A complete process for preparing large deformation ultra-fine diameter tungsten-rhenium alloy wire

Abstract

This invention discloses a complete process for preparing ultra-fine diameter tungsten-rhenium alloy wire with large deformation. The method includes: 1. Obtaining tungsten-rhenium mixed powder through spray drying and hydrogen reduction; 2. Pre-pressing and pre-sintering the tungsten-rhenium mixed powder to obtain a tungsten-rhenium alloy billet; 3. Performing hot isostatic pressing followed by heated forging to open the billet; 4. Performing heated rotary forging; 5. Performing high-temperature straightening, followed by surface polishing and cleaning; 6. Impregnating with a lubricant and heating to form a lubricating film; 7. Performing continuous wire drawing at high temperature using a single die in multiple passes and impregnating with graphite emulsion to obtain fine tungsten-rhenium alloy wires; 8. Performing alkaline washing, acid washing, and rinsing; 9. Performing high-temperature annealing. This invention enhances the lubrication effect of tungsten-rhenium alloy during high-temperature wire drawing by strictly controlling the wire drawing lubrication conditions, ensuring continuous deformation wire drawing of tungsten-rhenium alloy, preparing high-performance ultra-fine diameter tungsten-rhenium alloy wire with uniform structure and excellent mechanical properties, reducing damage to the die, and lowering production costs.

Description

Technical Field

[0001] This invention belongs to the field of ultra-fine diameter metal wire preparation technology, specifically relating to a complete process preparation method for large deformation ultra-fine diameter tungsten-rhenium alloy wire. Background Technology

[0002] Tungsten and tungsten alloys possess high melting points, high strength, and excellent plasticity, creep resistance, and machinability, making them widely used in aerospace, marine, electronic circuits, nuclear engineering, medical devices, weaponry, and many other fields. China has abundant tungsten reserves and has become the world's largest exporter of tungsten raw materials. However, there is a significant gap between China's deep processing of tungsten and tungsten alloys and that of foreign countries. Exported tungsten and tungsten alloys are mainly low- to mid-range products with low added value, such as sintered and powdered forms. High-performance, high-precision, and high-value-added tungsten alloy products still rely on imports.

[0003] Currently, with the rapid development of the photovoltaic industry, diamond wire cutting of silicon wafers has become a crucial step in improving wafer quality and reducing production costs. The cutting effect and economy of diamond wire cutting are closely related to the quality of the busbar. Commonly used diamond wire busbars include high-carbon steel wire and tungsten alloy wire. Compared to high-carbon steel wire, tungsten alloy wire has higher tensile strength, better toughness, and properties such as high-temperature resistance, oxidation resistance, and fatigue resistance. It also has a finer wire diameter, lower breakage rate, less loss during silicon wafer cutting, and better economic benefits, making it the most ideal diamond wire busbar material. However, China still heavily relies on imports for ultra-fine diamond wire busbar materials.

[0004] Domestic ultrafine wires have achieved remarkable results after decades of development. However, the tungsten and tungsten alloy wires produced still cannot meet the requirements for use as diamond wire conductors. The main reason is that the intrinsic brittleness of tungsten makes plastic processing of tungsten and tungsten alloys difficult, resulting in poor mechanical properties, large wire diameter, and a tendency to exhibit macroscopic defects such as uneven deformation, "bamboo joints," and cracking. Furthermore, plastic deformation, such as rotary forging and wire drawing, is unavoidable during the manufacturing process of tungsten and tungsten alloy wires. Due to their work-hardening characteristics, subsequent processing becomes extremely difficult, easily leading to damage to processing dies and significantly limiting the continuous manufacturing of tungsten and tungsten alloy wires. Existing research indicates that adding rhenium to tungsten and tungsten alloys is an effective way to improve their plastic processing and mechanical properties. The addition of rhenium can reduce the grain boundary resistance of dislocation movement, increase dislocation migration, and strengthen the matrix phase through solid solution, becoming an important means to improve the plastic processing performance of tungsten and tungsten alloys. Although the addition of rhenium is beneficial for the preparation of ultra-fine diameter tungsten and tungsten alloys, the lubricant is difficult to adhere to the surface of the wire during the high-temperature wire drawing process, which can easily lead to the damage of the wire drawing die. As a result, the tungsten and tungsten alloy wires prepared have a rough surface, uneven deformation, and poor mechanical properties.

[0005] Given that China currently relies heavily on imports for ultra-fine diameter filaments, there is an urgent need to develop high-performance ultra-fine diameter filaments to meet the needs of domestic industrial production. Summary of the Invention

[0006] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing a complete process for preparing ultra-fine diameter tungsten-rhenium alloy wire with large deformation. In the wire drawing stage of the entire process of preparing ultra-fine diameter tungsten-rhenium alloy wire, this method enhances the lubrication effect of tungsten-rhenium alloy during high-temperature wire drawing by strictly controlling the drawing lubrication conditions, ensuring continuous deformation drawing of tungsten-rhenium alloy, thereby preparing high-performance ultra-fine diameter tungsten-rhenium alloy wire with uniform microstructure and excellent mechanical properties. This solves the problem that high-temperature drawing of tungsten-rhenium alloy is difficult due to lubrication difficulties, hindering the processing into ultra-fine diameter wires.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a complete process preparation method for large deformation ultra-fine diameter tungsten-rhenium alloy wire, characterized in that the method includes the following steps:

[0008] Step 1: Dissolve ammonium metatungstate and ammonium rhenium in water, and use a spray drying device to spray dry them to prepare an alloy powder precursor. Then reduce it with hydrogen to obtain tungsten-rhenium mixed powder.

[0009] Step 2: The tungsten-rhenium mixed powder obtained in Step 1 is pre-pressed using a compression device, and then pre-sintered using hydrogen to obtain a tungsten-rhenium alloy billet.

[0010] Step 3: The tungsten-rhenium alloy billet obtained in Step 2 is densified by hot isostatic pressing, and then heated and forged by air hammer.

[0011] Step 4: The tungsten-rhenium alloy billet after the forging process in Step 3 is heated and forged using a rotary forging equipment to obtain tungsten-rhenium alloy coarse wire with a diameter matching the specifications of the wire drawing equipment.

[0012] Step 5: The tungsten-rhenium alloy coarse wire obtained in Step 5 is straightened by high-temperature heating using a straightening machine, then the surface is polished, and then ultrasonically cleaned with anhydrous ethanol and deionized water respectively to obtain a straight and smooth tungsten-rhenium alloy coarse wire after treatment.

[0013] Step 6: Apply lubricant to the surface of the treated tungsten-rhenium alloy coarse wire obtained in Step 5, and then heat it through a tube furnace by traction to generate a WS2 / MoS2 lubricating film on the surface of the tungsten-rhenium alloy coarse wire;

[0014] Step 7: The tungsten-rhenium alloy coarse wire with WS2 / MoS2 lubricating film on the surface from Step 6 is continuously drawn in a single die and multiple passes at high temperature using a wire drawing machine. During the single die and multiple passes continuous drawing process, graphite emulsion is applied for lubrication to obtain tungsten-rhenium alloy fine wire.

[0015] Step 8: The tungsten-rhenium alloy filaments obtained in Step 7 are subjected to alkaline washing to remove the residual WS2 / MoS2 lubricating film, graphite emulsion and metal oxides on the surface. Then, acid washing is performed to remove the residual alkaline solution on the surface. Finally, deionized water is rinsed to obtain the treated tungsten-rhenium alloy filaments.

[0016] Step 9: Place the processed tungsten-rhenium alloy filaments obtained in Step 8 into a vacuum environment for high-temperature annealing to obtain ultra-fine diameter tungsten-rhenium alloy wires.

[0017] The above-mentioned method for preparing large deformation ultra-fine diameter tungsten-rhenium alloy wire is characterized in that the mass purity of ammonium metatungstate and ammonium rhenium in step one is both above 99.99%.

[0018] The above-mentioned method for preparing large deformation ultra-fine diameter tungsten-rhenium alloy wire is characterized in that the tungsten-rhenium alloy billet in step two is a rod with a diameter of Φ40mm to Φ80mm.

[0019] The above-described complete process for preparing large-deformation, ultra-fine-diameter tungsten-rhenium alloy wire is characterized in that the density of the tungsten-rhenium alloy billet after hot isostatic pressing in step three is greater than 95%; the heating equipment used for the hot forging blanking process is a hydrogen furnace, the heating temperature is 1600℃~1800℃, the holding time is 0.5h~2h, and the diameter reduction percentage of the tungsten-rhenium alloy billet after each hot forging blanking process is 10%~20%, and the tungsten-rhenium alloy billet after forging blanking process is a bar with a diameter of Φ15mm~Φ25mm. The selection of these parameters is beneficial for obtaining a microstructure with a density greater than 98% and a finer grain size, facilitating further post-processing plastic deformation.

[0020] The above-mentioned complete process preparation method for large deformation ultra-fine diameter tungsten-rhenium alloy wire is characterized in that, in step four, the heating equipment used for the rotary forging process is a porous hydrogen heating furnace, the heating temperature is 1600℃~1700℃, the holding time is 20min~35min, and the diameter reduction percentage of the tungsten-rhenium alloy billet after each pass of rotary forging is 5%~10%, the feeding speed is 20mm / s~30mm / s, and the diameter of the tungsten-rhenium alloy coarse wire is Φ4mm~Φ8mm. The selection of these rotary forging process parameters ensures uniform stress distribution during the rotary forging process, avoiding uneven deformation caused by high local work hardening, which could affect further processing and deformation of the material.

[0021] The above-described complete process for preparing large-deformation, ultra-fine-diameter tungsten-rhenium alloy wire is characterized in that the heating equipment used for high-temperature heating straightening in step five is a hydrogen furnace, with a heating temperature of 800℃~1000℃, and the axial straightness of the tungsten-rhenium alloy coarse wire after high-temperature heating straightening does not exceed 2.0mm. Straightening using this method facilitates ensuring the processing accuracy and uniformity of deformation in subsequent material processing.

[0022] The above-described complete process for preparing large-deformation, ultra-fine-diameter tungsten-rhenium alloy wire is characterized in that, in step six, the lubricant is composed of molybdenum salt / tungsten salt and 150SN base oil, wherein the mass content of molybdenum salt / tungsten salt is 1%–6%; the traction linear speed is 20 mm / s–50 mm / s; and the heating temperature is 150℃–250℃. The high-temperature heating environment causes the tungsten / molybdenum salt to decompose and form stable nano-WS2 / MoS2. Typically, the molybdenum salt / tungsten salt is selected as tungsten dialkyldithiocarbamate / molybdenum salt.

[0023] The above-mentioned method for preparing a large deformation ultra-fine diameter tungsten rhenium alloy wire is characterized in that, in step seven, the temperature, feed rate, and diameter reduction percentage during the single-die multi-pass continuous wire drawing process are adjusted according to the specifications of the tungsten rhenium alloy coarse wire with a WS2 / MoS2 lubricating film on its surface. The specific process specifications are as follows: (1) When the diameter of the object being processed is greater than 8 mm, the temperature is 1500℃±50℃, the feed rate is 15 mm / s~20 mm / s, and the diameter reduction percentage is 10%~15%; (2) When the diameter of the object being processed is greater than 6 mm... When the diameter of the object being processed is greater than 2 mm but not more than 6 mm, the temperature is 1250℃~1400℃, the feeding speed is 20mm / s~25mm / s, and the reduction percentage is 8%~10%; (3) When the diameter of the object being processed is greater than 2 mm but not more than 6 mm, the temperature is 1200℃~1350℃, the feeding speed is 25mm / s~30mm / s, and the reduction percentage is 6%~8%; (4) When the diameter of the object being processed is less than 2 mm, the temperature is 1000℃±50℃, the feeding speed is 30mm / s~40mm / s, and the reduction percentage is 2%~6%. Through this processing technology, uniform deformation of the material can be achieved, avoiding changes in the dimensional accuracy of the finished product due to high local deformation.

[0024] The above-mentioned method for preparing large deformation ultra-fine diameter tungsten rhenium alloy wire is characterized in that the alkaline washing in step eight uses a molten alkaline solution containing NaOH and NaNO3, and the acid washing uses an acid washing solution containing HNO3 and water.

[0025] The above-described complete process for preparing large deformation ultrafine diameter tungsten-rhenium alloy wire is characterized by the following: the high-temperature annealing treatment in step nine is carried out at a temperature of 1450℃~1650℃ for 2 hours, followed by furnace cooling; the Re content in the ultrafine diameter tungsten-rhenium alloy wire is 5%~30% by mass, with the balance being W, and the diameter of the ultrafine diameter tungsten-rhenium alloy wire is as low as 0.1μm. Under these annealing temperatures and times, stress relief, improved microstructure, and enhanced mechanical properties of the large deformation ultrafine tungsten-rhenium alloy wire can be ensured.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] 1. This invention sequentially produces tungsten-rhenium alloy coarse wire through spray drying combined with hydrogen reduction powdering, pre-pressing and pre-sintering billet preparation, heated forging blanking, and heated rotary forging. Then, after straightening, polishing, and cleaning, it undergoes lubricant impregnation followed by heating, single-die multi-pass continuous wire drawing, alkaline washing, acid washing, deionized water rinsing, and high-temperature annealing. This completes the entire process of preparing ultra-fine diameter tungsten-rhenium alloy wire. In this preparation process, by impregnating the surface of the tungsten-rhenium alloy coarse wire with lubricant and heating it to generate a WS2 / MoS2 lubricating film, combined with graphite emulsion lubrication during wire drawing, the lubrication effect of the tungsten-rhenium alloy during high-temperature wire drawing is enhanced, ensuring continuous deformation and wire drawing of the tungsten-rhenium alloy. This results in high-performance ultra-fine diameter tungsten-rhenium alloy wire with uniform structure and excellent mechanical properties, solving the problem of difficult lubrication in the preparation of ultra-fine diameter tungsten-rhenium alloy wire.

[0028] 2. Compared with traditional wire drawing processes, this invention adopts a lubrication process that effectively combines oil-soluble molybdenum / tungsten salt and graphite emulsion, avoiding wire breakage caused by insufficient lubrication. It changes the frictional movement mode between the wire surface and the die surface, greatly reducing the friction coefficient between the two, improving the surface quality of ultra-fine diameter tungsten rhenium alloy wire, reducing damage to the die during high-temperature wire drawing, extending the service life of the wire drawing die under extreme working conditions, and reducing production costs.

[0029] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0030] Figure 1 This is a process flow diagram of the continuous preparation method of the present invention.

[0031] Figure 2 This is a schematic diagram of the lubricant generating a WS2 lubricating film by heating in this invention.

[0032] Figure 3 This is a schematic diagram illustrating the effect of WS2 lubricating film coupled with graphite emulsion lubrication during single-mold multi-pass continuous wire drawing according to the present invention.

[0033] Figure 4This is a physical image of the ultra-fine diameter tungsten-rhenium alloy wire prepared in Example 1 of the present invention.

[0034] Figure 5a This is a transverse microstructure diagram of the ultra-fine diameter tungsten-rhenium alloy wire prepared in Example 1 of the present invention.

[0035] Figure 5b This is a longitudinal microstructure diagram of the ultra-fine diameter tungsten-rhenium alloy wire prepared in Example 1 of the present invention. Detailed Implementation

[0036] like Figure 2 As shown, this invention employs tungsten salt of dialkyldithiodicarboxylate (molecular structural formula see...). Figure 2 A lubricant consisting of (a) and (b) and the balance 150SN base oil was applied to the surface of the treated tungsten-rhenium alloy coarse wire. Upon heating, it decomposed to generate a stable two-dimensional material WS2 lubricating film (see...). Figure 2 (c)

[0037] like Figure 3 As shown, in the single-mold multi-pass continuous wire drawing process of the present invention, graphite emulsion is impregnated onto the tungsten rhenium alloy coarse wire with a WS2 lubricating film on its surface to form a lubricating layer composed of two-dimensional materials (WS2 and graphite C), which improves the lubrication effect of the wire drawing process and ensures the dimensional accuracy of the tungsten rhenium alloy fine wire.

[0038] Example 1

[0039] like Figure 1 As shown, this embodiment includes the following steps:

[0040] Step 1: Dissolve ammonium metatungstate and ammonium rhenium, both with a purity of 99.99%, in water at a mass ratio of 7:3. Use a spray drying device to spray dry the mixture to produce an alloy powder precursor, and then reduce it with hydrogen to obtain a tungsten-rhenium mixed powder.

[0041] Step 2: The tungsten-rhenium mixed powder obtained in Step 1 is pre-pressed using a compression device, and then pre-sintered using hydrogen to obtain a tungsten-rhenium alloy billet, which is a rod with a diameter of Φ40mm.

[0042] Step 3: The tungsten-rhenium alloy billet obtained in Step 2 is densified by hot isostatic pressing to a density greater than 95%. Then, it is heated and forged using an air hammer. The heating equipment used is a hydrogen furnace with a heating temperature of 1600℃ and a holding time of 0.5h. The diameter reduction percentage of the tungsten-rhenium alloy billet after each heating and forging process is 10%. The tungsten-rhenium alloy billet after forging is a bar with a diameter of Φ15mm.

[0043] Step 4: The tungsten-rhenium alloy billet after the forging and blanking process in Step 3 is subjected to heating and rotary forging using a rotary forging equipment. The heating equipment used is a porous hydrogen heating furnace, the heating temperature is 1600℃, the holding time is 20min, and the diameter reduction percentage of the tungsten-rhenium alloy billet after each heating and rotary forging process is 5%. The feeding speed is 20mm / s, and a tungsten-rhenium alloy coarse wire with a diameter of Φ4mm is obtained.

[0044] Step 5: The tungsten-rhenium alloy coarse wire obtained in Step 5 is straightened by high-temperature heating using a straightening machine. The heating equipment used is a hydrogen furnace, and the heating temperature is 800℃. The axial straightness of the tungsten-rhenium alloy coarse wire after high-temperature heating and straightening does not exceed 2.0mm. Then, the surface is polished, and then ultrasonically cleaned with anhydrous ethanol and deionized water for 20 minutes respectively to obtain a straight and smooth and clean tungsten-rhenium alloy coarse wire.

[0045] Step 6: The lubricant, consisting of 1% by mass of tungsten dialkyl dithiodicarboxylate and the remainder of 150SN base oil, is applied to the surface of the treated tungsten-rhenium alloy coarse wire obtained in Step 5. Then, it is pulled through a tube furnace heated at 150°C at a speed of 20 mm / s to generate a fresh WS2 lubricating film on the surface of the tungsten-rhenium alloy coarse wire.

[0046] Step 7: Using a wire drawing machine, the tungsten-rhenium alloy coarse wire with WS2 lubricating film on its surface from Step 6 is continuously drawn in a single die and multiple passes at high temperature. When the diameter of the object being processed is greater than 2 mm but not more than 6 mm, the temperature is 1200℃, the feed rate is 30 mm / s, and the reduction percentage is 6%. When the diameter of the object being processed is less than 2 mm, the temperature is 1000℃±50℃, the feed rate is 40 mm / s, and the reduction percentage is 2%. During the single die and multiple passes of continuous wire drawing, graphite emulsion is used for lubrication to obtain tungsten-rhenium alloy fine wire.

[0047] Step 8: The tungsten-rhenium alloy wire obtained in Step 7 is subjected to alkaline washing at a temperature of 300℃ using a molten alkaline solution containing 97% NaOH and 3% NaNO3 by mass to remove the residual WS2 lubricating film, graphite emulsion and metal oxides on the surface. Then, an acid pickling solution containing 7% HNO3 by mass is used to remove the residual alkaline solution on the surface. Finally, the wire is rinsed with deionized water for 5 minutes to obtain the treated tungsten-rhenium alloy wire.

[0048] Step 9: The treated tungsten-rhenium alloy wire obtained in Step 8 is subjected to high-temperature annealing in a vacuum environment at 1450℃ for 2 hours, followed by furnace cooling to obtain ultra-fine tungsten-rhenium alloy wire with a diameter of 0.1 μm. Figure 4 As shown; the mass content of Re in the ultra-fine diameter tungsten-rhenium alloy wire is 30%, and the balance is W.

[0049] Figure 5a and Figure 5b These are transverse and longitudinal microstructure images of the ultra-fine diameter tungsten-rhenium alloy wire prepared in this embodiment. Figure 5a and 5b It can be seen that the transverse direction of this fine-diameter tungsten-rhenium alloy wire is composed of uniform equiaxed grains, while the longitudinal direction is composed of elongated deformed grains and a small number of fine recovery grains.

[0050] Example 2

[0051] like Figure 1 As shown, this embodiment includes the following steps:

[0052] Step 1: Dissolve ammonium metatungstate and ammonium rhenium, both with a purity of 99.99%, in water at a mass ratio of 19:1. Spray dry the mixture to produce an alloy powder precursor, and then reduce it with hydrogen to obtain a tungsten-rhenium mixed powder.

[0053] Step 2: The tungsten-rhenium mixed powder obtained in Step 1 is pre-pressed using a compression device, and then pre-sintered using hydrogen to obtain a tungsten-rhenium alloy billet, which is a rod with a diameter of Φ80mm.

[0054] Step 3: The tungsten-rhenium alloy billet obtained in Step 2 is densified by hot isostatic pressing to a density greater than 95%. Then, it is heated and forged using an air hammer. The heating equipment used is a hydrogen furnace, the heating temperature is 1800℃, and the holding time is 3h. The diameter reduction percentage of the tungsten-rhenium alloy billet after each heating and forging process is 20%. The tungsten-rhenium alloy billet after forging is a bar with a diameter of Φ25mm.

[0055] Step 4: The tungsten-rhenium alloy billet after the forging and blanking process in Step 3 is subjected to heating and rotary forging using a rotary forging equipment. The heating equipment used is a porous hydrogen heating furnace with a heating temperature of 1700℃ and a holding time of 35min. The diameter reduction percentage of the tungsten-rhenium alloy billet after each heating and rotary forging process is 10%, and the feeding speed is 30mm / s, resulting in tungsten-rhenium alloy coarse wire with a diameter of Φ8mm.

[0056] Step 5: The tungsten-rhenium alloy coarse wire obtained in Step 5 is straightened by high-temperature heating using a straightening machine. The heating equipment used is a hydrogen furnace, and the heating temperature is 1000℃. The axial straightness of the tungsten-rhenium alloy coarse wire after high-temperature heating and straightening does not exceed 2.0mm. Then, the surface is polished, and then ultrasonically cleaned with anhydrous ethanol and deionized water for 20 minutes respectively to obtain a straight and smooth tungsten-rhenium alloy coarse wire.

[0057] Step 6: The lubricant, consisting of 6% by mass of tungsten dialkyl dithiodicarboxylate and the remainder of 150SN base oil, is applied to the surface of the treated tungsten-rhenium alloy coarse wire obtained in Step 5. Then, it is pulled through a tube furnace heated at 250°C at a speed of 50 mm / s to generate a fresh WS2 lubricating film on the surface of the tungsten-rhenium alloy coarse wire.

[0058] Step 7: Using a wire drawing machine, the tungsten-rhenium alloy coarse wire with the WS2 lubricating film on its surface from Step 6 is continuously drawn in a single die with multiple passes at high temperature. When the diameter of the object being processed is greater than 6 mm but not more than 8 mm, the temperature is 1400℃, the feed rate is 20 mm / s, and the drawdown percentage is 8%–10%. When the diameter of the object being processed is greater than 2 mm but not more than 6 mm, the temperature is 1200℃, the feed rate is 30 mm / s, and the drawdown percentage is 6%. When the diameter of the object being processed is less than 2 mm, the temperature is 1000℃, the feed rate is 40 mm / s, and the drawdown percentage is 2%. During the single die multi-pass continuous wire drawing process, a graphite emulsion dipping method is used for lubrication to obtain tungsten-rhenium alloy fine wire.

[0059] Step 8: The tungsten-rhenium alloy wire obtained in Step 7 is subjected to alkaline washing at a temperature of 300℃ using a molten alkaline solution containing 97% NaOH and 3% NaNO3 by mass to remove the residual WS2 / MoS2 lubricating film, graphite emulsion and metal oxides on the surface. Then, an acid pickling solution containing 7% HNO3 by mass is used to remove the residual alkaline solution on the surface. Finally, the wire is rinsed with deionized water for 5 minutes to obtain the treated tungsten-rhenium alloy wire.

[0060] Step 9: The treated tungsten-rhenium alloy wire obtained in Step 8 is placed in a vacuum environment for high-temperature annealing at 1650℃ for 2 hours and then cooled in the furnace to obtain an ultra-fine tungsten-rhenium alloy wire with a diameter of 0.1μm. The mass content of Re in the ultra-fine tungsten-rhenium alloy wire is 5%, and the balance is W.

[0061] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the inventive essence shall still fall within the protection scope of the present invention.

Claims

1. A complete process method for preparing large deformation ultra-fine diameter tungsten-rhenium alloy wire, characterized in that, The method includes the following steps: Step 1: Dissolve ammonium metatungstate and ammonium rhenium in water, and use a spray drying device to spray dry them to prepare an alloy powder precursor. Then reduce it with hydrogen to obtain tungsten-rhenium mixed powder. Step 2: The tungsten-rhenium mixed powder obtained in Step 1 is pre-pressed using a compression device, and then pre-sintered using hydrogen to obtain a tungsten-rhenium alloy billet. Step 3: The tungsten-rhenium alloy billet obtained in Step 2 is densified by hot isostatic pressing, and then heated and forged by air hammer. Step 4: The tungsten-rhenium alloy billet after the heating and forging process in Step 3 is subjected to heating and spinning forging using a rotary forging equipment to obtain tungsten-rhenium alloy coarse wire with a diameter matching the specifications of the wire drawing equipment. Step 5: The tungsten-rhenium alloy coarse wire obtained in Step 4 is straightened by high-temperature heating using a straightening machine, then the surface is polished, and then ultrasonically cleaned with anhydrous ethanol and deionized water respectively to obtain a straight and smooth tungsten-rhenium alloy coarse wire after treatment. Step 6: Apply lubricant to the surface of the treated tungsten-rhenium alloy coarse wire obtained in Step 5, and then heat it through a tube furnace by traction to generate a WS2 lubricating film on the surface of the tungsten-rhenium alloy coarse wire; the lubricant consists of tungsten dialkyl dithiodimethylformate salt and the balance 150SN base oil; Step 7: Using a wire drawing machine, the tungsten-rhenium alloy coarse wire with WS2 lubricating film on its surface from Step 6 is continuously drawn in a single mold and multiple passes at high temperature. During the single mold and multiple passes continuous drawing process, a graphite emulsion is dipped in for lubrication to obtain tungsten-rhenium alloy fine wire. Step 8: The tungsten-rhenium alloy filaments obtained in Step 7 are subjected to alkaline washing to remove the residual WS2 lubricating film, graphite emulsion and metal oxides on the surface, followed by acid washing to remove the residual alkaline solution on the surface, and then rinsed with deionized water to obtain the treated tungsten-rhenium alloy filaments. Step 9: Place the processed tungsten-rhenium alloy filaments obtained in Step 8 into a vacuum environment for high-temperature annealing to obtain ultra-fine diameter tungsten-rhenium alloy wires.

2. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, The mass fraction of ammonium metatungstate and ammonium rhenium in step one is both above 99.99%.

3. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, The tungsten-rhenium alloy billet mentioned in step two is a bar with a diameter of Φ40mm~Φ80mm.

4. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, In step three, the density of the tungsten-rhenium alloy billet after hot isostatic pressing is greater than 95%. The heating equipment used for the hot forging blanking process is a hydrogen furnace, with a heating temperature of 1600℃~1800℃ and a holding time of 0.5h~2h. The diameter reduction percentage of the tungsten-rhenium alloy billet after each hot forging blanking process is 10%~20%. The tungsten-rhenium alloy billet after the hot forging blanking process is a bar with a diameter of Φ15mm~Φ25mm.

5. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, The heating equipment used in the heating and rotary forging process in step four is a porous hydrogen heating furnace, with a heating temperature of 1600℃~1700℃ and a holding time of 20min~35min. The diameter reduction percentage of the tungsten-rhenium alloy billet after each heating and rotary forging process is 5%~10%, the feeding speed is 20mm / s~30mm / s, and the diameter of the tungsten-rhenium alloy coarse wire is Φ4mm~Φ8mm.

6. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, The heating equipment used for high-temperature heating straightening in step five is a hydrogen furnace, with a heating temperature of 800℃~1000℃, and the axial straightness of the tungsten rhenium alloy coarse wire after high-temperature heating straightening does not exceed 2.0mm.

7. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, In step six, the mass fraction of the dialkyldithiodimethylformate tungsten salt is 1% to 6%; the traction linear speed is 20 mm / s to 50 mm / s; and the temperature of the traction-heated tubular furnace is 150°C to 250°C.

8. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, In step seven, the temperature, feed rate, and diameter reduction percentage during the single-die multi-pass continuous wire drawing process are adjusted according to the specifications of the tungsten rhenium alloy coarse wire with a WS2 lubricating film on its surface. The specific process specifications are as follows: (1) When the diameter of the object being processed is greater than 8 mm, the temperature is 1500℃±50℃, the feed rate is 15mm / s~20mm / s, and the diameter reduction percentage is 10%~15%; (2) When the diameter of the object being processed is greater than 6 mm but not exceeding 8 mm, the temperature is 1250℃~1 400℃, feeding speed is 20mm / s~25mm / s, diameter reduction percentage is 8%~10%; (3) When the diameter of the object being processed is greater than 2mm and does not exceed 6mm, the temperature is 1200℃~1350℃, feeding speed is 25mm / s~30mm / s, diameter reduction percentage is 6%~8%; (4) When the diameter of the object being processed is less than 2mm, the temperature is 1000℃±50℃, feeding speed is 30mm / s~40mm / s, diameter reduction percentage is 2%~6%.

9. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, The alkaline washing in step eight uses a molten alkaline solution containing NaOH and NaNO3, and the acid washing uses an acid washing solution containing HNO3 and water.

10. The complete process preparation method of large deformation ultra-fine diameter tungsten-rhenium alloy wire according to claim 1, characterized in that, The high-temperature annealing treatment in step nine is carried out at a temperature of 1450℃~1650℃ for 2 hours, followed by furnace cooling. The mass fraction of Re in the ultra-fine diameter tungsten-rhenium alloy wire is 5%~30%, with the balance being W, and the diameter of the ultra-fine diameter tungsten-rhenium alloy wire is as low as 0.1μm.

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