A method for preparing fine titanium-based high-entropy alloy wire

Abstract

The present invention provides a method for preparing fine titanium-based high-entropy alloy wire, which relates to the technical field of titanium-based high-entropy alloy preparation. The preparation method includes the following steps: selecting and processing raw materials for the wires; twisting the raw materials for the wires; continuously warm-drawing a primary titanium-based high-entropy composite strand; twisting a primary titanium-based high-entropy composite wire; continuously warm-drawing a secondary titanium-based high-entropy composite strand; multiple warm-drawings of the titanium-based high-entropy composite wire; continuous extrusion of the titanium-based high-entropy wire; and diffusion homogenization of the titanium-based high-entropy alloy wire. The present invention, through multiple twistings, multiple continuous hot-drawings combined with a final diffusion homogenization annealing, can directly prepare titanium-based high-entropy alloy wire with uniform composition distribution at a relatively low temperature, effectively avoiding a high-temperature melting process. The composition and 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 in the preparation and extrusion processes. The method is highly flexible, simple to operate, widely applicable, and low-cost, making it very suitable for large-scale industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of titanium-based high-entropy alloy preparation, and in particular to a method for preparing a fine titanium-based high-entropy alloy wire. Background Art

[0002] High-entropy alloys (HEAs) are a new type of alloy composed of five or more main components mixed in equiatomic or near-equiatomic ratios. Their four specific effects (high entropy effect, lattice distortion effect, delayed diffusion effect, and cocktail effect) give HEAs numerous exceptional properties, including high strength, high hardness, excellent thermal stability, and superior corrosion resistance. The addition of titanium to HEAs, forming a titanium-based HEA, effectively reduces alloy density and increases hardness and strength. This holds important implications for the development of high-temperature structural materials for next-generation high-thrust-to-weight and high-power-to-weight aircraft engines. In recent years, with the continuous development of large aircraft, aeroengines, and new-generation launch vehicles, the structures of aerospace components have become increasingly integrated and complex. Traditional methods of casting, forging, and machining are no longer sufficient to efficiently and cost-effectively manufacture these complex structures.

[0003] Currently, additive manufacturing of titanium-based high-entropy alloys has become a key research area within the scientific community. Based on a bottom-up, layer-by-layer additive manufacturing process, additive manufacturing offers excellent capabilities for complex molding. Depending on the feeding method, it can be categorized into three types: powder laying, powder feeding, and wire feeding. However, powder additive manufacturing requires high-quality raw materials, resulting in slow deposition rates during the preparation process. Furthermore, due to limitations in existing powder production technology, powders are expensive. In contrast, fused filament additive manufacturing, which uses wire as a raw material, offers fast deposition rates, low production costs, and greater molding freedom.

[0004] Therefore, additive manufacturing of titanium-based high-entropy alloys has shown great application prospects in the aerospace field. Among them, fused filament additive manufacturing of titanium-based high-entropy alloys can break through shape constraints while having the advantages of high forming efficiency and low production cost, and is 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, they are difficult to draw. Existing titanium-based high-entropy alloy fused filament additive manufacturing mostly uses dual-wire or multi-wire feeding methods, but these methods have complex operating mechanisms and high equipment costs. Even single-wire feeding methods use titanium-based high-entropy composite wire as the raw material, which has problems such as complex wire preparation, uneven composition distribution, and high cost. Therefore, it is urgent to invent a method for preparing titanium-based high-entropy alloy wire to meet the needs of high-quality titanium-based high-entropy alloy fused filament additive manufacturing.

[0006] For example, Chinese patent CN117127081A discloses a high-entropy alloy wire for additive manufacturing and a method for preparing the same. The wire uses specific atomic percentages of Fe, Co, Cr, Ni, Al, and Ti metal elements as raw materials, and includes steps such as raw material preparation, smelting, forging, hot rolling, drawing, and adjustment. This method uses traditional processes to prepare high-entropy alloy wire. Although the prepared high-entropy alloy rod undergoes repeated smelting, its composition distribution is uneven. In particular, the subsequent hot rolling and drawing exacerbate this 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 loaded into a metal seamless tube and then sealed. The wire is obtained by rotary forging more than 10 times. 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 components.

[0008] Chinese patent CN114032435A discloses a high-entropy alloy micron wire for antioxidant additive manufacturing and its synthesis method. Obviously, this synthesis method requires a special device structure to be implemented. The vacuum suction cast rod is affected by the process, and its composition distribution in various parts of the rod is not uniform. The subsequent vacuum melting copper roller 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 during the preparation 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 the uneven distribution of components of titanium-based high entropy alloy raw wires, component segregation, and poor room temperature plasticity, which make it impossible to draw and form, and 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 components 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 solution is as follows:

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

[0011] S1. Selection and processing of wire raw materials: According to the mass ratio of the target titanium-based high-entropy alloy wire, select a corresponding number of Ti wires and other component wire raw materials in corresponding proportions; and ultrasonically clean the wire raw materials using commercially available cleaning agents 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 stranded 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 the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is divided into multiple equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine to obtain a secondary titanium-based high-entropy composite twisted wire with a multi-helical structure;

[0015] S5. Continuous warm drawing of secondary titanium-based high-entropy composite strands: The secondary titanium-based high-entropy composite strands prepared in S4 are subjected to continuous multi-pass hot drawing, with the entire process being automatically transmitted to obtain secondary titanium-based high-entropy composite wires;

[0016] 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, repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, 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 number of passes 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 entire 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 can use existing brand wire, or be customized to adjust the 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 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 each drawing of 10-20%, and a total deformation amount of multi-pass drawing of 20-90%; 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 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%.

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

[0026] Optionally, the temperature of the diffusion homogenization treatment in S8 is 800-1300°C, the holding time is 60-120 minutes, and the vacuum degree is 10 -1 ~10 -3 Pa, the yield strength of uniformly composed micro-titanium-based high-entropy alloy wire is 800-2600 MPa, 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 fine titanium-based high-entropy alloy wire, which can solve the technical bottleneck of preparing titanium-based high-entropy alloy wire due to the poor room temperature plasticity of titanium-based high-entropy alloy and the inability to draw and form it, thereby solving the problem of limited application of titanium-based high-entropy alloy wire. Traditional single-filament additive manufacturing technology using titanium-based high-entropy composite wire as raw material has problems such as complex wire preparation and uneven finished product composition. The fine titanium-based high-entropy alloy wire obtained by the present invention has uniform composition and structure, dense structure, smooth surface, and no defects such as oxidation, cracking, and porosity. The performance of various parts of the fused filament additive manufacturing products 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. There are no special restrictions on the raw material brand, composition, etc., and a wide range of raw materials can be selected. Additive manufacturing can prepare a large number of complex shapes and titanium alloys with different compositions, which is conducive to large-scale industrial production and commercial promotion and application.

[0031] The present invention utilizes the good room temperature plasticity of 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 twisting. 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 or wire breakage occurs 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, thereby significantly improving the preparation efficiency of the titanium-based high-entropy alloy wire.

[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 die diameter. This avoids the high-temperature melting process and solves the technical bottleneck of the difficulty in preparing alloy wires due to the brittleness of titanium-based high-entropy alloys at room temperature, and effectively reduces the volatilization of low-melting-point elements during the preparation of titanium-based high-entropy alloy wires.

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

[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, ensuring 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 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 wires for the preparation and extrusion of titanium-based high-entropy composite wires. 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 This 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 an "exemplary" in the present invention should not be interpreted as being preferred or advantageous over other embodiments or designs. Rather, the use of the word "exemplary" is intended to present concepts in a concrete manner. Furthermore, in the embodiments of the present invention, "and / or" can mean both or either of the two.

[0042] In the embodiments of the present invention, "image" and "picture" may sometimes be used interchangeably. It should be noted that, when the distinction between them is not emphasized, the meanings they convey are the same. "of," "corresponding," and "corresponding" may sometimes be used interchangeably. It should be noted that, when the distinction between them is not emphasized, the meanings they convey 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 clearer, 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 wire raw materials: According to the mass ratio of the target titanium-based high-entropy alloy wire, select a corresponding number of Ti wires and other component wire raw materials in corresponding proportions; and ultrasonically clean the wire raw materials using commercially available cleaning agents 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 stranded 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 the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is divided into multiple equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a twisting machine to obtain a secondary titanium-based high-entropy composite twisted wire with a multi-helical structure;

[0050] S5. Continuous warm drawing of secondary titanium-based high-entropy composite strands: The secondary titanium-based high-entropy composite strands prepared in S4 are subjected to continuous multi-pass hot drawing, with the entire process being automatically transmitted to obtain secondary titanium-based high-entropy composite wires;

[0051] 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, repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, 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 number of passes 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 entire 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 material in S1 uses existing brand 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 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, the length of the stranded wire after stranding is 70-90% of the wire raw material; and 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 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 of each drawing of 10-20%, and a total deformation of multi-pass drawing of 20-90%; 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 50-600 MPa 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 1-20 m / min, the wire drawing machine temperature is 600-1200°C, the extrusion die diameter is 0.8-5 mm and the diameter decreases gradually by 0.2-1 mm. The target extrusion passes are matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter and the diameter reduction per pass. The yield strength of the titanium-based high-entropy alloy wire is 800-2500 MPa, and the elongation is 3-15%.

[0061] In particular, the temperature of the 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 micro-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 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 titanium-based high entropy alloy wire is as follows:

[0065] S1. Selection and processing of wire raw materials: Based on 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 were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 40 kHz and a power of 360 W to obtain surface-cleaned wire raw materials;

[0066] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 1000 rpm. The length of the twisted wire is 75% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a double helical structure;

[0067] 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. The strand is first heated to 500°C and the drawing die is preheated to 470°C. Continuous multi-pass drawing is then performed at a drawing rate of 12 m / min. The deformation of each drawing is 13%, and the total deformation of the multi-pass drawing is 65%. The entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The primary titanium-based high-entropy composite wire has a yield strength of 320 MPa and an elongation of 15%.

[0068] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 at a twisting machine speed of 1000 rpm. The length of the twisted wire is 75% of half of the primary titanium-based high-entropy composite wire, thereby obtaining 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 was subjected to continuous multi-pass hot drawing. The wire was first heated to 530°C and the drawing die was preheated to 500°C. Continuous multi-pass drawing was then performed at a drawing rate of 16 m / min. The deformation of each drawing was 16%, and the total deformation of the multi-pass drawing was 75%. The entire process was automatically transmitted to obtain a secondary titanium-based high-entropy composite wire. The yield strength of the secondary titanium-based high-entropy composite wire was 430 MPa and the elongation was 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, 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 8 m / min, the wire drawing machine temperature is 850°C, the extrusion die diameter is 4 mm, and the diameter decreases by 0.5 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped, thereby obtaining a titanium-based high-entropy alloy wire. The yield strength of the titanium-based high-entropy alloy wire is 880 MPa, 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 minutes, 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 1028 MPa and an elongation of 3%.

[0073] The fine titanium-based high-entropy alloy wire obtained in this embodiment has a diameter of 1 mm, uniform composition and microstructure, dense structure, smooth surface, no defects such as oxidation, cracking, and porosity, and no wire breakage 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 wire raw materials: Based on the mass ratio of the target titanium-based high-entropy alloy wire, three Ti wires with a diameter of 3 mm and other wires of corresponding proportions were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 60 kHz and a power of 720 W to obtain surface-cleaned wire raw materials;

[0077] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 800 rpm. The length of the twisted wire is 80% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a multi-helical structure;

[0078] 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. The strand is first heated to 400°C and the drawing die is preheated to 380°C. Continuous multi-pass drawing is then performed at a drawing rate of 20 m / min. The deformation of each drawing is 18%, and the total deformation of the multi-pass drawing is 80%. The entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The primary titanium-based high-entropy composite wire has a yield strength of 280 MPa and an elongation of 12%.

[0079] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 wire is 80% of one-third of the primary titanium-based high-entropy composite wire, thereby obtaining a secondary titanium-based high-entropy composite strand 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. The wire is first heated to 500°C and the drawing die is preheated to 430°C. Continuous multi-pass drawing is then performed at a drawing rate of 25 m / min. The deformation of each drawing is 20%, and the total deformation of the multi-pass drawing is 75%. The entire 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 320 MPa and the elongation is 10%.

[0081] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: The number of warm drawing passes is determined according to the uniformity of the titanium-based high-entropy composite wire. The continuous warm drawing passes are 3 times. S4-S5 are repeated, i.e., the previous titanium-based high-entropy composite wire is divided into multiple equal parts along the cross section. The cut titanium-based high-entropy composite wires are tightly twisted together by a stranding machine, and then the next warm drawing is performed until the third warm drawing is completed 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%.

[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 15 m / min, the wire drawing machine temperature is 1000°C, the extrusion die diameter is 5 mm, and the diameter decreases by 0.2 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped to obtain a titanium-based high-entropy alloy wire. The yield strength of the titanium-based high-entropy alloy wire is 907 MPa, 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 1000 MPa 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 microstructure, dense structure, smooth surface, no defects such as oxidation, cracking, and porosity, and no wire breakage during the preparation process.

[0085] Comparative Example 1

[0086] 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 Ti 35 Ni 25 Fe 10 Hf 10 Nb20 The preparation method of the fine titanium-based high entropy alloy wire is as follows:

[0087] S1. Selection and processing of wire raw materials: Based on 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 were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 40 kHz and a power of 360 W to obtain surface-cleaned wire raw materials;

[0088] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 1000 rpm. The length of the twisted wire is 75% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a double helical structure;

[0089] 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, first heated to 500°C and preheated to 470°C, followed by continuous multi-pass drawing at a drawing rate of 12 m / min. The deformation of each drawing is 13%, and the total deformation of the multi-pass drawing is 65%. The entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The primary titanium-based high-entropy composite wire has a yield strength of 320 MPa and an elongation of 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 8 m / min, the wire drawing machine temperature is 850°C, the extrusion die diameter is 4 mm, and the diameter decreases by 0.5 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped to obtain a titanium-based high-entropy alloy wire. The yield strength of the titanium-based high-entropy alloy wire is 807 MPa, 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 minutes, 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 one time, the various component wires are mixed unevenly, and the obtained fine titanium-based high-entropy alloy wire 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 wire raw materials: Based on the mass ratio of the target titanium-based high-entropy alloy wire, three Ti wires with a diameter of 3 mm and other wires of corresponding proportions were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 60 kHz and a power of 720 W to obtain surface-cleaned wire raw materials;

[0096] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 800 rpm. The length of the twisted wire is 80% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a multi-helical structure;

[0097] 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. The strand is first heated to 400°C and the drawing die is preheated to 380°C. Continuous multi-pass drawing is then performed at a drawing rate of 20 m / min. The deformation of each drawing is 18%, and the total deformation of the multi-pass drawing is 80%. The entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The primary titanium-based high-entropy composite wire has a yield strength of 280 MPa and an elongation of 12%.

[0098] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 wire is 80% of one-third of the primary titanium-based high-entropy composite wire, thereby obtaining a secondary titanium-based high-entropy composite strand 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. The wire is first heated to 500°C and the drawing die is preheated to 430°C. Continuous multi-pass drawing is then performed at a drawing rate of 25 m / min. The deformation of each drawing is 20%, and the total deformation of the multi-pass drawing is 75%. The entire 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 320 MPa and the elongation is 10%.

[0100] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: The number of warm drawing passes is determined according to the uniformity of the titanium-based high-entropy composite wire. The continuous warm drawing passes are 3 times. S4-S5 are repeated, that is, the previous titanium-based high-entropy composite wire is divided into multiple equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together by a stranding machine. Then, the next warm drawing is carried out until the third time is completed 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 10 m / min, the wire drawing machine temperature is 300°C, the extrusion die diameter is 5 mm, and the diameter decreases by 0.2 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped to obtain a titanium-based high-entropy alloy wire. The yield strength of the titanium-based high-entropy alloy wire is 787 MPa, 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 minutes, 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 microstructure, 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 passes, continuous extrusion parameters, and diffusion homogenization parameters will all affect the uniformity of the final fine titanium-based high-entropy alloy wire. Inappropriate parameter settings may also lead to problems such as wire breakage, cracking, and oxidation during the wire preparation process. Therefore, in actual operation, it is necessary to reasonably set each parameter based on the target titanium-based high-entropy alloy wire properties to obtain high-quality titanium-based high-entropy alloy wire with uniform composition and microstructure, dense structure, smooth surface, and no defects such as oxidation, cracking, and porosity.

[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 is as follows:

[0107] S1. Selection and processing of wire raw materials: Based on the mass ratio of the target titanium-based high-entropy alloy wire, four Ti wires with a diameter of 1 mm and other component wires in corresponding proportions were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 20 kHz and a power of 240 W to obtain surface-cleaned wire raw materials;

[0108] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 500 rpm. The length of the twisted wire is 85% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a multi-helical structure;

[0109] S3. Continuous warm drawing of a primary titanium-based high-entropy composite strand: The primary titanium-based high-entropy composite strand prepared in S2 was subjected to continuous multi-pass hot drawing. The strand was first heated to 750°C and the drawing die was preheated to 300°C. Continuous multi-pass drawing was then performed at a drawing rate of 7 m / min. The deformation of each drawing was 10%, and the total deformation of the multi-pass drawing was 62%. The entire process was automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The primary titanium-based high-entropy composite wire had a yield strength of 401 MPa and an elongation of 10%.

[0110] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 at a twisting machine speed of 1500 rpm. The length of the twisted wire is 70% of one-quarter of the primary titanium-based high-entropy composite wire, thereby obtaining a secondary titanium-based high-entropy composite twisted wire 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 was subjected to continuous multi-pass hot drawing. The wire was first heated to 800°C and the drawing die was preheated to 480°C. Continuous multi-pass drawing was then performed at a drawing rate of 9 m / min. The deformation of each drawing was 13%, and the total deformation of the multi-pass drawing was 70%. The entire process was automatically transmitted to obtain a secondary titanium-based high-entropy composite wire. The yield strength of the secondary titanium-based high-entropy composite wire was 443 MPa and the elongation was 8.8%.

[0112] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: The number of warm drawing passes is determined according to the uniformity of the titanium-based high-entropy composite wire. The continuous warm drawing passes are 6 times. S4-S5 are repeated, that is, the previous titanium-based high-entropy composite wire is divided into multiple equal parts along the cross section. The cut titanium-based high-entropy composite wires are tightly twisted together by a stranding machine, and then the next warm drawing is performed until the target number of passes is completed to obtain the titanium-based high-entropy composite wire. The yield strength of the titanium-based high-entropy composite wire is 567 MPa 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 6 m / min, the wire drawing machine temperature is 750°C, the extrusion die diameter is 3 mm, and the diameter decreases by 0.2 mm each time. The target extrusion pass matches the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped, thereby obtaining a titanium-based high-entropy alloy wire. The yield strength of the titanium-based high-entropy alloy wire is 898 MPa, 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 fine titanium-based high-entropy alloy wire with uniform composition had a yield strength of 1070 MPa and an elongation of 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 microstructure, dense structure, smooth surface, no defects such as oxidation, cracking, and porosity, and no wire breakage 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 wire raw materials: Based on 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 were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 40 kHz and a power of 360 W to obtain surface-cleaned wire raw materials;

[0119] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 1000 rpm. The length of the twisted wire is 75% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a double helical structure;

[0120] 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. The strand is first heated to 500°C and the drawing die is preheated to 480°C. Continuous multi-pass drawing is then performed at a drawing rate of 14 m / min. The deformation of each drawing is 15%, and the total deformation of the multi-pass drawing is 65%. The entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The primary titanium-based high-entropy composite wire has a yield strength of 365 MPa and an elongation of 10%.

[0121] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 at a twisting machine speed of 1000 rpm. The length of the twisted wire is 75% of half of the primary titanium-based high-entropy composite wire, thereby obtaining 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 was subjected to continuous multi-pass hot drawing. The wire was first heated to 500°C and the drawing die was preheated to 480°C. Continuous multi-pass drawing was then performed at a drawing rate of 16 m / min. The deformation of each drawing was 15%, and the total deformation of the multi-pass drawing was 75%. The entire process was automatically transmitted to obtain a secondary titanium-based high-entropy composite wire. The yield strength of the secondary titanium-based high-entropy composite wire was 417 MPa and the elongation was 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, 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 8 m / min, the wire drawing machine temperature is 850°C, the extrusion die diameter is 4 mm, and the diameter decreases by 0.5 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped, thereby obtaining 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 minutes, 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 936 MPa and an elongation of 4.5%.

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

[0127] Example 5

[0128] 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 Ti 35 Ni 25 Fe 10 Hf 10 Nb 20 The preparation method of the fine titanium-based high entropy alloy wire is as follows:

[0129] S1. Selection and processing of wire raw materials: Based on the mass ratio of the target titanium-based high-entropy alloy wire, four Ti wires with a diameter of 1 mm and other component wires in corresponding proportions were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 20 kHz and a power of 240 W to obtain surface-cleaned wire raw materials;

[0130] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 500 rpm. The length of the twisted wire is 85% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a multi-helical structure;

[0131] S3. Continuous warm drawing of a primary titanium-based high-entropy composite strand: The primary titanium-based high-entropy composite strand prepared in S2 was subjected to continuous multi-pass hot drawing. The strand was first heated to 550°C and the drawing die was preheated to 300°C. Continuous multi-pass drawing was then performed at a drawing rate of 8 m / min. The deformation of each drawing was 10%, and the total deformation of the multi-pass drawing was 63%. The entire process was automatically transmitted to obtain a primary titanium-based high-entropy composite wire. The yield strength of the primary titanium-based high-entropy composite wire was 294 MPa, and the elongation was 16.2%.

[0132] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 at a twisting machine speed of 1500 rpm. The length of the twisted wire is 70% of one-quarter of the primary titanium-based high-entropy composite wire, thereby obtaining a secondary titanium-based high-entropy composite twisted wire 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 was subjected to continuous multi-pass hot drawing. The wire was first heated to 600°C and the drawing die was preheated to 480°C. Continuous multi-pass drawing was then performed at a drawing rate of 10 m / min. The deformation of each drawing was 13%, and the total deformation of the multi-pass drawing was 70%. The entire process was automatically transmitted to obtain a secondary titanium-based high-entropy composite wire. The yield strength of the secondary titanium-based high-entropy composite wire was 401 MPa and the elongation was 12.3%.

[0134] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: The number of warm drawing passes is determined according to the uniformity of the titanium-based high-entropy composite wire. The continuous warm drawing passes are 4 times. S4-S5 are repeated, that is, the previous titanium-based high-entropy composite wire is divided into multiple equal parts along the cross section. The cut titanium-based high-entropy composite wires are tightly twisted together by a stranding machine, and then the next warm drawing is performed until the target number of passes is completed to obtain the titanium-based high-entropy composite wire. The yield strength of the titanium-based high-entropy composite wire is 557 MPa 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 6 m / min, the wire drawing machine temperature is 750°C, the extrusion die diameter is 3 mm, and the diameter decreases by 0.2 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped to obtain a titanium-based high-entropy alloy wire. The tensile strength of the titanium-based high-entropy alloy wire is 895 MPa, the yield strength is 895 MPa, 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 fine titanium-based high-entropy alloy wire with uniform composition had a yield strength of 1053 MPa and an elongation of 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 microstructure, dense structure, smooth surface, no defects such as oxidation, cracking, and porosity, and no wire breakage 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 is as follows:

[0140] S1. Selection and processing of wire raw materials: Based on the mass ratio of the target titanium-based high-entropy alloy wire, three Ti wires with a diameter of 3 mm and other wires of corresponding proportions were selected as wire raw materials; the wire raw materials were ultrasonically cleaned using commercially available cleaning agents at a frequency of 60 kHz and a power of 720 W to obtain surface-cleaned wire raw materials;

[0141] S2. Twisting of the raw materials of the wire: The raw materials of the wire in S1 are tightly twisted together by a twisting machine at a speed of 800 rpm. The length of the twisted wire is 80% of the raw materials of the wire, thereby obtaining a primary titanium-based high-entropy composite strand with a multi-helical structure;

[0142] 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, first heated to 450°C and the drawing die preheated to 380°C, followed by continuous multi-pass drawing at a drawing rate of 20 m / min, with a deformation of 16% per drawing and a total deformation of 80% over the multi-pass drawing. The entire process is automatically transmitted to obtain a primary titanium-based high-entropy composite wire; the primary titanium-based high-entropy composite wire has a yield strength of 427 MPa and an elongation of 9.5%.

[0143] S4, twisting of the primary titanium-based high-entropy composite wire: the primary titanium-based high-entropy composite wire prepared in S3 is 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 800 rpm, and the length of the twisted wire is 80% of half of the primary titanium-based high-entropy composite wire, thereby obtaining 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 was subjected to continuous multi-pass hot drawing. The wire was first heated to 500°C and the drawing die was preheated to 420°C. Continuous multi-pass drawing was then performed at a drawing rate of 25 m / min. The deformation of each drawing was 20%, and the total deformation of the multi-pass drawing was 75%. The entire process was automatically transmitted to obtain a secondary titanium-based high-entropy composite wire. The yield strength of the secondary titanium-based high-entropy composite wire was 439 MPa and the elongation was 9%.

[0145] S6. Multiple warm drawing of the titanium-based high-entropy composite wire: The number of warm drawing passes is determined according to the uniformity of the titanium-based high-entropy composite wire. The continuous warm drawing passes are 3 times. S4-S5 are repeated, that is, the previous titanium-based high-entropy composite wire is divided into multiple equal parts along the cross section, and the cut titanium-based high-entropy composite wires are tightly twisted together through a stranding machine. Then, the next warm drawing is carried out until the third time is completed 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 16 m / min, the wire drawing machine temperature is 1000°C, the extrusion die diameter is 5 mm, and the diameter decreases by 0.2 mm each time. The target extrusion pass is matched with the diameter of the titanium-based high-entropy pre-alloyed wire, the extrusion die diameter, and the diameter reduction per pass. The entire process is automatically transmitted until the target pass is stopped to obtain a titanium-based high-entropy alloy wire. The yield strength of the titanium-based high-entropy alloy wire is 954 MPa, 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 fine titanium-based high-entropy alloy wire with uniform composition had a yield strength of 1068 MPa and an elongation of 6.4%.

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

[0149] The above scheme, the present invention proposes a method for preparing fine titanium-based high-entropy alloy wire, which can solve the technical bottleneck of preparing titanium-based high-entropy alloy wire due to the poor room temperature plasticity of titanium-based high-entropy alloy and the inability to draw and form it, thereby solving the problem of limited application of titanium-based high-entropy alloy wire. Traditional single-filament additive manufacturing technology using titanium-based high-entropy composite wire as raw material has problems such as complex wire preparation and uneven finished product composition. The fine titanium-based high-entropy alloy wire obtained by the present invention has uniform composition and structure, dense structure, smooth surface, and no defects such as oxidation, cracking, and porosity. The performance of various parts of the fused filament additive manufacturing products 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. There are no special restrictions on the raw material brand and composition, and a wide range of raw materials can be selected. Additive manufacturing can prepare a large number of complex shapes and titanium alloys with different compositions, which is conducive to large-scale industrial production and commercial promotion and application.

[0151] The present invention utilizes the good room temperature plasticity of 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 twisting. 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 or wire breakage occurs 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, thereby significantly improving the preparation efficiency of the titanium-based high-entropy alloy wire.

[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 die diameter. This avoids the high-temperature melting process and solves the technical bottleneck of the difficulty in preparing alloy wires due to the brittleness of titanium-based high-entropy alloys at room temperature, and effectively reduces the volatilization of low-melting-point elements during the preparation of titanium-based high-entropy alloy wires.

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

[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, ensuring 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 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 wires for the preparation and extrusion of titanium-based high-entropy composite wires. 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" as used herein simply describes a relationship between associated objects, indicating that three possible relationships exist. For example, "A and / or B" can represent: A alone, A and B together, or B alone. A and B can be singular or plural. Furthermore, the character " / " as used herein generally indicates an "or" relationship between the associated objects, but it may also indicate an "and / or" relationship. For specific understanding, please refer to the context.

[0159] In this disclosure, "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 or plural items. For example, "at least one of a, b, or c" can mean: a, b, c, ab, ac, bc, or abc, where a, b, and c can be single or plural.

[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 description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection 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 fine titanium-based high-entropy alloy wire comprises the following steps: S1. Selection and processing of wire raw materials: According to the mass ratio of the target titanium-based high-entropy alloy wire, select corresponding multiple Ti wires with corresponding proportions of other wire raw materials; and ultrasonically cleaning the raw wire materials with cleaning agents to obtain raw wire 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 stranded 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 primary titanium-based high-entropy composite wires together using 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 strands: The secondary titanium-based high-entropy composite strands prepared in S4 are subjected to continuous multi-pass hot drawing, with the entire process being automatically transmitted to obtain secondary titanium-based high-entropy composite wires; 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, repeat S4-S5, that is, divide the previous titanium-based high-entropy composite wire into multiple equal parts along the cross section, use a stranding machine to tightly twist the cut previous titanium-based high-entropy composite wires together, and then perform the next warm drawing until the target number of passes is completed to obtain the titanium-based high-entropy composite wire; S7. Continuous extrusion of titanium-based high-entropy composite wire: The titanium-based high-entropy composite wire prepared in S6 is continuously drawn and extruded through a continuous wire drawing machine, with the entire process automatically conveyed until the target pass is stopped, thereby obtaining a titanium-based high-entropy alloy wire; the extrusion rate of the continuous drawing and extrusion is 1-20 m / min, the wire drawing machine temperature is 600-1200°C, the extrusion die diameter is 0.8-5 mm and the diameter decreases gradually by 0.2-1 mm, and the yield strength of the titanium-based high-entropy alloy wire is 800-2500 MPa, and the elongation is 3-15%; 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; the diffusion homogenization treatment temperature is 800-1300°C, the holding time is 60-120min, and the vacuum degree is 10 -1 ~10 -3 Pa, the yield strength of uniformly composed micro-titanium-based high-entropy alloy wire is 800-2600 MPa, and the elongation is 3-10%.

2. The method for preparing a fine titanium-based high-entropy alloy wire 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 or Zr; X=Al, Fe or Mo; Y=Nb, Cu, W or Co; Z=V, Hf, Ta or Mn, where a: 20-80at.%, b, c, d and e: 3-40at.%, a≥b, a≥c, a≥d, a≥e, and a+b+c+d+e=100; the diameter of the wire 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 or higher structure.

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, then performing continuous multi-pass drawing, with a drawing rate of 5-30m / min, a deformation of 10-20% per drawing, and a total deformation 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 is 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 50-600 MPa 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 number of warm drawing passes in the multiple warm drawing process of 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%.

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