Preparation method of fine titanium-based high-entropy alloy wire

Abstract

The invention provides a preparation method of a fine titanium-based high-entropy alloy wire, and relates to the technical field of titanium-based high-entropy alloy preparation. The preparation method comprises the steps of raw material selection and treatment of a wire, raw material twisting of the wire, continuous warm drawing of a primary titanium-based high-entropy composite stranded wire, twisting of the primary titanium-based high-entropy composite wire, continuous warm drawing of a secondary titanium-based high-entropy composite stranded wire, multiple times of warm drawing of the titanium-based high-entropy composite wire and continuous extrusion of the titanium-based high-entropy wire which are sequentially carried out. And diffusion homogenization of the titanium-based high-entropy alloy wire is carried out. According to the preparation method, the titanium-based high-entropy alloy wire with uniformly distributed components can be directly prepared at a relatively low temperature by combining multiple wire twisting, multiple continuous hot drawing and final diffusion homogenizing annealing, so that a high-temperature melting process is effectively avoided; the components and the diameter of the titanium-based high-entropy alloy wire can be designed according to the requirements of the target titanium-based high-entropy alloy wire for the preparation of the titanium-based high-entropy composite wire and the pass in the extrusion process, and the titanium-based high-entropy alloy wire is high in flexibility, easy 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 titanium-based high-entropy alloy preparation, in particular to a method for preparing a fine titanium-based high-entropy alloy wire. Background Art

[0002] High entropy alloy is a new type of alloy composed of five or more main components, mixed in an equiatomic ratio or approximately equiatomic ratio. Its four specific effects (high entropy effect, lattice distortion effect, hysteresis diffusion effect, cocktail effect) make high entropy alloy have many excellent properties, such as high strength, high hardness, good thermal stability, excellent corrosion resistance, etc. Adding titanium 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, aeroengines, and new generation launch vehicles, the structure of aerospace parts tends to be integrated and complex. The traditional casting, forging and machining forming method can no longer meet the high-efficiency and low-cost complex structure manufacturing needs.

[0003] At present, additive manufacturing of titanium-based high-entropy alloys has become one of the key research directions in the scientific and technological community. Additive manufacturing technology is based on the principle of layer-by-layer accumulation from the bottom up, so it has excellent complex molding capabilities. According to different feeding methods, it can be divided into three types: powder laying, powder feeding, and wire feeding. However, powder additive manufacturing technology has high requirements on the quality of powder raw materials, and the deposition speed is slow during the preparation process; and due to the limitations of existing powder making technology, the powder is expensive. In comparison, the fused wire additive manufacturing technology using wire as raw material has a fast deposition speed, low production cost, and large molding freedom.

[0004] Therefore, additively manufactured titanium-based high-entropy alloys have shown great application prospects in the aerospace field. Among them, fused filament additively manufactured titanium-based high-entropy alloys can break through shape constraints while having the advantages of high forming efficiency and low production cost, and are expected to further enhance the engineering application of complex structure titanium-based high-entropy alloys.

[0005] However, due to the poor room temperature plasticity of titanium-based high entropy alloys, it is difficult to draw wires. The existing titanium-based high entropy alloy fused wire additive manufacturing mostly adopts double-wire or multi-wire wire feeding methods, but its operating mechanism is complex and the equipment cost is high. Even the single-wire wire feeding method uses titanium-based high entropy composite wire as raw material, which has problems such as complex wire preparation, uneven component distribution, and high cost. Therefore, it is urgent to invent a method for preparing titanium-based high entropy alloy wire to meet the high-quality fused wire additive manufacturing needs of titanium-based high entropy alloys.

[0006] For example: Chinese patent CN117127081A discloses a high entropy alloy wire for additive manufacturing and a preparation method thereof, which uses Fe, Co, Cr, Ni, Al, and Ti metal elements with specific atomic percentages as raw materials, including raw material preparation, smelting, forging, hot rolling, drawing, and adjustment steps; this method prepares high entropy alloy wires through traditional processes, and although the prepared high entropy alloy rods are repeatedly smelted, the composition distribution is not uniform; in particular, the subsequent hot rolling and drawing will increase the uneven distribution.

[0007] Chinese patent CN114507802A discloses a low-cost high-entropy alloy powder core wire for laser additive manufacturing and a preparation method thereof. The high-entropy alloy powder core wire comprises a metal outer tube and pure metal or alloy powder located inside. The pure metal or alloy powder is filled into a metal seamless tube and then sealed, and the wire is obtained by more than 10 rotary forging passes. Even if the alloy powder is evenly distributed in the tube, after multiple rotary forging passes, the components of the outer tube will be mixed into the powder core wire, resulting in uneven distribution of the components.

[0008] Chinese patent CN114032435A discloses a high-entropy alloy micron wire for antioxidant additive manufacturing and a synthesis method thereof. Obviously, the synthesis method requires a special device structure to be implemented. The vacuum suction cast rod is affected by the process, and its composition is not evenly distributed in various parts of the rod. The subsequent vacuum melting copper roller wire spinning process will increase this difference. Summary of the invention

[0009] In order to solve the problem that titanium-based high entropy alloys are difficult to be drawn and formed into fine titanium-based high entropy alloy wires due to poor room temperature plasticity in the preparation process of fuses in the prior art, resulting in the inability to meet the urgent demand for titanium-based high entropy alloy wires in the application market. In addition, there are many technical problems such as uneven distribution of components of titanium-based high entropy alloy raw wires, component segregation, and poor room temperature plasticity, which lead to the inability to draw and form, as well as the complex structure of the device used in the preparation process, high difficulty in operation, high cost, and low efficiency. As a result, it is difficult to ensure the performance of titanium-based high entropy alloy parts and the uniformity of components in each part during the deposition process of fuse additive manufacturing, further causing technical problems such as poor stability of titanium-based high entropy alloy products; therefore, the embodiment of the present invention provides a method for preparing a fine titanium-based high entropy alloy wire with low cost, simple preparation method, uniform component distribution, high mechanical properties, low temperature toughness and fatigue strength. The technical scheme is as follows:

[0010] A method for preparing a fine titanium-based high-entropy alloy wire, the method for preparing the fine titanium-based high-entropy alloy wire comprising the following steps:

[0011] S1. Selection and processing of raw materials for wire: According to the mass ratio of the components of the target titanium-based high-entropy alloy wire, select a corresponding number of Ti wires with corresponding proportions of other component wire raw materials; and use commercially available cleaning agents to ultrasonically clean the wire raw materials to obtain surface-cleaned wire raw materials;

[0012] S2, twisting the raw materials of the wire: the raw materials of the wire in S1 are tightly twisted together by a twisting machine to obtain a primary titanium-based high-entropy composite twisted wire with a multi-helical structure;

[0013] S3, continuous warm drawing of a primary titanium-based high-entropy composite strand: the primary titanium-based high-entropy composite strand prepared in S2 is subjected to continuous multi-pass hot drawing, and the entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire;

[0014] S4, twisting of primary titanium-based high-entropy composite wires: dividing the primary titanium-based high-entropy composite wires prepared in S3 into multiple equal parts along the cross section, and tightly twisting the cut titanium-based high-entropy composite wires together by a twisting machine to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure;

[0015] S5, continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: the secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, and the entire process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire;

[0016] S6, multiple warm drawing of the titanium-based high-entropy composite wire: according to the uniformity of the titanium-based high-entropy composite wire, determine the warm drawing pass, repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a stranding machine to tightly twist the cut titanium-based high-entropy composite wires together, and then perform the next warm drawing until the target pass is completed to obtain the titanium-based high-entropy composite wire;

[0017] S7, continuous extrusion of titanium-based high entropy wire: the titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, and the whole process is automatically transmitted until the target pass is stopped, thereby obtaining a titanium-based high entropy alloy wire;

[0018] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 is subjected to diffusion homogenization treatment in a vacuum furnace, and after cooling in the furnace, a fine titanium-based high entropy alloy wire with uniform composition is obtained.

[0019] Optionally, the wire material in S1 uses existing wire grades, or is customized to adjust the composition; the target titanium-based high entropy alloy wire mainly consists 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%; the diameter of the wire raw material is 1-5mm; the frequency of ultrasonic cleaning is 20-60kHz, and the power is 240-720W.

[0020] Optionally, the speed of the stranding machine in S2 and S4 is greater than 500 rpm, and the length of the stranded wire after stranding is 70-90% of the wire raw material; the multi-helix structure is a double helix structure or a structure with more than double helix.

[0021] Optionally, the continuous multi-pass hot drawing in S3 and S5 is specifically as follows: first heating to 300-900°C and preheating the drawing die to 300-700°C, and then performing continuous multi-pass drawing, with a drawing rate of 5-30m / min, a deformation amount of 10-20% for each drawing, and a total deformation amount of 20-90% for multi-pass drawing; the yield strength of the primary titanium-based high-entropy composite wire is 50-600MPa, and the elongation is 6-30%.

[0022] Optionally, S4 is divided into two or more equal parts.

[0023] Optionally, the yield strength of the secondary titanium-based high-entropy composite wire in S5 is 50-600 MPa and the elongation is 6-30%.

[0024] Optionally, the continuous warm drawing passes in S6 are 2-10 times, the yield strength of the titanium-based high-entropy composite wire is 50-600 MPa, and the elongation is 6-30%.

[0025] Optionally, the extrusion rate of the continuous drawing extrusion in S7 is 1-20m / min, the wire drawing machine temperature is 600-1200°C, the extrusion die diameter is 0.8-5mm and the diameter decreases gradually by 0.2-1mm, the extrusion target pass matches the titanium-based high-entropy pre-alloyed wire diameter, the extrusion die diameter and the diameter reduction per pass, and the yield strength of the titanium-based high-entropy alloy wire is 800-2500MPa, and the elongation is 3-15%.

[0026] Optionally, the temperature of the diffusion homogenization treatment in S8 is 800-1300°C, the insulation time is 60-120 minutes, and the vacuum degree is 10 -1 ~10 -3 Pa, the yield strength of uniformly composed fine titanium-based high-entropy alloy wire is 800-2600MPa, and the elongation is 3-10%.

[0027] Optionally, the preparation method described in S1-S8 is not only applicable to titanium-based high entropy alloys, but also to the preparation of other high entropy alloy wires.

[0028] Compared with the prior art, the above technical solution has at least the following beneficial effects:

[0029] The above scheme, the present invention proposes a method for preparing a fine titanium-based high-entropy alloy wire, which can solve the technical bottleneck of preparing titanium-based high-entropy alloy wire by drawing due to poor room temperature plasticity of titanium-based high-entropy alloy, and further solve the problem of limited application of titanium-based high-entropy alloy wire. The traditional process of single-wire additive manufacturing technology using titanium-based high-entropy composite wire as raw material has problems such as complex wire preparation and uneven finished product components. The fine titanium-based high-entropy alloy wire obtained by the present invention has uniform composition and organization, dense structure, smooth surface, and no defects such as oxidation, cracking, and pores. The performance of each part of the fused wire additive manufacturing product using this as raw material is stable and consistent, providing high-quality raw materials for expanding the application of titanium-based high-entropy alloys.

[0030] The present invention is not limited to the preparation of titanium-based high-entropy alloy wires, but is also applicable to the preparation of other high-entropy alloy wires, and has no special restrictions on raw material grades, components, etc., and has a wide range of selectable raw materials. Additive manufacturing can prepare a large number of complex shapes and titanium-containing alloys with different components, which is conducive to large-scale industrial production and commercial promotion and application.

[0031] The present invention utilizes the good room temperature plasticity of a single metal wire or alloy wire, adopts the alloy single metal wire 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 alloy single metal to be compounded can be achieved at a relatively low temperature. The operation is convenient and the cost is low, and it can be applied to the fused additive manufacturing of complex-shaped titanium-based high-entropy alloy wires with different performance requirements.

[0032] Compared with the cold drawing method, the continuous warm drawing method adopted in the present invention can improve the plastic deformation ability of the titanium-based high-entropy alloy wire during the drawing process, reduce the deformation resistance, ensure that no cracking, wire breakage, etc. occur during the deformation process, and can effectively reduce the number of drawing passes and reduce the internal stress of the prepared titanium-based high-entropy alloy wire, so that the preparation efficiency of the titanium-based high-entropy alloy wire is significantly improved.

[0033] The present invention can completely alloy the pre-alloyed titanium-based high-entropy composite wire by continuously drawing and extruding it at a relatively low temperature with a gradually decreasing diameter of the extrusion die, thereby avoiding a high-temperature melting process and solving the technical bottleneck of titanium-based high-entropy alloys being difficult to prepare alloy wires due to their brittleness at room temperature, and effectively reducing the volatilization of low-melting-point elements during the preparation of the titanium-based high-entropy alloy wires.

[0034] The diffusion homogenization annealing treatment adopted in the present invention can make the heterogeneous elements in the titanium-based high-entropy alloy wire further diffuse with each other, ensure that the obtained titanium-based high-entropy alloy wire has a completely uniform distribution of components, increase the uniformity of the distribution of components after the wire is melted in the additive manufacturing process, and improve the yield of printed products.

[0035] The automatic conveying device adopted in the present invention can greatly improve the production efficiency of titanium-based high-entropy alloy wire, effectively reduce its production cost, eliminate manual interference in alloy wire preparation, and further improve the production quality of titanium-based high-entropy alloy wire.

[0036] The present invention can make adaptive adjustments in the selection of passes in the preparation and extrusion process of the titanium-based high-entropy composite wire according to the component ratio and diameter of the target titanium-based high-entropy alloy wire, to ensure that the components of the titanium-based high-entropy alloy wires with different compositions are evenly distributed and the diameters meet the requirements, and the titanium-based high-entropy alloy wires all have high quality and high performance.

[0037] In summary, compared with other traditional methods, the method of the present invention can directly prepare titanium-based high-entropy alloy wires with uniform composition distribution at a lower temperature through multiple wire twisting, multiple continuous hot drawing and final diffusion homogenization annealing, effectively avoiding the high-temperature melting process. The composition and diameter can be designed according to the requirements of the target titanium-based high-entropy alloy wire for the preparation of titanium-based high-entropy composite wires and the passes in the extrusion process. It has high flexibility, simple operation, wide applicability and low cost, and is very suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] 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.

[0039] Figure 1 It is a process flow chart of a method for preparing a fine titanium-based high-entropy alloy wire of the present invention. DETAILED DESCRIPTION

[0040] The technical solution of the present invention is described below in conjunction with the accompanying drawings.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] A method for preparing a fine titanium-based high entropy alloy wire, such as Figure 1 As shown, the preparation method of the fine titanium-based high entropy alloy wire comprises the following steps:

[0046] S1. Selection and processing of raw materials for wire: According to the mass ratio of the components of the target titanium-based high-entropy alloy wire, select a corresponding number of Ti wires with corresponding proportions of other component wire raw materials; and use commercially available cleaning agents to ultrasonically clean the wire raw materials to obtain surface-cleaned wire raw materials;

[0047] S2, twisting the raw materials of the wire: the raw materials of the wire in S1 are tightly twisted together by a twisting machine to obtain a primary titanium-based high-entropy composite twisted wire with a multi-helical structure;

[0048] S3, continuous warm drawing of a primary titanium-based high-entropy composite strand: the primary titanium-based high-entropy composite strand prepared in S2 is subjected to continuous multi-pass hot drawing, and the entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire;

[0049] S4, twisting of primary titanium-based high-entropy composite wires: dividing the primary titanium-based high-entropy composite wires prepared in S3 into multiple equal parts along the cross section, and tightly twisting the cut titanium-based high-entropy composite wires together by a twisting machine to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure;

[0050] S5, continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: the secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, and the entire process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire;

[0051] S6, multiple warm drawing of the titanium-based high-entropy composite wire: according to the uniformity of the titanium-based high-entropy composite wire, determine the warm drawing pass, repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a stranding machine to tightly twist the cut titanium-based high-entropy composite wires together, and then perform the next warm drawing until the target pass is completed to obtain the titanium-based high-entropy composite wire;

[0052] S7, continuous extrusion of titanium-based high entropy wire: the titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, and the whole process is automatically transmitted until the target pass is stopped, thereby obtaining a titanium-based high entropy alloy wire;

[0053] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 is subjected to diffusion homogenization treatment in a vacuum furnace, and after cooling in the furnace, a fine titanium-based high entropy alloy wire with uniform composition is obtained.

[0054] In particular, the wire raw material in S1 uses existing brands of wire, or customizes the design and composition; the main component of the target titanium-based high-entropy alloy wire 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%; the diameter of the wire raw material is 1-5mm; the frequency of ultrasonic cleaning is 20-60kHz, and the power is 240-720W.

[0055] In particular, in S2 and S4, the speed of the stranding machine is greater than 500 rpm, and the length of the stranded wire after stranding is 70-90% of the wire raw material; the multi-helix structure is a double helix structure or a structure with more than double helix.

[0056] In particular, the continuous multi-pass hot drawing in S3 and S5 is as follows: first heating to 300-900°C and preheating the drawing die to 300-700°C, and then performing continuous multi-pass drawing, with a drawing rate of 5-30m / min, a deformation amount of 10-20% for each drawing, and a total deformation amount of 20-90% for multi-pass drawing; the yield strength of the primary titanium-based high entropy composite wire is 50-600MPa, and the elongation is 6-30%.

[0057] In particular, S4 is divided into two or more equal parts.

[0058] In particular, the yield strength of the secondary titanium-based high-entropy composite wire in S5 is 50-600MPa and the elongation is 6-30%.

[0059] In particular, the number of continuous warm drawing passes in S6 is 2-10 times, the yield strength of the titanium-based high-entropy composite wire is 50-600 MPa, and the elongation is 6-30%.

[0060] In particular, the extrusion rate of continuous drawing extrusion in S7 is 1-20m / min, the wire drawing machine temperature is 600-1200℃, the extrusion die diameter is 0.8-5mm and the diameter decreases by 0.2-1mm each time, the extrusion target pass matches the titanium-based high-entropy pre-alloyed wire diameter, the extrusion die diameter and the diameter reduction per pass, and the yield strength of the titanium-based high-entropy alloy wire is 800-2500MPa, and the elongation is 3-15%.

[0061] In particular, the temperature of the diffusion homogenization treatment in S8 is 800-1300°C, the holding time is 60-120 min, and the vacuum degree is 10 -1 ~10 -3 Pa, the yield strength of uniformly composed fine titanium-based high-entropy alloy wire is 800-2600MPa, and the elongation is 3-10%.

[0062] In particular, the preparation method described in S1-S8 is not only applicable to titanium-based high entropy alloys, but also to the preparation of other high entropy alloy wires.

[0063] Example 1

[0064] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the titanium-based high-entropy alloy wire has a component content mass ratio of Ti 35 Ni 25 Fe 10 Hf 10 Nb 20 The preparation method of the fine titanium-based high entropy alloy wire comprises the following steps:

[0065] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, two Ti wires with a diameter of 2 mm and other wires of corresponding proportions are selected as wire raw materials; and the wire raw materials are ultrasonically cleaned with commercially available cleaning agents, and the frequency of ultrasonic cleaning is 40 kHz and the power is 360 W to obtain a wire raw material with a clean surface;

[0066] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 1000rmp, and the length of the twisted wire after twisting is 75% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a double helix structure;

[0067] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 470°C, and then continuously drawn in multiple passes, with a drawing rate of 12m / min, a deformation amount of 13% for each drawing, and a total deformation amount of 65% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 320MPa, and the elongation is 15%;

[0068] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into two equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 1000rmp, and the length of the twisted wires after twisting is 75% of one half of the primary titanium-based high-entropy composite wires, to obtain a secondary titanium-based high-entropy composite twisted wire with a double helix structure;

[0069] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 530°C and the wire drawing die is preheated to 500°C, and then continuously drawn in multiple passes, with a drawing rate of 16m / min, a deformation amount of 16% per drawing, and a total deformation amount of 75% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 430MPa, and the elongation is 11%;

[0070] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire. The number of continuous warm drawing passes is 2 times, and there is no need to repeat S4-S5;

[0071] S7, continuous extrusion of titanium-based high entropy wire: The secondary titanium-based high entropy composite wire prepared in S5 is continuously drawn and extruded through a continuous wire drawing machine, the extrusion rate of the continuous drawing and extrusion is 8m / min, the temperature of the wire drawing machine is 850°C, the diameter of the extrusion die is 4mm and the diameter decreases by 0.5mm each time, the extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the extrusion die diameter and the diameter reduction amount of each pass, the whole process is automatically transmitted until the target pass stops, and the titanium-based high entropy alloy wire is obtained; the yield strength of the titanium-based high entropy alloy wire is 880MPa, and the elongation is 5%;

[0072] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 800°C, the holding time was 80 min, and the vacuum degree was 10 -1 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the yield strength of the fine titanium-based high-entropy alloy wire with uniform composition was 1028MPa, and the elongation was 3%.

[0073] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 1 mm, uniform composition and organizational morphology, dense structure, smooth surface, no defects such as oxidation, cracking, and pores, and no broken wire during the preparation process.

[0074] Example 2

[0075] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the mass ratio of the components of the titanium-based high-entropy alloy wire is TiAlFeMgZn; the method for preparing the fine titanium-based high-entropy alloy wire comprises the following steps:

[0076] S1. Selection and processing of raw materials for wire: According to the mass ratio of the components of the target titanium-based high-entropy alloy wire, three Ti wires with a diameter of 3 mm and other component wires in corresponding proportions are selected as wire raw materials; and the wire raw materials are ultrasonically cleaned using commercially available cleaning agents, with the frequency of ultrasonic cleaning being 60 kHz and the power being 720 W to obtain wire raw materials with clean surfaces;

[0077] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 800 rpm, and the length of the twisted wire after twisting is 80% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a multi-helical structure;

[0078] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 400°C and the wire drawing die is preheated to 380°C, and then continuously drawn in multiple passes, with a drawing rate of 20m / min, a deformation amount of 18% for each drawing, and a total deformation amount of 80% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 280MPa, and the elongation is 12%;

[0079] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into three equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 800 rpm, and the length of the twisted wires after twisting is 80% of one third of the primary titanium-based high-entropy composite wires, to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure;

[0080] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 430°C, and then continuously drawn in multiple passes, with a drawing rate of 25m / min, a deformation amount of 20% for each drawing, and a total deformation amount of 75% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 320MPa, and the elongation is 10%;

[0081] S6. Multiple warm drawing of titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire, and the continuous warm drawing passes are 3 times. Repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a stranding machine to tightly twist the cut titanium-based high-entropy composite wires together before the next warm drawing. After the 3 times are completed, the titanium-based high-entropy composite wire is obtained. The yield strength of the titanium-based high-entropy composite wire is 410 MPa, and the elongation is 7%;

[0082] S7, continuous extrusion of titanium-based high entropy wire: The titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, the extrusion rate of the continuous drawing and extrusion is 15m / min, the temperature of the wire drawing machine is 1000°C, the diameter of the extrusion die is 5mm and the diameter decreases by 0.2mm each time, the extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the diameter of the extrusion die and the diameter reduction of each pass, the whole process is automatically transmitted until the target pass stops, and the titanium-based high entropy alloy wire is obtained; the yield strength of the titanium-based high entropy alloy wire is 907MPa, and the elongation is 5.5%;

[0083] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 900°C, the holding time was 80 min, and the vacuum degree was 10 -2 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition is obtained; the fine titanium-based high-entropy alloy wire with uniform composition has a yield strength of 1000MPa and an elongation of 4.8%.

[0084] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 2 mm, uniform composition and organizational morphology, dense structure, smooth surface, no defects such as oxidation, cracking, and pores, and no broken wire during the preparation process.

[0085] Comparative Example 1

[0086] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the titanium-based high-entropy alloy wire has a component content mass ratio of Ti 35 Ni 25 Fe 10 Hf 10 Nb20 The preparation method of the fine titanium-based high entropy alloy wire comprises the following steps:

[0087] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, two Ti wires with a diameter of 2 mm and other wires of corresponding proportions are selected as wire raw materials; and the wire raw materials are ultrasonically cleaned with commercially available cleaning agents, and the frequency of ultrasonic cleaning is 40 kHz and the power is 360 W to obtain a wire raw material with a clean surface;

[0088] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 1000rmp, and the length of the twisted wire after twisting is 75% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a double helix structure;

[0089] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 470°C, and then continuously drawn in multiple passes, with a drawing rate of 12m / min, a deformation amount of 13% for each drawing, and a total deformation amount of 65% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 320MPa, and the elongation is 8%;

[0090] S4, continuous extrusion of titanium-based high entropy wire: The secondary titanium-based high entropy composite wire prepared in S5 is continuously drawn and extruded through a continuous wire drawing machine. The extrusion rate of the continuous drawing and extrusion is 8m / min, the temperature of the wire drawing machine is 850°C, the diameter of the extrusion die is 4mm and the diameter decreases by 0.5mm each time. The extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the extrusion die diameter and the diameter reduction of each pass. The whole process is automatically transmitted until the target pass stops to obtain a titanium-based high entropy alloy wire. The yield strength of the titanium-based high entropy alloy wire is 807MPa and the elongation is 3.5%;

[0091] S5. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 800°C, the holding time was 80 min, and the vacuum degree was 10 -1 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the fine titanium-based high-entropy alloy wire with uniform composition had a yield strength of 933 MPa and an elongation of 1.3%.

[0092] The diameter of the fine titanium-based high-entropy alloy wire obtained in this comparative example is 1 mm. Since the continuous warm drawing pass is only once, the wire components are mixed unevenly, and the fine titanium-based high-entropy alloy wire obtained has the problem of uneven composition and organizational morphology.

[0093] Comparative Example 2

[0094] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the mass ratio of the components of the titanium-based high-entropy alloy wire is TiAlFeMgZn; the method for preparing the fine titanium-based high-entropy alloy wire comprises the following steps:

[0095] S1. Selection and processing of raw materials for wire: According to the mass ratio of the components of the target titanium-based high-entropy alloy wire, three Ti wires with a diameter of 3 mm and other component wires in corresponding proportions are selected as wire raw materials; and the wire raw materials are ultrasonically cleaned using commercially available cleaning agents, with the frequency of ultrasonic cleaning being 60 kHz and the power being 720 W to obtain wire raw materials with clean surfaces;

[0096] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 800 rpm, and the length of the twisted wire after twisting is 80% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a multi-helical structure;

[0097] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 400°C and the wire drawing die is preheated to 380°C, and then continuously drawn in multiple passes, with a drawing rate of 20m / min, a deformation amount of 18% for each drawing, and a total deformation amount of 80% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 280MPa, and the elongation is 12%;

[0098] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into three equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 800 rpm, and the length of the twisted wires after twisting is 80% of one third of the primary titanium-based high-entropy composite wires, to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure;

[0099] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 430°C, and then continuously drawn in multiple passes, with a drawing rate of 25m / min, a deformation amount of 20% for each drawing, and a total deformation amount of 75% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 320MPa, and the elongation is 10%;

[0100] S6. Multiple warm drawing of titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire, and the continuous warm drawing passes are 3 times. Repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a twisting machine to tightly twist the cut titanium-based high-entropy composite wires together before performing the next warm drawing. Repeat the process until the third time to obtain the titanium-based high-entropy composite wire. The yield strength of the titanium-based high-entropy composite wire is 410 MPa, and the elongation is 7%.

[0101] S7, continuous extrusion of titanium-based high entropy wire: The titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, the extrusion rate of the continuous drawing and extrusion is 10m / min, the temperature of the wire drawing machine is 300°C, the diameter of the extrusion die is 5mm and the diameter decreases by 0.2mm each time, the extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the diameter of the extrusion die and the diameter reduction of each pass, the whole process is automatically transmitted until the target pass stops, and the titanium-based high entropy alloy wire is obtained; the yield strength of the titanium-based high entropy alloy wire is 787MPa, and the elongation is 4.2%;

[0102] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 500°C, the holding time was 80 min, and the vacuum degree was 10 -2 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the fine titanium-based high-entropy alloy wire with uniform composition had a yield strength of 801 MPa and an elongation of 0.5%.

[0103] The diameter of the fine titanium-based high-entropy alloy wire obtained in this comparative example is 2 mm, but due to the low temperature of continuous extrusion and diffusion homogenization annealing, the prepared fine titanium-based high-entropy alloy wire has problems such as uneven composition and organizational morphology, and rough surface. In addition, wire breakage and cracking occur during the extrusion process, and the performance of the obtained titanium-based high-entropy alloy wire is poor.

[0104] In summary, by comparing the examples with the comparative examples, it can be found that the setting of the continuous warm drawing pass, continuous extrusion parameters, and diffusion homogenization parameters will affect the uniformity of the final fine titanium-based high-entropy alloy wire. Inappropriate parameter settings may also lead to wire breakage, cracking, oxidation and other problems during the wire preparation process. Therefore, in the actual operation process, it is necessary to combine the target titanium-based high-entropy alloy wire performance and reasonably set each parameter to obtain high-quality titanium-based high-entropy alloy wire with uniform composition and organizational morphology, dense structure, smooth surface, and no defects such as oxidation, cracking, and pores.

[0105] Example 3

[0106] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the mass ratio of the titanium-based high-entropy alloy wire is TiAlNbVZr 0.5The preparation method of the fine titanium-based high entropy alloy wire comprises the following steps:

[0107] 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 wires of corresponding proportions as raw materials for wire; and use commercially available cleaning agents to ultrasonically clean the raw materials for wire, with the frequency of ultrasonic cleaning being 20 kHz and the power being 240 W to obtain raw materials for wire with clean surfaces;

[0108] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 500 rpm, and the length of the twisted wire after twisting is 85% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a multi-helical structure;

[0109] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 750°C and the wire drawing die is preheated to 300°C, and then continuously drawn in multiple passes, with a drawing rate of 7m / min, a deformation of 10% each time, and a total deformation of 62% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 401 MPa, and the elongation is 10%;

[0110] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into four equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 1500rmp, and the length of the twisted wires after twisting is 70% of one quarter of the primary titanium-based high-entropy composite wires, so as to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure;

[0111] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 800°C and the wire drawing die is preheated to 480°C, and then continuously drawn in multiple passes, with a drawing rate of 9m / min, a deformation amount of 13% per drawing, and a total deformation amount of 70% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 443MPa, and the elongation is 8.8%;

[0112] S6. Multiple warm drawing of titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire, and the continuous warm drawing passes are 6 times. Repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a stranding machine to tightly twist the cut titanium-based high-entropy composite wires together before performing the next warm drawing until the target pass is completed to obtain the titanium-based high-entropy composite wire; the yield strength of the titanium-based high-entropy composite wire is 567MPa, and the elongation is 6.3%;

[0113] S7, continuous extrusion of titanium-based high-entropy wire: The titanium-based high-entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, the extrusion rate of the continuous drawing and extrusion is 6m / min, the temperature of the wire drawing machine is 750°C, the diameter of the extrusion die is 3mm and the diameter decreases by 0.2mm each time, the extrusion target pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the diameter of the extrusion die and the diameter reduction of each pass, the whole process is automatically transmitted until the target pass stops, and the titanium-based high-entropy alloy wire is obtained; the yield strength of the titanium-based high-entropy alloy wire is 898MPa, and the elongation is 4.7%;

[0114] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 960°C, the holding time was 110 min, and the vacuum degree was 10 -3 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the yield strength of the fine titanium-based high-entropy alloy wire with uniform composition was 1070MPa, and the elongation was 4.4%.

[0115] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 0.8 mm, uniform composition and organizational morphology, dense structure, smooth surface, no defects such as oxidation, cracking, and pores, and no broken wires during the preparation process.

[0116] Example 4

[0117] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the mass ratio of the components of the titanium-based high-entropy alloy wire is TiAlFeMgZn; the method for preparing the fine titanium-based high-entropy alloy wire comprises the following steps:

[0118] S1. Selection and processing of raw materials for wire: According to the mass ratio of the target titanium-based high-entropy alloy wire, two Ti wires with a diameter of 2 mm and other wires of corresponding proportions are selected as wire raw materials; and the wire raw materials are ultrasonically cleaned with commercially available cleaning agents, and the frequency of ultrasonic cleaning is 40 kHz and the power is 360 W to obtain a wire raw material with a clean surface;

[0119] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 1000rmp, and the length of the twisted wire after twisting is 75% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a double helix structure;

[0120] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 480°C, and then continuously drawn in multiple passes, with a drawing rate of 14m / min, a deformation amount of 15% for each drawing, and a total deformation amount of 65% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 365MPa, and the elongation is 10%;

[0121] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into two equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 1000 rmp, and the length of the twisted wires after twisting is 75% of one half of the primary titanium-based high-entropy composite wires, to obtain a secondary titanium-based high-entropy composite twisted wire with a double helix structure;

[0122] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 480°C, and then continuously drawn in multiple passes, with a drawing rate of 16m / min, a deformation amount of 15% each time, and a total deformation amount of 75% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 417MPa, and the elongation is 6.8%;

[0123] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire. The number of continuous warm drawing passes is 2 times, and there is no need to repeat S4-S5;

[0124] S7, continuous extrusion of titanium-based high entropy wire: The secondary titanium-based high entropy composite wire prepared in S5 is continuously drawn and extruded through a continuous wire drawing machine. The extrusion rate of the continuous drawing and extrusion is 8m / min, the temperature of the wire drawing machine is 850°C, the diameter of the extrusion die is 4mm and the diameter decreases by 0.5mm each time. The extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the diameter of the extrusion die and the diameter reduction of each pass. The whole process is automatically transmitted until the target pass stops to obtain a titanium-based high entropy alloy wire. The yield strength of the titanium-based high entropy alloy wire is 858 MPa and the elongation is 5.6%;

[0125] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 800°C, the holding time was 80 min, and the vacuum degree was 10 -1 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the yield strength of the fine titanium-based high-entropy alloy wire with uniform composition was 936MPa, and the elongation was 4.5%.

[0126] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 1 mm, uniform composition and organizational morphology, dense structure, smooth surface, no defects such as oxidation, cracking, and pores, and no broken wire during the preparation process.

[0127] Example 5

[0128] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the titanium-based high-entropy alloy wire has a component content mass ratio of Ti 35 Ni 25 Fe 10 Hf 10 Nb 20 The preparation method of the fine titanium-based high entropy alloy wire comprises the following steps:

[0129] 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 wires of corresponding proportions as raw materials for wire; and use commercially available cleaning agents to ultrasonically clean the raw materials for wire, with the frequency of ultrasonic cleaning being 20 kHz and the power being 240 W to obtain raw materials for wire with clean surfaces;

[0130] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 500 rpm, and the length of the twisted wire after twisting is 85% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a multi-helical structure;

[0131] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 550°C and the wire drawing die is preheated to 300°C, and then continuously drawn in multiple passes, with a drawing rate of 8m / min, a deformation amount of 10% for each drawing, and a total deformation amount of 63% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 294MPa, and the elongation is 16.2%;

[0132] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into four equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 1500rmp, and the length of the twisted wires after twisting is 70% of one quarter of the primary titanium-based high-entropy composite wires, so as to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure;

[0133] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 600°C and the wire drawing die is preheated to 480°C, and then continuously drawn in multiple passes, with a drawing rate of 10m / min, a deformation amount of 13% each time, and a total deformation amount of 70% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 401MPa, and the elongation is 12.3%;

[0134] S6. Multiple warm drawing of titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire, and the continuous warm drawing passes are 4 times. Repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a stranding machine to tightly twist the cut titanium-based high-entropy composite wires together before performing the next warm drawing until the target pass is completed to obtain the titanium-based high-entropy composite wire; the yield strength of the titanium-based high-entropy composite wire is 557MPa, and the elongation is 7.1%;

[0135] S7, continuous extrusion of titanium-based high entropy wire: The titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, the extrusion rate of the continuous drawing and extrusion is 6m / min, the temperature of the wire drawing machine is 750°C, the diameter of the extrusion die is 3mm and the diameter decreases by 0.2mm each time, the extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the diameter of the extrusion die and the diameter reduction of each pass, the whole process is automatically transmitted until the target pass stops, and the titanium-based high entropy alloy wire is obtained; the tensile strength of the titanium-based high entropy alloy wire is a yield strength of 895MPa, and the elongation is 5.7%;

[0136] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 960°C, the holding time was 110 min, and the vacuum degree was 10 -3 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the yield strength of the fine titanium-based high-entropy alloy wire with uniform composition was 1053MPa, and the elongation was 4.6%.

[0137] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 0.8 mm, uniform composition and organizational morphology, dense structure, smooth surface, no defects such as oxidation, cracking, and pores, and no broken wires during the preparation process.

[0138] Example 6

[0139] A method for preparing a fine titanium-based high-entropy alloy wire, wherein the mass ratio of the titanium-based high-entropy alloy wire is TiAlNbVZr 0.5 The preparation method of the fine titanium-based high entropy alloy wire comprises the following steps:

[0140] S1. Selection and processing of raw materials for wire: According to the mass ratio of the components of the target titanium-based high-entropy alloy wire, three Ti wires with a diameter of 3 mm and other component wires in corresponding proportions are selected as wire raw materials; and the wire raw materials are ultrasonically cleaned using commercially available cleaning agents, with the frequency of ultrasonic cleaning being 60 kHz and the power being 720 W to obtain wire raw materials with clean surfaces;

[0141] S2, twisting of raw materials of wire: the raw materials of wire in S1 are tightly twisted together by a twisting machine, the speed of the twisting machine is 800 rpm, and the length of the twisted wire after twisting is 80% of the raw materials of wire, so as to obtain a primary titanium-based high entropy composite twisted wire with a multi-helical structure;

[0142] S3, continuous warm drawing of primary titanium-based high-entropy composite stranded wire: The primary titanium-based high-entropy composite stranded wire prepared in S2 is subjected to continuous multi-pass hot drawing, first heated to 450°C and the wire drawing die is preheated to 380°C, and then continuously drawn in multiple passes, with a drawing rate of 20m / min, a deformation of 16% each time, and a total deformation of 80% for multiple drawing passes; the whole process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the yield strength of the primary titanium-based high-entropy composite wire is 427MPa, and the elongation is 9.5%;

[0143] S4, twisting of primary titanium-based high-entropy composite wires: the primary titanium-based high-entropy composite wires prepared in S3 are divided into two equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine, the twisting machine speed is 800rmp, and the length of the twisted wires after twisting is 80% of half of the primary titanium-based high-entropy composite wires, to obtain a secondary titanium-based high-entropy composite twisted wire with a double helix structure;

[0144] S5. Continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: The secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, first heated to 500°C and the wire drawing die is preheated to 420°C, and then continuously drawn in multiple passes, with a drawing rate of 25m / min, a deformation amount of 20% for each drawing, and a total deformation amount of 75% for multiple drawing passes; the whole process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; the yield strength of the secondary titanium-based high-entropy composite wire is 439MPa, and the elongation is 9%;

[0145] S6. Multiple warm drawing of titanium-based high-entropy composite wire: Determine the number of warm drawing passes according to the uniformity of the titanium-based high-entropy composite wire, and the continuous warm drawing passes are 3 times. Repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a twisting machine to tightly twist the cut titanium-based high-entropy composite wires together before performing the next warm drawing. Repeat the process until the third time to obtain the titanium-based high-entropy composite wire. The yield strength of the titanium-based high-entropy composite wire is 468 MPa, and the elongation is 8.3%.

[0146] S7, continuous extrusion of titanium-based high entropy wire: The titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, the extrusion rate of the continuous drawing and extrusion is 16m / min, the temperature of the wire drawing machine is 1000°C, the diameter of the extrusion die is 5mm and the diameter decreases by 0.2mm each time, the extrusion target pass is matched with the diameter of the titanium-based high entropy pre-alloyed wire, the extrusion die diameter and the diameter reduction of each pass, the whole process is automatically transmitted until the target pass stops, and the titanium-based high entropy alloy wire is obtained; the yield strength of the titanium-based high entropy alloy wire is 954MPa, and the elongation is 7%;

[0147] S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 was subjected to diffusion homogenization treatment in a vacuum furnace. The temperature of the diffusion homogenization treatment was 900°C, the holding time was 80 min, and the vacuum degree was 10 -2 Pa, and after cooling in the furnace, a fine titanium-based high-entropy alloy wire with uniform composition was obtained; the yield strength of the fine titanium-based high-entropy alloy wire with uniform composition was 1068MPa, and the elongation was 6.4%.

[0148] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 3 mm, uniform composition and organizational morphology, dense structure, smooth surface, no defects such as oxidation, cracking, and pores, and no broken wire during the preparation process.

[0149] The above scheme, the present invention proposes a method for preparing a fine titanium-based high-entropy alloy wire, which can solve the technical bottleneck of preparing titanium-based high-entropy alloy wire by drawing due to poor room temperature plasticity of titanium-based high-entropy alloy, and further solve the problem of limited application of titanium-based high-entropy alloy wire. The traditional process of single-wire additive manufacturing technology using titanium-based high-entropy composite wire as raw material has problems such as complex wire preparation and uneven finished product components. The fine titanium-based high-entropy alloy wire obtained by the present invention has uniform composition and organization, dense structure, smooth surface, and no defects such as oxidation, cracking, and pores. The performance of each part of the fused wire additive manufacturing product using this as raw material is stable and consistent, providing high-quality raw materials for expanding the application of titanium-based high-entropy alloys.

[0150] The present invention is not limited to the preparation of titanium-based high-entropy alloy wires, but is also applicable to the preparation of other high-entropy alloy wires, and has no special restrictions on raw material grades, components, etc., and has a wide range of selectable raw materials. Additive manufacturing can prepare a large number of complex shapes and titanium-containing alloys with different components, which is conducive to large-scale industrial production and commercial promotion and application.

[0151] The present invention utilizes the good room temperature plasticity of a single metal wire or alloy wire, adopts the alloy single metal wire 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 alloy single metal to be compounded can be achieved at a relatively low temperature. The operation is convenient and the cost is low, and it can be applied to the fused additive manufacturing of complex-shaped titanium-based high-entropy alloy wires with different performance requirements.

[0152] Compared with the cold drawing method, the continuous warm drawing method adopted in the present invention can improve the plastic deformation ability of the titanium-based high-entropy alloy wire during the drawing process, reduce the deformation resistance, ensure that no cracking, wire breakage, etc. occur during the deformation process, and can effectively reduce the number of drawing passes and reduce the internal stress of the prepared titanium-based high-entropy alloy wire, so that the preparation efficiency of the titanium-based high-entropy alloy wire is significantly improved.

[0153] The present invention can completely alloy the pre-alloyed titanium-based high-entropy composite wire by continuously drawing and extruding it at a relatively low temperature with a gradually decreasing diameter of the extrusion die, thereby avoiding a high-temperature melting process and solving the technical bottleneck of titanium-based high-entropy alloys being difficult to prepare alloy wires due to their brittleness at room temperature, and effectively reducing the volatilization of low-melting-point elements during the preparation of the titanium-based high-entropy alloy wires.

[0154] The diffusion homogenization annealing treatment adopted in the present invention can make the heterogeneous elements in the titanium-based high-entropy alloy wire further diffuse with each other, ensure that the obtained titanium-based high-entropy alloy wire has a completely uniform distribution of components, increase the uniformity of the distribution of components after the wire is melted in the additive manufacturing process, and improve the yield of printed products.

[0155] The automatic conveying device adopted in the present invention can greatly improve the production efficiency of titanium-based high-entropy alloy wire, effectively reduce its production cost, eliminate manual interference in alloy wire preparation, and further improve the production quality of titanium-based high-entropy alloy wire.

[0156] The present invention can make adaptive adjustments in the selection of passes in the preparation and extrusion process of the titanium-based high-entropy composite wire according to the component ratio and diameter of the target titanium-based high-entropy alloy wire, to ensure that the components of the titanium-based high-entropy alloy wires with different compositions are evenly distributed and the diameters meet the requirements, and the titanium-based high-entropy alloy wires all have high quality and high performance.

[0157] In summary, compared with other traditional methods, the method of the present invention can directly prepare titanium-based high-entropy alloy wires with uniform composition distribution at a lower temperature through multiple wire twisting, multiple continuous hot drawing and final diffusion homogenization annealing, effectively avoiding the high-temperature melting process. The composition and diameter can be designed according to the requirements of the target titanium-based high-entropy alloy wire for the preparation of titanium-based high-entropy composite wires and the passes in the extrusion process. It has high flexibility, simple operation, wide applicability and low cost, and is very suitable for large-scale industrial production.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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 a fine titanium-based high-entropy alloy wire, characterized in that: The preparation method of the micro-titanium-based high-entropy alloy wire comprises the following steps: S1. Selection and processing of raw materials for wire: According to the mass ratio of the components of the target titanium-based high-entropy alloy wire, select corresponding proportions of other component wire raw materials of a corresponding number of Ti wires; The silk material raw materials are ultrasonically cleaned by using commercially available cleaning agents to obtain silk material raw materials with clean surfaces; S2, twisting the raw materials of the wire: the raw materials of the wire in S1 are tightly twisted together by a twisting machine to obtain a primary titanium-based high-entropy composite twisted wire with a multi-helical structure; S3, continuous warm drawing of a primary titanium-based high-entropy composite strand: the primary titanium-based high-entropy composite strand prepared in S2 is subjected to continuous multi-pass hot drawing, and the entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; S4, twisting of primary titanium-based high-entropy composite wires: dividing the primary titanium-based high-entropy composite wires prepared in S3 into multiple equal parts along the cross section, and tightly twisting the cut titanium-based high-entropy composite wires together by a twisting machine to obtain secondary titanium-based high-entropy composite twisted wires with a multi-helical structure; S5, continuous warm drawing of secondary titanium-based high-entropy composite stranded wire: the secondary titanium-based high-entropy composite stranded wire prepared in S4 is subjected to continuous multi-pass hot drawing, and the entire process is automatically transmitted to obtain a secondary titanium-based high-entropy composite wire; S6, multiple warm drawing of the titanium-based high-entropy composite wire: according to the uniformity of the titanium-based high-entropy composite wire, determine the warm drawing pass, repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, and use a stranding machine to tightly twist the cut titanium-based high-entropy composite wires together, and then perform the next warm drawing until the target pass is completed to obtain the titanium-based high-entropy composite wire; S7, continuous extrusion of titanium-based high entropy wire: the titanium-based high entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, and the whole process is automatically transmitted until the target pass is stopped, thereby obtaining a titanium-based high entropy alloy wire; S8. Diffusion homogenization of titanium-based high entropy alloy wire: The titanium-based high entropy alloy wire prepared in S7 is subjected to diffusion homogenization treatment in a vacuum furnace, and after cooling in the furnace, a fine titanium-based high entropy alloy wire with uniform composition is obtained.

2. The method for preparing a fine titanium-based high entropy alloy wire according to claim 1, characterized in that: The wire material in S1 uses existing brands of wire, or customizes the design and composition; the main component of the target titanium-based high entropy alloy wire 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%; the diameter of the wire raw material is 1-5mm; the frequency of ultrasonic cleaning is 20-60kHz, and the power is 240-720W.

3. The method for preparing a fine titanium-based high-entropy alloy wire according to claim 1, characterized in that: In S2 and S4, the speed of the stranding machine is greater than 500 rpm, and the length of the stranded wire after stranding is 70-90% of the wire raw material; the multi-helix structure is a double helix structure or a structure above a double helix.

4. The method for preparing a fine titanium-based high-entropy alloy wire according to claim 1, characterized in that: The continuous multi-pass hot drawing in S3 and S5 is specifically as follows: first heating to 300-900°C and preheating the drawing die to 300-700°C, and then performing continuous multi-pass drawing, with a drawing rate of 5-30m / min, a deformation amount of 10-20% for each drawing, and a total deformation amount of 20-90% for multi-pass drawing; the yield strength of the primary titanium-based high entropy composite wire is 50-600MPa, and the elongation is 6-30%.

5. The method for preparing a fine titanium-based high-entropy alloy wire according to claim 1, characterized in that: S4 can be divided into two or more equal parts.

6. The method for preparing a fine titanium-based high entropy alloy wire according to claim 1, characterized in that: The yield strength of the secondary titanium-based high-entropy composite wire in S5 is 50-600MPa and the elongation is 6-30%.

7. The method for preparing a fine titanium-based high entropy alloy wire according to claim 1, characterized in that: The continuous warm drawing passes in S6 are 2-10 times, the yield strength of the titanium-based high-entropy composite wire is 50-600MPa, and the elongation is 6-30%.

8. The method for preparing a fine titanium-based high-entropy alloy wire according to claim 1, characterized in that: The extrusion rate of continuous drawing extrusion in S7 is 1-20m / min, the temperature of the wire drawing machine is 600-1200℃, the diameter of the extrusion die is 0.8-5mm and the diameter decreases by 0.2-1mm each time, the extrusion target pass matches the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter and the diameter reduction of each pass, and the yield strength of the titanium-based high-entropy alloy wire is 800-2500MPa, and the elongation is 3-15%.

9. The method for preparing a fine titanium-based high entropy alloy wire according to claim 1, characterized in that: The temperature of diffusion homogenization treatment in S8 is 800-1300℃, the holding time is 60-120min, and the vacuum degree is 10 -1 ~10 -3 Pa, the yield strength of uniformly composed fine titanium-based high-entropy alloy wire is 800-2600MPa, and the elongation is 3-10%.

10. The method for preparing a fine titanium-based high-entropy alloy wire according to claim 1, characterized in that: The preparation methods described in S1-S8 are not only applicable to titanium-based high entropy alloys, but also to the preparation of other high entropy alloy wires.

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