Preparation method of high-solute, high-plasticity Cu-Sn-Ti alloy

Abstract

This invention discloses a method for preparing a high-solute, high-plasticity Cu-Sn-Ti alloy, comprising the following steps: 1. Filling a copper cladding with Cu-Sn-Ti alloy powder; 2. Performing vacuum and heat preservation treatment on the copper cladding; 3. Performing hot isostatic pressing on the copper cladding; 4. Performing heat treatment and quenching on the copper cladding, and removing the copper cladding to obtain the finished product. The preparation method of this invention ensures the high solute content and high plasticity of δ-Cu alloys. 41 Sn 11 The phase will not use oxides as nucleation sites, thus preventing segregation and making it easier for sintering necks to form between powders; vacuuming of the copper cladding at room temperature and high temperature environments further removes air from the powder gaps; the higher hot-pressing environment is beneficial for improving the tensile strength and plasticity of the alloy; it solves the problem of the alloy being difficult to clamp and move due to its large size and weight; and it enables δ-Cu 41 Sn 11 The phase transformation results in more β, γ, and ε phases in the slip system, which significantly improves the plasticity of the alloy.

Description

Technical Field

[0001] This invention belongs to the field of powder metallurgy technology and relates to a method for preparing a high-solute, high-plasticity Cu-Sn-Ti alloy. Background Technology

[0002] Currently, the key raw material required for preparing "Nb3Sn low-temperature superconducting wires using the bronze method" is a large-size high-solute bronze (abbreviated as Cu-Sn-Ti alloy, in which the Sn content is ≥15wt.%, the Ti content is 0.3wt.%, and the balance is Cu). With the rapid development of the superconducting field, the demand is increasing day by day. Internationally, the large-size high-solute bronze used for wire manufacturing is mainly prepared and supplied by Osaka Alloy Co., Ltd. of Japan using the "Mizuta method", and its alloy has excellent strength and ductility.

[0003] However, my country currently lacks the capability to prepare high-solute, high-plasticity Cu-Sn-Ti alloys. The main reasons are: ① While the commonly used traditional water-cooled casting and powder-mixing cold-pressing followed by hot-pressing sintering techniques for preparing high-solute Cu-Sn-Ti alloys can easily meet the large-size requirements for wire rod fabrication, these techniques suffer from problems such as the non-equilibrium solidification process of the alloy melt and the large size and insufficient diffusion of Sn powder particles. These factors result in large, hard, and brittle δ-Cu phases existing between the α-Cu phase crystals in the room-temperature microstructure of the alloy. 41 Sn 11 Phase segregation, coupled with the poor overall performance of coarse α-Cu phase grains, leads to poor alloy plasticity, resulting in problems such as core breakage and wire breakage during wire fabrication; ② Currently used domestic technologies such as directional solidification, multi-atmosphere continuous sintering of alloy powders, and thermo-mechanical-electric multi-field coupling rapid sintering of alloy powders can optimize the grain orientation and size of the α-Cu phase and promote the growth of δ-Cu phases. 41 Sn 11 The phase is uniformly dispersed to prepare Cu-Sn-Ti alloys with high solute and high plasticity. However, due to the limitations of the furnace size in the preparation process, it is impossible to meet the requirements of large size and high solute and high plasticity required for production lines.

[0004] Therefore, there is an urgent need to develop a new method for preparing large-sized, high-solute, high-plasticity Cu-Sn-Ti alloys to solve the aforementioned technical problems in preparation. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a high-solute, high-plasticity Cu-Sn-Ti alloy, which solves the problem that the Cu-Sn-Ti alloy prepared by the prior art cannot simultaneously achieve high solute and high plasticity in terms of wire forming requirements.

[0006] The technical solution adopted in this invention is a method for preparing a high-solute, high-plasticity Cu-Sn-Ti alloy, which is implemented according to the following steps:

[0007] Step 1: Fill the copper cladding with Cu-Sn-Ti alloy powder;

[0008] Step 2: Perform vacuum and heat insulation treatment on the copper cladding;

[0009] Step 3: Perform hot isostatic pressing on the copper cladding;

[0010] Step 4: Heat treat and quench the copper cladding, remove the copper cladding, and obtain a high-solute, high-plasticity Cu-Sn-Ti alloy product.

[0011] The beneficial effects of this invention are that the preparation method of this invention, based on the limitation of grain size by alloy powder and δ-Cu 41 Sn 11 The microstructure advantage of phase segregation lays the foundation for the alloy's high plasticity. High-solute Cu-Sn-Ti alloy powder with specific properties fully leverages the interstitial filling advantage of small-particle-size powder and the excellent flowability of large-particle-size powder. By controlling the specific parameters of the powder particle size range and median particle size, the tap density of the powder can be ensured to approach the theoretical maximum value of natural gradation. Simultaneously, limiting the oxygen content of the powder guarantees the δ-Cu... 41 Sn 11 The phase does not use oxides as nucleation sites, thus avoiding exacerbating segregation. Simultaneously, it reduces powder surface energy, facilitating the formation of sintering necks between powder particles. Mechanical compaction, replacing manual compaction, ensures higher compaction density, reduces porosity between powder particles, and improves alloy density. Controlling the powder loading amount to 500–1000g per batch allows for timely filling of pores by the powder's own weight during compaction. Positive and negative axial compaction addresses the issue of low compaction density at the initial powder loading end, achieving uniform axial compaction and avoiding axial property differences in the alloy. The method of sequentially vacuuming the copper sheath at room temperature and high temperature facilitates more thorough powder removal. The air in the gaps is eliminated; the holding temperature of 400–500℃ ensures that the alloy powder does not pre-sinter and densify, and causes the alloy powder to expand thermally and squeeze each other, thus expelling the air in the gaps; the hot isostatic pressing process achieves isostatic sintering and densification of the alloy powder, and the alloy structure and properties are anisotropic; the high hot pressing environment promotes the formation of sintering necks between alloy powders, which is beneficial to improving the density of the alloy. At the same time, the dynamic recovery and recrystallization process of hot isostatic pressing further introduces a large number of large-angle grain boundaries and annealing twins, which is beneficial to improving the tensile strength of the alloy. Moreover, the increase in grain boundaries after grain refinement further promotes δ-Cu 41 Sn 11The dispersed distribution of the phase at the grain boundaries and the refinement of its size reduce stress concentration during plastic deformation, thereby improving the alloy's plasticity. Furthermore, hot isostatic pressing (HIP) technology, due to its large furnace size, is advantageous for the preparation of large-size alloys. Heat treatment in a box furnace equipped with a lifting rotating disk ensures more uniform heating of the sample, and this method facilitates the movement and water quenching of large-size alloys, solving the problem of difficulty in clamping and moving alloys due to their large size and weight. Simultaneously, a reasonable heat treatment temperature range and time allow for the efficient handling of δ-Cu alloys. 41 Sn 11 The phase transformation results in more β, γ, and ε phases in the slip system, which significantly improves the plasticity of the alloy. Attached Figure Description

[0012] Figure 1 This is a microstructure image of the high-solute, high-plasticity Cu-Sn-Ti alloy prepared in Example 4 of the present invention;

[0013] Figure 2 These are density variation curves of high-solute, high-plasticity Cu-Sn-Ti alloys prepared in the four embodiments of the present invention.

[0014] Figure 3 These are the mechanical property curves of the high-solute, high-plasticity Cu-Sn-Ti alloys prepared in the four embodiments of the present invention. Detailed Implementation

[0015] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0016] The preparation method of the high-solute, high-plasticity Cu-Sn-Ti alloy of the present invention is as follows: First, high-solute Cu-Sn-Ti alloy powder with specific indicators is injected into a copper cladding and fully vibrated. Then, the copper cladding is vacuumed and the copper conduit is sealed under room temperature and high temperature conditions respectively. Then, it is sintered and densified under hot isostatic pressing. Finally, the copper cladding is subjected to solid solution treatment to obtain the high-solute, high-plasticity Cu-Sn-Ti alloy.

[0017] The preparation method of the present invention is specifically implemented according to the following steps:

[0018] Step 1: Fill the copper cladding with Cu-Sn-Ti alloy powder.

[0019] The specific process is as follows:

[0020] 1.1) When the vacuum degree is ≤10 -1In the glove box of Pa, dry Cu-Sn-Ti alloy powder is gradually injected into a copper cladding (using a large-size T2 copper cladding) through the powder injection hole on the upper end face. During this process, the amount of powder injected each time is controlled between 500 and 1000 g. The dry Cu-Sn-Ti alloy powder has a Sn content of 15-20 wt.%, a Ti content of 0.3 wt.%, and the balance is Cu. The particle size of the Cu-Sn-Ti alloy powder is 0.1-150 μm, the median particle size is 10-40 μm, and the oxygen content is ≤120 ppm.

[0021] 1.2) Mechanically compact the powder using a powder compactor at a frequency of 300-400 times / min for 60-120 seconds to ensure dense powder filling.

[0022] 1.3) Repeat the powder injection and mechanical compaction process until the powder completely fills the copper sleeve and no further injection can be carried out after compaction, then seal the powder injection hole on the upper end face.

[0023] 1.4) Then the copper sleeve is inverted, and a new powder injection hole is machined in the center of the lower end face of the copper sleeve. Cu-Sn-Ti alloy powder is gradually injected and mechanically compacted to fill the gaps between the powders until no more powder can be injected. At this point, the Cu-Sn-Ti alloy powder in the copper sleeve is completely and uniformly compacted.

[0024] 1.5) Then, using SCu5210 tin bronze welding wire as the welding material, argon arc welding was used to weld the copper conduit (the copper conduit was made of T2 copper material) at the powder injection hole on the lower end face.

[0025] Step 2: Perform vacuum and heat insulation treatment on the copper cladding.

[0026] The specific process is as follows:

[0027] 2.1) At room temperature, a three-stage pump system consisting of a mechanical pump, a vacuum pump, and a diffusion pump is used to evacuate the copper cladding through a copper conduit, achieving a vacuum level ≤10 inside the copper cladding. -3 Maintain at Pa for 4–8 hours;

[0028] 2.2) Transfer the copper cladding to an argon atmosphere heat treatment furnace for high-temperature vacuuming, keeping the vacuum level inside the copper cladding constant. The holding temperature is 400-500℃ and the holding time is 8-12h. After the holding time is completed, allow the copper cladding to cool slowly with the furnace, continuously evacuating the vacuum until the copper cladding drops to room temperature.

[0029] 2.3) Remove the copper cladding from the heat treatment furnace, immediately seal the copper conduit with welding pliers, and then stop evacuating the copper cladding to ensure a high vacuum environment inside the copper cladding.

[0030] Step 3: Perform hot isostatic pressing on the copper cladding.

[0031] The specific process is as follows:

[0032] Place the copper cladding in a hot isostatic pressing (HIP) apparatus and evacuate the apparatus to a vacuum level ≤10. -1 At Pa, argon gas at 8 MPa is continuously injected into the pressurizing cylinder as an atmosphere protection and pressurizing medium; then, the holding temperature is raised to between 600 and 820°C at a heating rate of 2–5°C / min, the pressure inside the pressurizing cylinder is 120–200 MPa, and the holding time is 6–12 hours; after the holding is completed, the furnace is slowly cooled until the furnace temperature is ≤200°C, then the argon gas is removed and the copper cladding is taken out.

[0033] Step 4: Heat treat and quench the copper cladding, then remove the copper cladding to obtain the finished product.

[0034] The specific process is as follows:

[0035] 4.1) Do not remove the sintered and densified high-solute Cu-Sn-Ti alloy beforehand, and retain the copper cladding to ensure that the alloy is always in a high vacuum environment; place the copper cladding in a heat treatment box furnace equipped with a lifting rotary table for heat treatment in air, with a holding temperature of 600-700℃, a holding time of 60-96h, and a rotary table speed of 10-20r / min;

[0036] 4.2) After the heat preservation is completed, stop the rotation of the rotating disk, quickly control the lifting platform to move the copper cladding out of the heat dissipation area and lower it to a suitable height, and immediately push the copper cladding into the pre-prepared sufficient amount of cold water for quenching.

[0037] 4.3) Remove the copper cladding by turning to obtain a high-solute, high-plasticity Cu-Sn-Ti alloy.

[0038] The principle of the preparation method of this invention is: based on the restriction of grain size by alloy powder and δ-Cu 41 Sn 11 The microstructure advantage of phase segregation lays the foundation for the alloy's high plasticity. By controlling key powder parameters such as particle size distribution range and median particle size, the distribution composition of powder in each particle size range was optimized, achieving the theoretical maximum tap density of naturally graded powder. Controlling the single powder injection amount and tapping process based on powder parameters maximized the actual tap density of the powder. Vacuuming the copper cladding at room temperature to high temperature to remove air from the powder gaps as much as possible further reduced powder oxidation during sintering, promoting not only the formation of sintering necks but also preventing δ-Cu oxidation. 41 Sn 11The use of oxides as nucleation sites exacerbates segregation. Taking full advantage of hot isostatic pressing (HIP) for easily preparing large-size alloys, the formation of sintering necks in the alloy powder is promoted through reasonable control of the HIP process. Furthermore, based on the small grain size of the alloy powder, a large number of large-angle grain boundaries and annealing twins are introduced, further improving the tensile strength of the alloy. Simultaneously, grain refinement increases the number of alloy grain boundaries, further refining the δ-Cu phase. 41 Sn 11 The size of the phases is reduced and their dispersed distribution is improved, thus reducing stress concentration during plastic deformation and enhancing alloy plasticity. The lifting-type heat treatment method solves the problem of handling and moving large-size alloys due to their large size and weight, while rotary heating solves the problem of uneven heating in large-size alloys. Simultaneously, reasonable solution treatment parameters promote the growth of δ-Cu phases. 41 Sn 11 Beneficial phase transformations play a key role in improving the plasticity of alloys.

[0039] Example 1

[0040] Step 1, under a vacuum degree ≤10 -1 In a glove box of Pa, dry spherical Cu-Sn-Ti alloy powder (with a particle size range of 0.1–75 μm, a median particle size of 26 μm, and an oxygen content ≤120 ppm, wherein the Sn content is 16 wt.%, the Ti content is fixed at 0.3 wt.%, and the balance is Cu) is gradually injected into a large-size T2 copper sheath through the powder injection hole on the upper end face. Each injection is controlled at 650 g, followed by mechanical compaction on a powder compactor at a vibration frequency of 340 times / min for 100 s to ensure dense powder filling. The powder injection and mechanical compaction process is repeated until the copper sheath is completely filled with powder and vibration can no longer be continued, at which point the powder injection hole is sealed. Then, the copper cladding is inverted, and a powder injection hole is machined at the center of the original bottom end of the copper cladding. Alloy powder is gradually injected and the above process is reversed and mechanically compacted to fill the powder gaps and achieve uniform compaction of alloy powder in the axial direction of the copper cladding. Then, using SCu5210 tin bronze welding wire as welding material, T2 copper conduit is welded at the powder injection hole on the lower end face using argon arc welding.

[0041] Step 2: At room temperature, use a three-stage pump system (mechanical pump-vacuum pump-diffusion pump) to evacuate the copper sheath through a copper conduit, achieving a vacuum level ≤10 inside the copper sheath. -3 The copper cladding was held at a pressure of Pa for 5 hours. Then, it was transferred to an argon atmosphere heat treatment furnace for high-temperature vacuum evacuation, maintaining the vacuum level inside the cladding. The holding temperature was 475℃ for 9 hours. After the holding period, the copper cladding was allowed to cool slowly in the furnace, with continuous vacuum evacuation until it reached room temperature. The cladding was then removed from the furnace, and the copper conduit was immediately sealed with welding pliers. The vacuum evacuation was then stopped to ensure a high vacuum environment within the cladding.

[0042] Step 3: Place the copper cladding in a hot isostatic pressing (HIP) apparatus and evacuate the apparatus to a vacuum level ≤10. -1 At pressure of Pa, argon gas at 8 MPa was continuously injected into the pressurized cylinder as a protective atmosphere and pressurizing medium. Then, the holding temperature was increased to between 800℃ and 120 MPa at a heating rate of 5℃ / min, and the holding time was 12 hours. After the holding period, the furnace was slowly cooled until the furnace temperature was ≤200℃, at which point the argon gas was removed, and the copper cladding was taken out.

[0043] Step 4: Without removing the sintered and densified high-solute Cu-Sn-Ti alloy beforehand, retain the copper cladding to ensure the alloy remains in a high vacuum environment. Place the copper cladding in a heat treatment box furnace equipped with a lifting rotary table for air heat treatment at 700℃ for 60 hours, with the rotary table rotating at 20 r / min. After the heat treatment, stop the rotation of the rotary table, quickly control the lifting platform to remove the copper cladding from the heating element area and lower it to a suitable height. Immediately push the copper cladding into a sufficient amount of pre-prepared cold water for quenching. Subsequently, machine off the copper cladding to obtain the high-solute, high-plasticity Cu-Sn-Ti alloy.

[0044] The high-solute Cu-Sn-Ti alloy prepared in Example 1 was tested and found to have a density of 99.8%, an ultimate tensile strength of 464.6 MPa, a yield strength of 180.9 MPa, and an elongation of 35.8%.

[0045] Example 2

[0046] Step 1, under a vacuum degree ≤10 -1 In a glove box of Pa, dry spherical Cu-Sn-Ti alloy powder (with a particle size range of 0.1–106 μm, a median particle size of 19 μm, and an oxygen content ≤120 ppm, wherein the Sn content is 15 wt.%, the Ti content is fixed at 0.3 wt.%, and the balance is Cu) is gradually injected into a large-size T2 copper sheath through the powder injection hole on the upper end face. Each injection is controlled at 800 g, followed by mechanical compaction on a powder compactor at a vibration frequency of 375 times / min for 80 s to ensure dense powder filling. The powder injection and mechanical compaction process is repeated until the copper sheath is completely filled with powder and vibration can no longer be continued, at which point the powder injection hole on the upper end face is sealed. Then, the copper cladding is inverted, and a powder injection hole is machined at the center of the original bottom end of the copper cladding. Alloy powder is gradually injected and the above process is reversed and mechanically compacted to fill the powder gaps and achieve uniform compaction of alloy powder in the axial direction of the copper cladding. Then, using SCu5210 tin bronze welding wire as welding material, T2 copper conduit is welded at the powder injection hole on the lower end face using argon arc welding.

[0047] Step 2: At room temperature, use a three-stage pump system (mechanical pump-vacuum pump-diffusion pump) to evacuate the copper sheath through a copper conduit, achieving a vacuum level ≤10 inside the copper sheath. -3 The copper cladding was held at a pressure of Pa for 6 hours, then transferred to an argon atmosphere heat treatment furnace for high-temperature vacuum evacuation. The vacuum level inside the copper cladding remained constant, and the holding temperature was 500℃ for 8 hours. After the holding period, the copper cladding was allowed to cool slowly with the furnace, with continuous vacuum evacuation during this time, until the copper cladding reached room temperature. The copper cladding was then removed from the heat treatment furnace, and the copper conduit was immediately sealed with welding pliers. The vacuum evacuation of the copper cladding was then stopped to ensure a high vacuum environment inside the copper cladding.

[0048] Step 3: Place the copper cladding in a hot isostatic pressing (HIP) apparatus and evacuate the apparatus to a vacuum level ≤10. -1 At a pressure of 8 MPa, argon gas was continuously injected into the pressurized cylinder as a protective atmosphere and pressurizing medium. Then, the holding temperature was increased to between 740°C and 145 MPa at a heating rate of 3°C / min, and the holding time was 10 hours. After the holding period, the furnace was slowly cooled until the furnace temperature was ≤200°C, at which point the argon gas was removed, and the copper cladding was taken out.

[0049] Step 4: Without removing the sintered and densified high-solute Cu-Sn-Ti alloy beforehand, retain the copper cladding to ensure the alloy remains in a high vacuum environment. Place the copper cladding in a heat treatment box furnace equipped with a lifting rotary table for air heat treatment at 650℃ for 72 hours, with the rotary table rotating at 16 r / min. After the heat treatment, stop the rotary table and quickly control the lifting platform to remove the copper cladding from the heating element area and lower it to a suitable height. Immediately push the copper cladding into a sufficient amount of pre-prepared cold water for quenching. Subsequently, machine off the copper cladding to obtain the high-solute, high-plasticity Cu-Sn-Ti alloy.

[0050] The high-solute Cu-Sn-Ti alloy prepared in Example 2 was tested and found to have a density of 99.9%, an ultimate tensile strength of 580.5 MPa, a yield strength of 293.0 MPa, and an elongation of 67.2%.

[0051] Example 3

[0052] Step 1, under a vacuum degree ≤10 -1In a glove box of Pa, dry spherical Cu-Sn-Ti alloy powder (with a particle size range of 0.1–53 μm, a median particle size of 11 μm, and an oxygen content ≤120 ppm, wherein the Sn content is 20 wt.%, the Ti content is fixed at 0.3 wt.%, and the balance is Cu) is gradually injected into a large-size T2 copper sheath through the powder injection hole on the upper end face. Each injection is controlled at 500 g, followed by mechanical compaction on a powder compactor at a vibration frequency of 300 times / min for 120 s to ensure dense powder filling. The powder injection and mechanical compaction process is repeated until the copper sheath is completely filled with powder and vibration can no longer be continued, at which point the powder injection hole on the upper end face is sealed. Then, the copper cladding is inverted, and a powder injection hole is machined at the center of the original bottom end of the copper cladding. Alloy powder is gradually injected and the above process is reversed and mechanically compacted to fill the powder gaps and achieve uniform compaction of alloy powder in the axial direction of the copper cladding. Then, using SCu5210 tin bronze welding wire as welding material, T2 copper conduit is welded at the powder injection hole on the lower end face using argon arc welding.

[0053] Step 2: At room temperature, use a three-stage pump system (mechanical pump-vacuum pump-diffusion pump) to evacuate the copper sheath through a copper conduit, achieving a vacuum level ≤10 inside the copper sheath. -3 The copper cladding was held at a pressure of Pa for 4 hours, then transferred to an argon atmosphere heat treatment furnace for high-temperature vacuum evacuation. The vacuum level inside the copper cladding remained constant, and the holding temperature was 400℃ for 12 hours. After the holding period, the copper cladding was allowed to cool slowly in the furnace, with continuous vacuum evacuation until it reached room temperature. The copper cladding was then removed from the heat treatment furnace, and the copper conduit was immediately sealed with welding pliers. The vacuum evacuation of the copper cladding was then stopped to ensure a high vacuum environment inside the cladding.

[0054] Step 3: Place the copper cladding in a hot isostatic pressing (HIP) apparatus and evacuate the apparatus to a vacuum level ≤10. -1 At pressure of Pa, argon gas at 8 MPa was continuously injected into the pressurized cylinder as a protective atmosphere and pressurizing medium. Then, the holding temperature was increased to between 625°C and 200 MPa at a heating rate of 2°C / min, and the holding time was 8 hours. After the holding period, the furnace was slowly cooled until the furnace temperature was ≤200°C, at which point the argon gas was removed, and the copper cladding was taken out.

[0055] Step 4: Without removing the sintered and densified high-solute Cu-Sn-Ti alloy beforehand, retain the copper cladding to ensure the alloy remains in a high vacuum environment. Place the copper cladding in a heat treatment box furnace equipped with a lifting rotary table for air heat treatment at 600℃ for 96 hours, with the rotary table rotating at 10 r / min. After the heat treatment, stop the rotation of the rotary table, quickly control the lifting platform to remove the copper cladding from the heating element area and lower it to a suitable height, then immediately push the copper cladding into a sufficient amount of pre-prepared cold water for quenching. Subsequently, machine off the copper cladding to obtain the high-solute, high-plasticity Cu-Sn-Ti alloy.

[0056] The high-solute Cu-Sn-Ti alloy prepared in Example 3 was tested and found to have a density of 99.7%, an ultimate tensile strength of 566.4 MPa, a yield strength of 291.3 MPa, and an elongation of 14.1%.

[0057] Example 4

[0058] Step 1, under a vacuum degree ≤10 -1 In a glove box of Pa, dry spherical Cu-Sn-Ti alloy powder (with a particle size range of 0.1–150 μm, a median particle size of 38 μm, and an oxygen content ≤120 ppm, wherein the Sn content is 18 wt.%, the Ti content is fixed at 0.3 wt.%, and the balance is Cu) is gradually injected into a large-size T2 copper sheath through the powder injection hole on the upper end face. Each injection is controlled at 1000 g, followed by mechanical compaction on a powder compactor at a vibration frequency of 400 times / min for 60 seconds to ensure dense powder filling. The powder injection and mechanical compaction process is repeated until the copper sheath is completely filled with powder and vibration can no longer be continued, at which point the powder injection hole on the upper end face is sealed. Then, the copper cladding is inverted, and a powder injection hole is machined at the center of the original bottom end of the copper cladding. Alloy powder is gradually injected and the above process is reversed and mechanically compacted to fill the powder gaps and achieve uniform compaction of alloy powder in the axial direction of the copper cladding. Then, using SCu5210 tin bronze welding wire as welding material, T2 copper conduit is welded at the powder injection hole on the lower end face using argon arc welding.

[0059] Step 2: At room temperature, use a three-stage pump system (mechanical pump-vacuum pump-diffusion pump) to evacuate the copper sheath through a copper conduit, achieving a vacuum level ≤10 inside the copper sheath. -3 The copper cladding was held at a pressure of Pa for 8 hours, then transferred to an argon atmosphere heat treatment furnace for high-temperature vacuum evacuation. The vacuum level inside the copper cladding remained constant, and the holding temperature was 450℃ for 10 hours. After the holding period, the copper cladding was allowed to cool slowly in the furnace, with continuous vacuum evacuation during this time, until the copper cladding reached room temperature. The copper cladding was then removed from the heat treatment furnace, and the copper conduit was immediately sealed with welding pliers. The vacuum evacuation of the copper cladding was then stopped to ensure a high vacuum environment inside the cladding.

[0060] Step 3: Place the copper cladding in a hot isostatic pressing (HIP) apparatus and evacuate the apparatus to a vacuum level ≤10. -1 At pressure Pa, argon gas at a charging pressure of 8 MPa was continuously injected into the pressurized cylinder as a protective atmosphere and pressurizing medium. Subsequently, the holding temperature was increased to between 775°C and 180 MPa at a heating rate of 4°C / min, and the holding time was 6 hours. After the holding period, the furnace was slowly cooled until the furnace temperature ≤200°C, at which point the argon gas was removed, and the copper cladding was taken out.

[0061] Step 4: Without removing the sintered and densified high-solute Cu-Sn-Ti alloy beforehand, retain the copper cladding to ensure the alloy remains in a high vacuum environment. Place the copper cladding in a heat treatment box furnace equipped with a lifting rotary table for air heat treatment at 625℃ for 84 hours, with the rotary table rotating at 12 r / min. After the heat treatment, stop the rotation of the rotary table, quickly control the lifting platform to remove the copper cladding from the heating element area and lower it to a suitable height, then immediately push the copper cladding into a sufficient amount of pre-prepared cold water for quenching. Subsequently, machine off the copper cladding to obtain the high-solute, high-plasticity Cu-Sn-Ti alloy.

[0062] The high-solute Cu-Sn-Ti alloy prepared in Example 4 was tested and found to have a density of 99.9%, an ultimate tensile strength of 506.4 MPa, a yield strength of 228.8 MPa, and an elongation of 23.1%. Figure 1 This is the microstructure of the high-solute, high-plasticity Cu-Sn-Ti alloy prepared in Example 4. It can be seen that the alloy microstructure consists of fine equiaxed grains and numerous annealed twins, while δ-Cu... 41 Sn 11 The β, γ and ε phases are generated inside the phase, which are conducive to the plastic deformation of the alloy.

[0063] Figure 2 The figures show the density variation curves of the high-solute, high-plasticity Cu-Sn-Ti alloys in Examples 1, 2, 3, and 4 above. It can be seen that the alloys prepared in each example have high density, all above 99.7%.

[0064] Figure 3 These are the mechanical property curves of the high-solute, high-plasticity Cu-Sn-Ti alloys in Examples 1, 2, 3, and 4 above. It can be seen that the alloys prepared in each example have both high strength and plasticity, and the plasticity decreases with the increase of Sn content.

Claims

1. A method for producing a high-solute, high-ductility Cu-Sn-Ti alloy, characterized by, The following steps are implemented: Step 1: Inject Cu-Sn-Ti alloy powder into a copper sleeve, wherein the Sn content is 15-20 wt.%, the Ti content is fixed at 0.3 wt.%, and the balance is Cu; the particle size of the Cu-Sn-Ti alloy powder is 0.1-150 μm, the median particle size is 10-40 μm, and the oxygen content is ≤120 ppm, The specific process is: 1.1) in a glove box with a vacuum degree ≤ 10 -1 In a glove box with a vacuum degree ≤ 10 Pa, dry Cu-Sn-Ti alloy powder is gradually injected into a copper sleeve through a powder injection hole in the upper end surface, and the amount of powder injected each time is controlled to be between 500-1000 g; in the dry Cu-Sn-Ti alloy powder, the Sn content is 15-20 wt.%, the Ti content is fixed at 0.3 wt.%, and the balance is Cu; the particle size of the Cu-Sn-Ti alloy powder is 0.1-150 μm, the median particle size is 10-40 μm, and the oxygen content is ≤ 120 ppm; 1.2) Mechanical vibration on the powder compactor, vibration frequency is 300-400 times / min, vibration time is 60-120 s; 1.3) Repeat the powder injection and mechanical vibration process until the powder is completely filled in the copper sleeve, and the powder injection hole at the upper end face is sealed after vibration; 1.4) Then turn the copper sleeve upside down, and process a new powder injection hole at the center of the lower end face of the copper sleeve, gradually inject Cu-Sn-Ti alloy powder and mechanically vibrate to fill the powder gap, until no powder can be injected, at which point the Cu-Sn-Ti alloy powder in the copper sleeve is completely and uniformly vibrated; 1.5) Then use SCu5210 tin bronze welding wire as welding material to weld the copper conduit at the lower end face powder injection hole using argon arc welding; Step 2: Vacuum and heat treatment of the copper sleeve, the specific process is: 2.1) Copper jacket is evacuated by copper conduit at room temperature using a mechanical-pump-vacuum-pump-diffusion-pump three-stage pump system, and the vacuum degree inside the copper jacket is ≤10 -3 Pa, and the state is maintained for 4-8 h; 2.2) Transfer the copper sleeve to the argon atmosphere heat treatment furnace for high temperature vacuumizing, the internal vacuum degree of the copper sleeve remains unchanged, the holding temperature is 400-500℃, and the holding time is 8-12h; after holding, the copper sleeve is slowly cooled with the furnace, and vacuum is continuously extracted during the process until the copper sleeve is cooled to room temperature; 2.3) Take out the copper sleeve from the heat treatment furnace, immediately seal the copper conduit using a welding tongs, and then stop vacuumizing the copper sleeve; Step 3: Hot isostatic pressing treatment of the copper sleeve, the specific process is: The copper sheath is placed in a hot isostatic pressing device, the device is vacuumed to a vacuum degree ≤10 -1 When the temperature reaches 400~500℃, 8MPa argon is continuously injected into the pressure cylinder as atmosphere protection and pressurizing medium; then the temperature is raised to 600~820℃ at a heating rate of 2~5℃ / min, the pressure in the pressure cylinder is 120~200MPa, and the temperature holding and pressure holding time is 6~12h; after the temperature holding and pressure holding is completed, the argon is removed when the furnace temperature is ≤200℃, and the copper sheath is taken out. Step 4: Heat treatment and quenching of the copper sleeve, and removing the copper sleeve to obtain a high solute high plasticity Cu-Sn-Ti alloy product, the specific process is: 4.1) Place the copper sleeve in a heat treatment box furnace equipped with a lifting rotary disc for heat treatment in air, the holding temperature is 600-700℃, the holding time is 60-96h, and the rotation speed of the rotary disc is 10-20 r / min; 4.2) After holding, stop the rotation of the rotary disc, quickly control the lifting platform to move the copper sleeve out of the heating body range and lower it to an appropriate height, and immediately push the copper sleeve into a sufficient amount of cold water for quenching; 4.3) Remove the copper sleeve by turning and obtain a high solute high plasticity Cu-Sn-Ti alloy.

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