multiple.

[0164] It should be understood that in various embodiments of the present invention, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0165] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing fine low-oxygen spherical Ti-based high entropy alloy powder, characterized in that: The preparation method of the fine low-oxygen spherical Ti-based high-entropy alloy powder comprises the following steps: S1. Selection and processing of raw materials for wire: according to the mass ratio of the components of the target Ti-based high-entropy alloy wire, select a corresponding plurality of Ti wires and a plurality of wires of other components in a corresponding proportion as wire raw materials; and use commercially available cleaning agents to ultrasonically clean the wire raw materials to obtain wire raw materials with clean surfaces; S2, preparation of pre-alloyed wire: the wire raw materials in S1 are tightly twisted together by a twisting machine, and hot-drawn continuously for multiple times. After the first round of hot-drawing, the obtained wire is divided into multiple equal parts along the cross section, twisted by a twisting machine, and then hot-drawn for the second time, and then the process of dividing into multiple equal parts-twisting-drawing is repeated until a uniform pre-alloyed wire is obtained; S3, preparation of titanium-based high-entropy alloy wire: the pre-alloyed wire prepared in S2 is continuously drawn and extruded through a continuous wire drawing machine, and the entire process is automatically transmitted until the target pass is stopped. The extrusion target pass is related to the diameter of the titanium-based high-entropy alloy wire, the diameter of the extrusion die, and the amount of diameter reduction per pass. The obtained wire is placed in a vacuum furnace for heating and heat preservation to obtain a titanium-based high-entropy alloy wire; S4. Treatment of titanium-based high-entropy alloy wire: The titanium-based high-entropy alloy wire prepared in S3 is cleaned on the surface with a commercially available cleaning agent to remove oxide scale and impurities, thereby obtaining a titanium-based high-entropy alloy wire with a clean surface; S5. Establishment of gas system: adopt radio frequency plasma combined with gas atomization powder making equipment for powder making. Before powder making, the whole powder making system needs to be evacuated, and then filled with inert gas to establish the gas system and adjust the system pressure. S6, high-frequency induction preheating: the titanium-based high-entropy alloy wire whose surface is cleaned in S4 is preheated by the high-frequency induction heating equipment adjusted in S5 to obtain the preheated titanium-based high-entropy alloy wire; S7, radio frequency plasma melting: sending the titanium-based high entropy alloy wire preheated in S6 to the radio frequency plasma high temperature area for radio frequency plasma melting treatment to obtain titanium-based high entropy alloy droplets with low viscosity; S8, atomization powder making: sending the low viscosity titanium-based high entropy alloy droplets in S7 into the atomization reaction chamber for atomization reaction treatment, and obtaining fine low-oxygen spherical Ti-based high entropy alloy powder after cooling and solidification.

2. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The main component of the target titanium-based high entropy alloy wire in S1 is Ti a M b X c Y d Z e (M=Cr, Ni, Zr; X=Al, Fe, Mo; Y=Nb, Cu, W, Co; Z=V, Hf, Ta, Mn), where a: 20-80at.%, b, c, d, e: 3-40at.%, a≥b, c, d, e, and a+b+c+d+e=100%, diameter is 1-5mm; the frequency of ultrasonic cleaning is 20-60kHz, and the power is 240-720W.

3. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: In S2, the speed of the stranding machine is greater than 500rmp, and the length of the stranded wire after stranding is 70-90% of the wire raw material; the continuous multi-pass hot drawing is specifically as follows: the drawing temperature is 250-500°C, the drawing rate is 5-30m / min, and according to the uniformity of the pre-alloyed wire, the total number of drawing passes is 2-10 rounds, and the total deformation of the multi-pass drawing is 20-90%; the yield strength of the uniform pre-alloyed wire is 50-600MPa, and the elongation is 6-30%.

4. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The extrusion rate of the continuous drawing extrusion in S3 is 1-20m / min, the temperature of the wire drawing machine is 600-1200℃, and the vacuum degree of the vacuum furnace is 10 -1 ~10 -3 Pa, the diameter of the prepared titanium-based high-entropy alloy wire is 0.8-5mm, and the diameter decreases by 0.2-1mm until the target pass stops; The heating and heat preservation is heating to 800-1300° C. and keeping the temperature for 60-120 minutes; the yield strength of the titanium-based high entropy alloy wire is 800-2600 MPa, and the elongation is 4-12%.

5. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: After S5 is evacuated, the vacuum degree is 10 -1 ~10 -3 Pa, adjust the system pressure to -55kPa~+55kPa, the gas system has its own oxygen detection device, and the oxygen content of the whole system is ≤20ppm.

6. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The preheating temperature of the preheating treatment in S6 is 500-1000°C, the wire feeding speed is 1-20m / min, the high-frequency induction heating power is 10-75kW, and the oscillation frequency is 30-380kHz.

7. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The RF plasma power of the RF plasma melting treatment in S7 is 30-150kW, the oscillation frequency is 2-230MHz, the inert gas is argon or helium, the gas purity is ≥99.999%, and the main gas flow rate is 10-50L / min, and the side gas flow rate is 100-300L / min; the viscosity of the titanium-based high entropy alloy droplet is 10-100mPa·s.

8. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The high-pressure gas flow for atomization reaction treatment in S8 is argon or helium, with a gas purity of ≥99.999%, a pressure of 5-20MPa, and a gas flow rate of 4-20m 3 / min.

9. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The oxygen content of the fine low-oxygen spherical Ti-based high entropy alloy powder in S8 is ≤1000ppm, the powder particle size is 0-60μm, the sphericity is ≥95%, the spheroidization rate is about 100%, and the 0-50μm fine powder recovery rate is ≥90%.

10. The method for preparing fine low-oxygen spherical Ti-based high-entropy alloy powder according to claim 1, characterized in that: The preparation method described in S1-S8 is not only applicable to the preparation of fine low-oxygen spherical Ti-based high entropy alloy powder, but also applicable to the preparation of other spherical high entropy alloy powders.

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