Method for preparing tungsten-copper through pipe through one-step hot isostatic pressing method

Abstract

According to the method, tungsten powder, vanadium powder and titanium carbide powder are mixed and then subjected to hot pressed sintering, a composite tungsten plate is obtained, the vanadium element and titanium carbide are added into tungsten alloy, the compactness and thermal stability of the tungsten alloy are improved, a dispersed phase is formed, the pinning effect on grain boundaries and dislocation is achieved, and therefore the tungsten-copper penetrating pipe can be manufactured. A composite tungsten plate is machined into a composite tungsten block, an inner hole is machined in the center of the composite tungsten block, a copper layer is electrically deposited in the inner hole to obtain a composite W / Cu block, the composite W / Cu block, an oxygen-free copper pipe and a CuCrZr pipe are assembled, and the tungsten copper penetrating pipe facing the plasma component is obtained. According to the method for preparing the tungsten-copper through pipe through the one-step hot isostatic pressing method, the problem that according to an existing tungsten-copper through pipe preparation method, heating is conducted twice, the bonding strength of a W / Cu interface can be reduced, and finally the service life of a divertor component is affected is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of metal composite material preparation methods, and specifically relates to a method for preparing a tungsten copper through-tube by a one-step hot isostatic pressing method. Background Art

[0002] Nuclear fusion energy is considered to be the ultimate energy source to solve the energy problem of human beings in the future. During the nuclear fusion reaction, most of the energy is transported to the divertor area in the form of charged particles, and then the heat is taken away by the divertor cooling circulation system. At this time, the plasma-facing components of the divertor will be subjected to high heat loads, high-energy particle irradiation and other severe service environments. The plasma-facing components are mainly composed of materials directly facing the plasma and heat sink materials. Tungsten (W) has the advantages of high melting point, high thermal conductivity, low sputtering rate, and low fuel retention, and is generally used as a material directly facing the plasma. CuCrZr alloy has excellent thermal conductivity, ductility, machinability, and certain strength at high temperatures, and is generally used as a heat sink material.

[0003] The plasma-facing components of the divertor target plate are mainly tungsten-copper tube structures. The thermal expansion coefficients of W and CuCrZr alloys differ greatly. In order to reduce fatigue cracks at the interface between W and CuCrZr alloys during high heat flux cycle loading, oxygen-free Cu is generally added as a stress relief layer. The interface bonding between W and Cu heterogeneous materials is a difficult problem. At present, the preparation process of tungsten-copper tubes is mainly to compound W with Cu and W / Cu with CuCrZr by a two-step hot isostatic pressing method. However, the two-step hot isostatic pressing preparation process is complicated and environmentally unfriendly, and after two heatings, the bonding strength of the W / Cu interface will be reduced, which will eventually affect the service life of the divertor components. At the same time, as a plasma-facing material, tungsten is introduced into the plasma due to the aggregation and bubbling of hydrogen and helium particles in tungsten, which seriously affects the mechanical properties of the plasma-facing material and further affects its service life in the nuclear fusion reactor. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing a tungsten copper tube by a one-step hot isostatic pressing method, which solves the problem that the existing tungsten copper tube preparation method undergoes two heatings, the bonding strength of the W / Cu interface is reduced, and ultimately the service life of the divertor components is affected.

[0005] The technical scheme adopted by the present invention is: a method for preparing a tungsten copper tube by a one-step hot isostatic pressing method, tungsten powder, vanadium powder and titanium carbide powder are mixed and then hot-pressed and sintered to obtain a composite tungsten plate, vanadium element and titanium carbide are added to the tungsten alloy to improve the density and thermal stability of the tungsten alloy, and to form a dispersed phase to pin grain boundaries and dislocations, the composite tungsten plate is processed into a composite tungsten block and an inner hole is processed at the center position, a copper layer is electrodeposited in the inner hole to obtain a composite W / Cu block, and the composite W / Cu block is assembled with an oxygen-free copper tube and a CuCrZr tube to obtain a tungsten copper tube facing a plasma component.

[0006] The technical solution adopted by the present invention is also characterized in that: Further, a method for preparing a tungsten copper tube by a one-step hot isostatic pressing method is specifically prepared according to the following steps: Step 1, mixing the ingredients according to the mass percentage of tungsten powder 85-95.9%, vanadium powder 4-14% and titanium carbide powder 0.1-1%, and mixing the ingredients after mixing; Step 2, injecting the powder mixed in step 1 into the mold, placing the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite tungsten plate; Step 3, the composite tungsten plate is machined into a plurality of composite tungsten blocks, and an inner hole is cut at the center of the composite tungsten block by wire cutting; Step 4: After pre-treating the inner hole of the composite tungsten block, a copper layer is electrodeposited on the inner hole wall of the composite tungsten block to obtain a composite W / Cu block; Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; Step 6: Hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a tungsten copper tube facing the plasma component.

[0007] Furthermore, step 1 is specifically as follows: tungsten powder, vanadium powder and titanium carbide powder are mixed by a mixer, wherein the particle size of the tungsten powder and vanadium powder is 1-10 μm, the particle size of the titanium carbide powder is 50 nm-5 μm, the mixer speed is 100-500 r / min, and the mixing time is 5-15 h.

[0008] Furthermore, step 2 is as follows: the hot pressing sintering process adopts segmented insulation. In a vacuum environment, the temperature is raised to 800~1100℃ in the first period, and kept warm for 1~3h, with a heating rate of 8~10℃ / min. The temperature is raised to 1600~2000℃ in the second period, and kept warm for 2~5h, with a heating rate of 5~8℃ / min. A pressure of 30~100MPa is applied during the heating process.

[0009] Furthermore, in step 3, the size of the composite tungsten block is (20-30)×(20-30)×(10-20) mm, and the size of the central inner hole of the composite tungsten block is φ15-φ20 mm.

[0010] Furthermore, the electrodeposition process in step 4 is specifically as follows: Step 4.1, pre-treating the inner hole wall of the composite tungsten block by acid washing and alkali washing; The acid cleaning process is: soaking in H2SO4 solution with a pH value of 1 to 3 for 5 to 15 minutes; the alkaline cleaning process is: soaking in NaOH solution with a pH value of 10 to 13 for 5 to 15 minutes. After each step, ultrasonic cleaning is performed with deionized water. Step 4.2, coating the contact surface other than the inner hole wall of the composite tungsten block with epoxy resin for sealing, and during the electrodeposition, only the inner hole wall not protected by the resin can be deposited with copper film; Step 4.3: In the electrodeposition device, the copper plate is used as the anode, the composite tungsten block is used as the cathode, the electroplating solution is 100-200 g / L CuSO4 solution, and the current intensity is 5-20 A / dm 2 The electroplating time is 2h~15h, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0011] Furthermore, the assembly process of the tungsten copper tube in step 5 is as follows: Step 5.1, the tungsten copper tubes are CuCrZr tube, oxygen-free copper tube, electrodeposited copper layer and composite tungsten block from inside to outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu block after the electrodeposited copper layer; Step 5.2, fill both ends of the assembly with copper powder, use a stainless steel plate as a sheath, pass the sheath through the middle hole of the CuCrZr tube, seal the entire assembly and the copper powder at both ends, and obtain a tungsten copper tube assembly.

[0012] Furthermore, in the hot isostatic pressing process in step 6, the temperature is raised to 600-1000° C., kept at this temperature for 2-5 hours, and then cooled with the furnace. The pressure during the heating and keeping process is 100-200 MPa.

[0013] The beneficial effects of the present invention are: (1) The preparation method of the present invention adds V element to tungsten to achieve the effect of alloy strengthening, thereby improving the density and thermal stability of the tungsten alloy and improving its radiation resistance; TiC particles form a dispersed phase in the tungsten alloy, which pins the grain boundaries and dislocations and inhibits the growth of W grains, thereby improving the high-temperature mechanical properties of the alloy; the joint strengthening of V element and TiC particles can not only improve the mechanical properties of tungsten, but also become the gathering center of hydrogen and helium particles in tungsten, attracting, transporting and depositing them, avoiding the influence of hydrogen and helium particles on tungsten, thereby extending the service life of tungsten in fusion reactors; at the same time, the present invention can adjust the mechanical properties of tungsten alloy by adjusting the content of V and TiC, and setting different sintering temperatures and pressures.

[0014] (2) The physical and chemical properties of heterogeneous materials W and Cu are quite different. Directly combining W and Cu will reduce the W / Cu interface strength. However, the preparation method of the present invention enables Cu and W to form a strong chemical bond through electroplating, which has good adhesion, high interface bonding strength and is not easy to fall off. Therefore, Cu is electroplated as an intermediate transition layer to transform the heterogeneous material connection of W and Cu into the homogeneous material connection of Cu and Cu. At the same time, because the physical and chemical properties of Cu and CuCrZr are not much different, a one-step hot isostatic pressing connection can be achieved, that is, the Cu / Cu interface and the Cu / CuCrZr interface are simultaneously subjected to hot isostatic pressing to prepare a tungsten copper tube material. At the same time, the present invention can accurately control the thickness of the copper layer by adjusting the process parameters of the electroplating, thereby reducing the cost of machining. In addition, the copper deposition has high uniformity, which can ensure the performance consistency of each part of the hole wall in the tungsten block and avoid defects caused by welding. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a schematic diagram of the tungsten copper tube assembly prepared by the present invention; Figure 2 It is a flow chart of the preparation method of the present invention. DETAILED DESCRIPTION

[0016] The present invention is further described below through the accompanying drawings and specific embodiments.

[0017] The present invention provides a method for preparing a tungsten copper tube by a one-step hot isostatic pressing method, and the specific steps include: Step 1: Prepare W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a "V" type mixer; In step 1, the particle size of W powder and V powder is 1-10 μm, and the particle size of TiC powder is 50 nm-5 μm; W powder, V powder and TiC powder are weighed according to the mass percentage of 85-95.9%: 4-14%: 0.1-1%; When mixing using a "V" type mixer in step 1, the rotation speed is 100~500r / min and the mixing time is 5~15h.

[0018] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; In step 2, the hot pressing sintering process adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 800-1100°C for 1-3 hours at a heating rate of 8-10°C / min, and then raised to 1600-2000°C for 2-5 hours at a heating rate of 5-8°C / min. A pressure of 30-100 MPa is applied during the heating process.

[0019] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is (20~30)×(20~30)×(10~20) mm, and the size of the central inner hole of the composite tungsten block is φ15~φ20 mm.

[0020] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaking in a 1~5mol / L dilute H2SO4 solution for 5~15min, and the alkaline washing process is soaking in a 1~5mol / L NaOH solution for 5~15min. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 100~200g / L CuSO4 solution, and the current intensity is 5~20A / dm 2 The electroplating time is 2h~15h, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0021] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0022] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 600-1000°C, kept at this temperature for 2-5 hours, and then cooled with the furnace. The pressure during the heating and holding process is 100-200 MPa.

[0023] The method for preparing a tungsten copper tube by a one-step hot isostatic pressing method and the performance of the tungsten copper tube prepared by the present invention are further described below by means of specific examples.

[0024] Embodiment 1: Step 1: Prepare W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a "V" type mixer; In step 1, the particle sizes of W powder and V powder are 3 μm, and the particle size of TiC powder is 0.5 μm; W powder, V powder and TiC powder are weighed in a mass percentage of 85%:14%:1%; When mixing using a "V" type mixer in step 1, the rotation speed is 100 r / min and the mixing time is 15 h.

[0025] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; The hot pressing sintering process in step 2 adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 800°C for 3 hours at a heating rate of 10°C / min, and then raised to 1850°C for 5 hours at a heating rate of 8°C / min. A pressure of 80MPa is applied during the heating process.

[0026] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is 20×20×10 mm, and the size of the central inner hole of the composite tungsten block is φ15 mm.

[0027] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaked in a dilute H2SO4 solution with a pH value of 1 for 5 minutes, and the alkaline washing process is soaked in a NaOH solution with a pH value of 13 for 5 minutes. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 100g / L CuSO4 solution, and the current intensity is 10A / dm 2 The electroplating time is 12 hours, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0028] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0029] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 600° C., kept at this temperature for 5 hours, and then cooled with the furnace. The pressure during the heating and holding process is 100 MPa.

[0030] Embodiment 2: Step 1: Prepare W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a "V" type mixer; In step 1, the particle size of W powder and V powder is 6 μm, and the particle size of TiC powder is 2 μm; W powder, V powder and TiC powder are weighed in a mass percentage of 95.9%:4%:0.1%; When mixing using a "V" type mixer in step 1, the rotation speed is 300r / min and the mixing time is 10h.

[0031] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; The hot pressing sintering process in step 2 adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 1100°C for 2 hours at a heating rate of 9°C / min, and then raised to 1850°C for 3 hours at a heating rate of 7°C / min. A pressure of 60MPa is applied during the heating process.

[0032] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is 26×26×15 mm, and the size of the central inner hole of the composite tungsten block is φ17 mm.

[0033] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaked in a dilute H2SO4 solution with a pH value of 3 for 15 minutes, and the alkaline washing process is soaked in a NaOH solution with a pH value of 13 for 15 minutes. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 100g / L CuSO4 solution, and the current intensity is 15A / dm 2 The electroplating time is 8 hours, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0034] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0035] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 600° C., kept at this temperature for 2 hours, and then cooled with the furnace. The pressure during the heating and holding process is 200 MPa.

[0036] Embodiment 3: Step 1: Prepare W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a "V" type mixer; In step 1, the particle size of W powder and V powder is 9 μm, and the particle size of TiC powder is 5 μm; W powder, V powder and TiC powder are weighed in a mass percentage of 90%:9.8%:0.2%; When mixing using a "V" type mixer in step 1, the rotation speed is 500r / min and the mixing time is 5h.

[0037] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; The hot pressing sintering process in step 2 adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 1100°C for 1 hour at a heating rate of 8°C / min, and then raised to 2000°C for 2 hours at a heating rate of 5°C / min. A pressure of 40MPa is applied during the heating process.

[0038] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is 30×30×20 mm, and the size of the central inner hole of the composite tungsten block is φ20 mm.

[0039] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaked in a dilute H2SO4 solution with a pH value of 3 for 15 minutes, and the alkaline washing process is soaked in a NaOH solution with a pH value of 10 for 15 minutes. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 200g / L CuSO4 solution, and the current intensity is 15A / dm 2 The electroplating time is 12 hours, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0040] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0041] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 1000° C., kept at this temperature for 2 hours, and then cooled with the furnace. The pressure during the heating and holding process is 100 MPa.

[0042] Embodiment 4: Step 1: Mix W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a conical mixer; In step 1, the particle size of W powder and V powder is 1 μm, and the particle size of TiC powder is 2 μm; W powder, V powder and TiC powder are weighed in a mass percentage of 92%:7.5%:0.5%; When mixing using a conical mixer in step 1, the rotation speed is 500 r / min and the mixing time is 5 h.

[0043] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; The hot pressing sintering process in step 2 adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 1000°C for 1 hour at a heating rate of 8°C / min, and then raised to 1600°C for 2 hours at a heating rate of 5°C / min. A pressure of 40MPa is applied during the heating process.

[0044] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is 30×30×20 mm, and the size of the central inner hole of the composite tungsten block is φ20 mm.

[0045] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaking in a dilute H2SO4 solution with a pH value of 2 for 15 minutes, and the alkaline washing process is soaking in a NaOH solution with a pH value of 12 for 15 minutes. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 150g / L CuSO4 solution, and the current intensity is 5A / dm 2 The electroplating time is 2h, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0046] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0047] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 700° C., kept at this temperature for 4 hours, and then cooled with the furnace. The pressure applied during the heating and holding process is 160 MPa.

[0048] Example 5 Step 1: Prepare W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a "V" type mixer; In step 1, the particle size of W powder and V powder is 10 μm, and the particle size of TiC powder is 0.5 μm; W powder, V powder and TiC powder are weighed according to the mass percentage of 87.5%:12%:0.5%; When mixing using a "V" type mixer in step 1, the rotation speed is 100 r / min and the mixing time is 15 h.

[0049] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; The hot pressing sintering process in step 2 adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 800°C for 3 hours at a heating rate of 10°C / min, and then raised to 1850°C for 5 hours at a heating rate of 8°C / min. A pressure of 30MPa is applied during the heating process.

[0050] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is 20×20×10 mm, and the size of the central inner hole of the composite tungsten block is φ15 mm.

[0051] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaked in a dilute H2SO4 solution with a pH value of 1 for 9 minutes, and the alkaline washing process is soaked in a NaOH solution with a pH value of 13 for 9 minutes. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 100g / L CuSO4 solution, and the current intensity is 20A / dm 2 The electroplating time is 12 hours, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0052] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0053] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 600° C., kept at this temperature for 5 hours, and then cooled with the furnace. The pressure during the heating and holding process is 100 MPa.

[0054] Embodiment 6: Step 1: Prepare W powder, V powder and TiC powder according to the stoichiometric ratio and mix them using a "V" type mixer; In step 1, the particle size of W powder and V powder is 6 μm, and the particle size of TiC powder is 2 μm; W powder, V powder and TiC powder are weighed in a mass percentage of 95%:4%:1%; When mixing using a "V" type mixer in step 1, the rotation speed is 300r / min and the mixing time is 10h.

[0055] Step 2: inject the mixed powder into a mold, place the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite W plate; The hot pressing sintering process in step 2 adopts segmented heat preservation. In a vacuum environment, the temperature is raised to 1100°C for 2 hours at a heating rate of 9°C / min, and then raised to 1850°C for 3 hours at a heating rate of 7°C / min. A pressure of 100MPa is applied during the heating process.

[0056] Step 3, the composite W plate is machined into a plurality of composite W blocks, and an inner hole is cut at the center of the composite W block by wire cutting; In step 3, the size of the composite tungsten block is 26×26×15 mm, and the size of the central inner hole of the composite tungsten block is φ17 mm.

[0057] Step 4, after pre-treating the inner holes of the plurality of composite W blocks, electro-depositing a copper layer on the inner hole walls of the plurality of composite W blocks to obtain a plurality of composite W / Cu blocks; The electrodeposition process in step 4 is as follows: (1) the inner pore wall of the composite W block is pretreated by acid washing and alkaline washing; the acid washing process is soaked in a dilute H2SO4 solution with a pH value of 3 for 15 minutes, and the alkaline washing process is soaked in a NaOH solution with a pH value of 13 for 15 minutes. After each step, ultrasonic cleaning is performed with deionized water; (2) the contact surface other than the inner pore wall of the composite tungsten block is coated with epoxy resin for sealing. During electrodeposition, only the inner pore wall not protected by the resin can be deposited with copper film; (3) in the electrodeposition device, the copper plate is used as the anode, the composite W block is used as the cathode, the electroplating solution is a 100g / L CuSO4 solution, and the current intensity is 20A / dm 2 The electroplating time is 15 hours, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

[0058] Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; The assembly process of the tungsten copper tube in step 5 is as follows: (1) The tungsten copper tube is composed of a CuCrZr tube, an oxygen-free copper tube, an electrodeposited Cu layer and a composite W block from the inside to the outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu after the electrodeposited Cu layer; (2) Cu powder is used to fill both ends of the assembly, and a stainless steel plate is used as a sheath. The sheath passes through the middle hole of the CuCrZr tube to seal the entire assembly and the Cu powder at both ends to obtain a tungsten copper tube assembly.

[0059] Step 6, hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a plasma-facing tungsten copper tube; In the hot isostatic pressing process in step 6, the temperature is raised to 600° C., kept at this temperature for 2 hours, and then cooled with the furnace. The pressure during the heating and holding process is 200 MPa.

Claims

1. A method for preparing a tungsten copper tube by hot isostatic pressing, characterized in that: Tungsten powder, vanadium powder and titanium carbide powder are mixed and hot-pressed and sintered to obtain a composite tungsten plate. Vanadium and titanium carbide are added to the tungsten alloy to improve the density and thermal stability of the tungsten alloy and form a dispersed phase to pin the grain boundaries and dislocations. The composite tungsten plate is processed into a composite tungsten block and an inner hole is processed at the center. A copper layer is electrodeposited in the inner hole to obtain a composite W / Cu block. The composite W / Cu block is assembled with an oxygen-free copper tube and a CuCrZr tube to obtain a tungsten-copper through-tube facing a plasma component.

2. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 1, characterized in that: Specifically prepared according to the following steps: Step 1, mixing the ingredients according to the mass percentage of tungsten powder 85-95.9%, vanadium powder 4-14% and titanium carbide powder 0.1-1%, and mixing the ingredients after mixing; Step 2, injecting the powder mixed in step 1 into the mold, placing the mold filled with the powder in a hot pressing sintering furnace to perform hot pressing sintering to obtain a composite tungsten plate; Step 3, the composite tungsten plate is machined into a plurality of composite tungsten blocks, and an inner hole is cut at the center of the composite tungsten block by wire cutting; Step 4: After pre-treating the inner hole of the composite tungsten block, a copper layer is electrodeposited on the inner hole wall of the composite tungsten block to obtain a composite W / Cu block; Step 5, assembling a plurality of composite W / Cu blocks with oxygen-free copper tubes and CuCrZr tubes to obtain tungsten-copper tube assemblies; Step 6: Hot isostatic pressing the tungsten copper tube assembly, then removing the sheath and machining it to obtain a tungsten copper tube facing the plasma component.

3. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 2, characterized in that: The step 1 is specifically as follows: tungsten powder, vanadium powder and titanium carbide powder are mixed by a mixer, wherein the particle size of the tungsten powder and vanadium powder is 1-10 μm, the particle size of the titanium carbide powder is 50 nm-5 μm, the mixer speed is 100-500 r / min, and the mixing time is 5-15 h.

4. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 2, characterized in that: The specific details of step 2 are as follows: the hot pressing sintering process adopts segmented insulation. In a vacuum environment, the temperature is raised to 800-1100°C in the first period and kept for 1-3 hours at a heating rate of 8-10°C / min. The temperature is raised to 1600-2000°C in the second period and kept for 2-5 hours at a heating rate of 5-8°C / min. A pressure of 30-100 MPa is applied during the heating process.

5. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 4, characterized in that: In the step 3, the size of the composite tungsten block is (20-30)×(20-30)×(10-20) mm, and the size of the central inner hole of the composite tungsten block is φ15-φ20 mm.

6. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 4, characterized in that: The electrodeposition process in step 4 is specifically as follows: Step 4.1, pre-treating the inner hole wall of the composite tungsten block by acid washing and alkali washing; The acid cleaning process is: soaking in H2SO4 solution with a pH value of 1 to 3 for 5 to 15 minutes; the alkaline cleaning process is: soaking in NaOH solution with a pH value of 10 to 13 for 5 to 15 minutes. After each step, ultrasonic cleaning is performed with deionized water. Step 4.2, coating the contact surface other than the inner hole wall of the composite tungsten block with epoxy resin for sealing, and during the electrodeposition, only the inner hole wall not protected by the resin can be deposited with copper film; Step 4.3: In the electrodeposition device, the copper plate is used as the anode, the composite tungsten block is used as the cathode, the electroplating solution is 100-200 g / L CuSO4 solution, and the current intensity is 5-20 A / dm 2 The electroplating time is 2h~15h, and magnetic stirring is continuously used during the electroplating process to make the copper plating more uniform.

7. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 6, characterized in that: The specific process of assembling the tungsten copper tube in step 5 is as follows: Step 5.1, the tungsten copper tubes are CuCrZr tube, oxygen-free copper tube, electrodeposited copper layer and composite tungsten block from inside to outside; the outer diameter of the CuCrZr tube is slightly smaller than the inner diameter of the oxygen-free copper tube, and the outer diameter of the oxygen-free copper tube is slightly smaller than the inner diameter of the composite W / Cu block after the electrodeposited copper layer; Step 5.2, fill both ends of the assembly with copper powder, use a stainless steel plate as a sheath, pass the sheath through the middle hole of the CuCrZr tube, seal the entire assembly and the copper powder at both ends, and obtain a tungsten copper tube assembly.

8. The method for preparing tungsten copper tube by one-step hot isostatic pressing according to claim 1, characterized in that: In the hot isostatic pressing process in step 6, the temperature is raised to 600-1000° C., kept at this temperature for 2-5 hours, and then cooled with the furnace. The pressure during the heating and keeping process is 100-200 MPa.

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