Preparation method of ods-w / cucrzr through-pipe structure integrated module

Abstract

The application provides a preparation method of an oxidation dispersion strengthened tungsten / copper chromium zirconium penetrating pipe structure monoblock with a gradient intermediate layer and an oxidation dispersion strengthened tungsten / copper chromium zirconium penetrating pipe structure (ODS-W / CuCrZr Monoblock) monoblock with a gradient intermediate layer prepared by the method. The preparation method comprises the following steps: drilling a tungsten plate to form a through hole; forming a multilayer W-Cu intermediate layer blank in the through hole by using a ring gasket and a die; forming a CuCrZr layer blank by using a ring gasket and a die; and then performing SPS sintering. The oxidation dispersion strengthened tungsten / copper chromium zirconium penetrating pipe structure with a gradient intermediate layer has high thermal conductivity, good bonding strength and thermal load performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of dissimilar metal connection, and particularly relates to a preparation method of an oxidation dispersion strengthened tungsten / copper chromium zirconium monoblock (ODS-W / CuCrZr Monoblock) integral module with a gradient intermediate layer and an oxidation dispersion strengthened tungsten / copper chromium zirconium monoblock (ODS-W / CuCrZr Monoblock) integral module with a gradient intermediate layer prepared by the method. BACKGROUND

[0002] Controllable thermonuclear fusion energy is one of the ideal new energies to meet the future energy demand of mankind. In the tokamak device for fusion energy application, the divertor is one of the key core components, which can shield the impurities of the first wall, reduce the pollution to the central plasma, discharge the products (such as helium ash, etc.) of nuclear fusion reaction, withstand the high heat load of the plasma, and discharge the energy and particle flow generated thereby. Therefore, the preparation of high-performance divertor components is one of the great challenges faced by the current running and construction test devices (such as EAST and ITER) and the future CFETR.

[0003] The researches on W / CuCrZr Monoblock at home and abroad mainly focus on the optimization of the connection technology and the improvement of the interface bonding state of W / CuCrZr. Among them, the connection technology mainly includes brazing, diffusion welding, explosive welding and coating, and the improvement of the interface bonding of W / CuCrZr mainly adopts the introduction of an intermediate layer and the nanocrystallization of the surface of W. Overall, these technologies have made some progress, but there are still some deficiencies and limitations. For example, brazing can cause grain coarsening of the joint at high temperature, diffusion welding takes a long time, explosive welding can easily cause cracking of W, and the introduction of an intermediate layer can easily produce brittle metal compounds at the interface of the joint. At present, the divertor target plate for ITER and EAST mainly adopts W / oxygen-free copper (OFCU) / CuCrZr Monoblock components. The introduction of OFCU intermediate layer between W and CuCrZr can improve the interface bonding strength, but due to the large difference in the thermal expansion coefficient between W and Cu, stress concentration can easily occur at the interface between W and the OFCU connecting layer, leading to interface cracking and affecting the stability and reliability of the Monoblock module. Therefore, it is proposed to use W-Cu functional gradient material (W-Cu FGM) as an intermediate layer between W and CuCrZr instead of OFCU, that is, the side with high W content is combined with W, and the side with high Cu content is combined with CuCrZr, which is a possible solution to the high-performance connection problem of W / CuCrZr Monoblock, but there is still a lack of systematic research. On the other hand, the brittleness problem of plasma-facing W materials cannot be ignored, and the addition of second-phase oxide particles, such as Y2O3, ZrO2, La2O3 and Sm2O3, can effectively reduce the DBTT of the material and improve the toughness of the material, thereby improving the performance of the W material.

[0004] In summary, the preparation of the W / CuCrZr Monoblock module has the problems of low connection efficiency, complicated process, long time consumption and the like, and the overall component cannot be obtained directly in one step. At the same time, the inventors believe that optimizing the composition design of the W-Cu gradient layer in the W / CuCrZr Monoblock module and improving the W / Cu interface bonding state can effectively alleviate the thermal stress at the W / Cu interface, which is still one of the key problems of high-performance connection of W / CuCrZr in the Monoblock module. In addition, replacing pure W with ODS-W as a plasma-facing material is also one of the solutions to improve the Monoblock module. Therefore, it is urgent to develop a preparation method of a W / CuCrZr Monoblock integral module with high efficiency, high performance, repeatability and integrated forming. SUMMARY

[0005] TECHNICAL PROBLEM

[0006] In view of the above problems of the prior art, the present application aims to provide a preparation method of an ODS-W / CuCrZr Monoblock integrated module with a gradient intermediate layer and an ODS-W / CuCrZr Monoblock integrated module prepared by the method. The present application introduces a multilayer W-Cu intermediate layer between the oxide dispersion strengthened tungsten (ODS-W) and CuCrZr to reduce the thermal stress caused by the large difference in the thermal expansion coefficients of the two, so as to improve the stability and reliability of the Monoblock integrated module. The ODS-W / CuCrZr Monoblock integrated module directly prepared by the specific compaction forming process and SPS connection technology has excellent bonding strength and thermal load performance, and can better meet the performance requirements of the divertor material in the service environment of the fusion reactor.

[0007] Technical scheme

[0008] According to a first aspect of the present application, a preparation method of an oxide dispersion strengthened tungsten / copper chromium zirconium tube penetrating structure (ODS-W / CuCrZr Monoblock) integrated module with a gradient intermediate layer is provided, which comprises the following steps:

[0009] Step one: drilling a through hole in the oxide dispersion strengthened tungsten plate and performing cleaning treatment;

[0010] Step two: preparing a first annular gasket to an n+2th annular gasket, the first annular gasket to the n+1th annular gasket having different outer diameters and inner diameters, the outer diameters and the inner diameters of the first annular gasket to the n+1th annular gasket decreasing in turn, and the outer diameter of the first annular gasket being the same as the inner diameter of the through hole, the outer diameter of the second annular gasket being the same as the inner diameter of the first annular gasket, based on the same rule, the outer diameter of the n+1th annular gasket being the same as the inner diameter of the nth annular gasket, and the outer diameter of the n+2th annular gasket being the same as the outer diameter of the first annular gasket, and the inner diameter being the same as the inner diameter of the n+1th annular gasket;

[0011] Step three: preparing a first die to an n+1th die, the outer diameters of the first die to the n+1th die being the same as the inner diameters of the first annular gasket to the n+1th annular gasket, respectively, so that the die can be inserted and fixed in the hole of the annular gasket; specifically, the outer diameter of the first die is the same as the inner diameter of the first annular gasket, the outer diameter of the second die is the same as the inner diameter of the second annular gasket, the outer diameter of the third die is the same as the inner diameter of the third annular gasket, and so on until the outer diameter of the n+1th die is the same as the inner diameter of the n+1th annular gasket;

[0012] Step four: place two first annular gaskets at the bottom and top of the through hole respectively, and insert a first die punch into the hole of the first annular gasket, so that the first die punch is fixed in the through hole by the first annular gaskets at the bottom and top of the through hole; add first W-Cu mixed powder into the space enclosed by the inner wall of the through hole, the outer surface of the first die punch, and the first annular gaskets at the bottom and top of the through hole, remove the first annular gaskets at the bottom and top of the through hole after compaction, and then add first W-Cu mixed powder at the top and bottom, compact, and then remove the first die punch;

[0013] Step five: fill the second W-Cu mixed powder in the same way as step four using a second annular gasket and a second die punch, compact, and remove the second annular gasket and the second die punch; and sequentially fill and compact the third W-Cu mixed powder in the same way until the nth W-Cu mixed powder is filled and compacted;

[0014] Step six: fill the CuCrZr powder in the same way as step four using an (n+1)th annular gasket with an inner diameter smaller than the nth annular gasket and an (n+1)th die punch with an outer diameter smaller than the nth die punch, compact, remove the (n+1)th annular gasket, fill the CuCrZr powder, compact, and then insert an (n+2)th annular gasket into the bottom and top of the (n+1)th die punch respectively;

[0015] Step seven: place the oxide dispersion strengthened tungsten plate obtained in step six, which has a compacted billet formed by the first W-Cu mixed powder to the nth W-Cu mixed powder and the CuCrZr powder in the through hole, and the (n+2)th annular gasket and the (n+1)th die punch, into a spark plasma sintering furnace for sintering treatment. During the sintering process, a pressure head is used to apply pressure to the compacted billet of the through hole. After sintering is completed, the (n+2)th annular gasket and the (n+1)th die punch are removed, thereby obtaining an ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer,

[0016] wherein n is an integer from 3 to 6, preferably 3, 4, 5, or 6, the first W-Cu mixed powder to the nth W-Cu mixed powder are all mixtures composed of W powder and Cu powder, and the content of W in the first W-Cu mixed powder to the nth W-Cu mixed powder decreases in gradient, and the total thickness of the gradient intermediate layer ranges from 2 to 6 mm.

[0017] Preferably, the difference between the outer diameter and the inner diameter of each of the first annular gasket to the nth annular gasket ranges from 0.6 mm to 4 mm, more preferably from 1 mm to 3.5 mm, and the outer diameter and the inner diameter of the (n+1)th annular gasket are fixed at φ = 15 mm and φ = 12 mm respectively.

[0018] Preferably, n is 3 or 4;

[0019] When n is 3, the Cu content of the first W-Cu layer is 25wt%-45wt%, preferably 30wt%-40wt%, based on the total weight of the W-Cu mixed powder of 100wt%; the Cu content of the second W-Cu layer is 45wt%-65wt%, preferably 50wt%-60wt%; the Cu content of the third W-Cu layer is 65wt%-85wt%, preferably 70wt%-80wt%;

[0020] When n is 4, the Cu content of the first W-Cu layer is 15wt%-35wt%, preferably 20wt%-30wt%, based on the total weight of the W-Cu mixed powder of 100wt%; the Cu content of the second W-Cu layer is 35wt%-55wt%, preferably 40wt%-50wt%; the Cu content of the third W-Cu layer is 55wt%-70wt%, preferably 60wt%-70wt%; the Cu content of the fourth W-Cu layer is 70wt%-85wt%, preferably 75wt%-85wt%.

[0021] Preferably, when n=3, the radial thickness ratio of the first W-Cu layer, the second W-Cu layer and the third W-Cu layer formed by the first W-Cu mixed powder, the second W-Cu mixed powder and the third W-Cu mixed powder is 3-5:2-4:3, more preferably 4:3:3.

[0022] When n=3, the outer diameter of the third annular gasket is the same as the inner diameter of the second annular gasket, and the outer diameter of the fourth annular gasket is the same as the inner diameter of the third annular gasket.

[0023] Preferably, when n=4, the radial thickness ratio of the first W-Cu layer, the second W-Cu layer, the third W-Cu layer and the fourth W-Cu layer formed by the first W-Cu mixed powder, the second W-Cu mixed powder, the third W-Cu mixed powder and the fourth W-Cu mixed powder is 2-4:2-4:1-3:2, more preferably 3:3:2:2.

[0024] When n=4, the outer diameter of the third annular gasket is the same as the inner diameter of the second annular gasket, the outer diameter of the fourth annular gasket is the same as the inner diameter of the third annular gasket, and the outer diameter of the fifth annular gasket is the same as the inner diameter of the fourth annular gasket.

[0025] Preferably, in step one, processing is performed by one or more of internal grinding, milling, and wire cutting, and polishing is performed; the cleaning treatment is ultrasonic cleaning of the processed oxide dispersion strengthened tungsten plate in a solvent selected from acetone, ethanol or methanol.

[0026] Preferably, the diameter of the through hole is 17mm-27mm.

[0027] Preferably, in step one, the density of the ODS-W plate is ≥ 99%.

[0028] Preferably, in step two, the first W-Cu mixed powder to the n-th W-Cu mixed powder are prepared by solution combustion synthesis-hydrogen reduction method, and the average particle size is 100 nm to 800 nm.

[0029] Preferably, in steps four to six, the W-Cu mixed powder and the CuCrZr powder can be added in multiple stages, that is, after adding a portion of the W-Cu mixed powder or the CuCrZr powder, compaction is performed, and then after adding the W-Cu mixed powder or the CuCrZr powder, compaction is performed until it is filled.

[0030] Preferably, the CuCrZr powder is a CuCrZr alloy powder, wherein, based on the weight of 100 wt% of the CuCrZr alloy powder, the content of Cr element is 0.05 wt% to 0.9 wt%, the content of Zr element is 0.1 wt% to 0.6 wt%, and the balance is Cu element. Preferably, the average particle size of the CuCrZr powder is 10 to 30 μm.

[0031] Preferably, the material of the first annular gasket to the n-th annular gasket is cemented carbide, and the thickness is 0.5 to 1.5 mm.

[0032] Preferably, the annular gasket can move along the vertical direction of the die punched in the through hole.

[0033] Preferably, in step seven, the SPS sintering temperature is 900 to 1050°C, the holding time is 5 to 20 min, the pressure is 50 to 75 MPa, and the heating rate is 50 to 150°C / min, wherein the pressure is applied to the powder formed compact by the n+2-th annular gasket.

[0034] According to a second aspect of the present application, there is provided an ODS-W / CuCrZr tube-through structure integrated module with a gradient intermediate layer, which is prepared by the preparation method according to the present application.

[0035] Preferably, the room temperature tensile strength of the ODS-W / CuCrZr tube-through structure integrated module with a gradient intermediate layer according to the present application is 270 MPa or more, and the tensile strength at 600°C is 210 MPa or more.

[0036] Preferably, the average thermal conductivity of the ODS-W / CuCrZr tube-through structure integrated module with a gradient intermediate layer according to the present application is 245 W / (m·K) or more.

[0037] Advantages

[0038] The technical scheme of the present application has the following beneficial effects:

[0039] 1) By introducing a W-Cu gradient interlayer between ODS-W and CuCrZr, and being a multi-layer structure, according to the designed W content (or Cu content) of each gradient layer, the composition and performance of the Monoblock module can be slowly transitioned, the thermal stress caused by the large difference in thermal expansion coefficient between W and CuCrZr during high temperature or cooling process can be relieved, the heterogeneous connection of ODS-W and CuCrZr is more reliable, and the service life of the Monoblock module is prolonged. At the same time, compared with other interlayers, the W-Cu gradient interlayer maintains the consistency of the composition and the integrity of the structure of the Monoblock whole module, which is beneficial to improve the comprehensive performance of the component.

[0040] 2) The special pressing forming process and SPS rapid connection technology used in the method can realize the integrated forming preparation of the ODS-W / CuCrZr Monoblock whole module, avoid some defects caused by multi-step connection process, save cost and time.

[0041] 3) The ODS-W / CuCrZr Monoblock whole module prepared by the method has good interface bonding, high thermal conductivity, good bonding strength and thermal load performance, and can withstand 5-20 MW / m 2 The electron beam cycle thermal load can meet the use environment of high thermal load, especially for the divertor material of nuclear fusion reactor. Moreover, the process is simple to operate, does not use extreme process parameters, has high connection efficiency and good repeatability. BRIEF DESCRIPTION OF DRAWINGS

[0042] In order to more clearly illustrate the technical scheme of the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0043] Figure 1 It is a schematic diagram of the assembly of the mold parts designed in steps one and two according to embodiment 1 of the present application and ODS-W plate;

[0044] Figure 2 It is a schematic diagram of SPS preparation of ODS-W / CuCrZr Monoblock whole module with gradient interlayer according to step seven of embodiment 1 of the present application;

[0045] Figure 3This is a schematic diagram showing the dimensions of each layer of the ODS-W / CuCrZrMonoblock monoblock module with a gradient intermediate layer prepared according to Example 1 of the present invention.

[0046] Figure 4 The images show the SEM morphology and corresponding EDS energy spectrum of the ODS-W / CuCrZrMonoblock monolithic module with a gradient intermediate layer prepared according to Example 1 of the present invention, along different regions of the cross-section.

[0047] Figure 5 EDS line scan analysis image of the ODS-W / CuCrZrMonoblock monolithic module with a gradient intermediate layer prepared according to Example 1 of the present invention;

[0048] Figure 6 This is a microhardness distribution diagram along the cross-section of the ODS-W / CuCrZrMonoblock monolithic module with a gradient intermediate layer prepared according to Example 1 of the present invention.

[0049] Figure 7 To illustrate the ODS-W / CuCrZrMonoblock and ODS-W / Cu / CuCrZrMonoblock monoblock modules with gradient intermediate layers prepared according to Example 1 and Comparative Example 1 of the present invention, at a speed of 15 MW / m 2 Temperature distribution under heat flux.

[0050] Figure 8 The stress distribution diagrams of the ODS-W / CuCrZrMonoblock and ODS-W / Cu / CuCrZr Monoblock monoblock modules with gradient intermediate layers prepared according to Example 1 and Comparative Example 1 of the present invention are shown under a heat flux of 15 MW / m2. Detailed Implementation

[0051] The embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0052] It should be noted that, in the absence of conflict, the following embodiments and features can be combined with each other; and, based on the embodiments of this disclosure, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this disclosure.

[0053] It is important to note that the various aspects of the embodiments described below are within the scope of the appended claims. It should be apparent that the aspects described herein can be embodied in a wide variety of forms and that any specific structure and / or function described herein is merely illustrative. Based on the teachings provided herein one skilled in the art should appreciate that an aspect described herein can be implemented independently of any other aspects and that an aspect described herein can be implemented both as any claim and over multiple claims. Likewise, a reference to "an aspect" in the description can mean any aspect described herein, not only an aspect belonging to a single category of aspects. For example, an aspect can be implemented alone, in combination with any other aspect or in combination with even other aspects. Various aspects are described for convenience and to provide a clear and understanding of the present disclosure. Reference to an "aspect" is not meant to limit the aspect to only include the features of the aspect. Rather, an aspect can include a combination of features described herein or any number of the features described herein.

[0054] Test methods:

[0055] Microhardness: The microhardness of the ODS-W / CuCrZr Monoblock integral module was measured according to GB / T 27552-2011 Standard Test Method for Microhardness of Welded Joints by Vickers Pyramid Number for Metallic Materials. The microhardness values near the interface were measured every 300 pm. Two points were punched on the ODS-W side, each W-Cu gradient intermediate layer and the Cu side, and five points were punched in the vertical direction along the same position, respectively, and the average value was taken.

[0056] Tensile strength: The high-temperature tensile strength of the ODS-W / CuCrZr Monoblock module was measured according to GB-T 4338-2006 Standard Test Method for High Temperature Tensile Test of Metallic Materials.

[0057] Thermal conductivity: The thermal conductivity of the ODS-W / CuCrZr Monoblock module was measured according to ASTM E1952-17 Standard Test Method for Modulated Temperature Differential Scanning Calorimetry Determination of Thermal Conductivity and Thermal Diffusivity.

[0058] Temperature field and thermal stress distribution: The temperature distribution and stress distribution of the ODS-W / CuCrZr Monoblock module and the ODS-W / Cu / CuCrZr Monoblock module with gradient intermediate layer under the superposition of transient heat flow were simulated and analyzed by using the finite element analysis software ANSYS.

[0059] Example 1

[0060] The ODS-W / CuCrZr Monoblock integral module with gradient intermediate layer was prepared according to the following steps:

[0061] Step one: processing of ODS-W plate (made by Beijing Antai Technology Co., Ltd. by rolling process, with the content of Y2O3 being 0.5 wt.%, the cross section being a square with a side length of 28 mm, and the height being 10 mm)

[0062] A through hole with an inner diameter of φ = 23 mm was machined on the ODS-W plate by wire cutting, and after polishing, it was placed in an acetone solution for ultrasonic cleaning for 10 min;

[0063] Step two: preparing the first to fifth annular gaskets, wherein the thickness of the gasket is 1 mm, the material is hard alloy, the outer diameter and inner diameter of the first annular gasket are 23 mm and 20.6 mm respectively; the outer diameter and inner diameter of the second annular gasket are 20.6 mm and 18.2 mm respectively; the outer diameter and inner diameter of the third annular gasket are 18.2 mm and 16.6 mm respectively; the outer diameter and inner diameter of the fourth annular gasket are 16.6 mm and 15 mm respectively, the outer diameter and inner diameter of the fifth annular gasket are 15 mm and 12 mm respectively, and the outer diameter and inner diameter of the sixth annular gasket are 23 mm and 12 mm respectively, each specification is prepared in pairs;

[0064] Step three: preparing the first to fifth die punches, which are all made of graphite, wherein the outer diameter of the first die punch is 20.6 mm; the outer diameter of the second die punch is 18.2 mm; the outer diameter of the third die punch is 16.6 mm; the outer diameter of the fourth die punch is 15 mm, and the outer diameter of the fifth die punch is 12 mm;

[0065] Step four: placing the first annular gasket at the bottom and top of the through hole respectively, and inserting the first die punch with the same outer diameter as the inner diameter of the hole of the first annular gasket into the hole of the first annular gasket, so that the first die punch is fixed in the through hole by the first annular gasket at the bottom and top of the through hole; adding first W-Cu mixed powder to the space enclosed by the inner wall of the through hole, the outer surface of the first die punch, and the first annular gasket at the bottom and top of the through hole; the first W-Cu mixed powder is added in three stages, first, about one-third of the depth of the through hole of the first W-Cu mixed powder is added for compaction; then another one-third of the depth of the through hole of the first W-Cu mixed powder is added for compaction; finally, the remaining first W-Cu mixed powder is added for compaction; then the first annular gasket at the bottom of the through hole and the first annular gasket at the top of the through hole are removed, and the first W-Cu mixed powder is added at the top and bottom, compacted, and then the first die punch is removed, wherein the first W-Cu mixed powder is W-30wt.% Cu mixed powder (average particle size is 732 nm);

[0066] Step five: and in the same way as step four, the second W-Cu mixed powder, the third W-Cu mixed powder and the fourth W-Cu mixed powder are added and compacted, wherein the second W-Cu mixed powder is a W-45wt.%Cu mixed powder (average particle size is 783nm), the third W-Cu mixed powder is a W-60wt.%Cu mixed powder (average particle size is 637nm), and the fourth W-Cu mixed powder is a W-75wt.%Cu mixed powder (average particle size is 694nm); after each time of powder laying and compaction, the annular gasket is taken out, the W-Cu mixed powder is added, and the fifth annular gasket is taken out after compaction;

[0067] Step six: the fifth annular gasket and the fifth die are used to fill the CuCrZr powder in the same way as step five, compact, take out the fifth annular gasket, add CuCrZr powder (CuCrZr alloy powder, average particle size is 10μm), compact, and then pass the sixth annular gasket through the top and bottom of the fifth die;

[0068] Step seven: the ODS-W plate formed with the green body obtained in step six and the sixth annular gasket and the fifth die are placed into a spark plasma sintering furnace for sintering treatment to obtain an ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer, and the sintering conditions are as follows: the SPS sintering temperature is 1050℃, the sintering time is 10min, the pressure is 60MPa, and the heating rate is 100℃ / min, wherein the pressure head applies pressure to the compacted green body of the through hole through the sixth annular gasket.

[0069] Figure 4 The SEM morphology of the ODS-W / CuCrZr Monoblock integral module with a four-layer W-Cu gradient intermediate layer prepared according to embodiment 1 of the present application is shown in (a), which is the SEM morphology along the cross-section of the Monoblock integral module, (b-f) are the SEM morphologies along different regions of the cross-section, and (g-l) are the EDS spectra of the corresponding different regions. From the SEM morphology of the Monoblock integral module along the cross-section, it can be seen that the Monoblock integral module has a four-layer W-Cu gradient intermediate layer, and the W content of the Monoblock integral module gradually decreases from the W layer to the Cu layer. Figure 4It can be seen that the ODS-W / CuCrZr Monoblock integral module only contains two elements of W and Cu, the morphology and organization of each region are uniformly distributed, and W and Cu are gradiently distributed along the cross-sectional direction, the content of W gradually decreases (100-0wt.%), and the content of Cu gradually increases (0-100wt.%); the EDS detection results can be seen that in region I (ODS-W region): the content of Cu is 0wt.%; in region II (intermediate layer region formed by the first W-Cu mixed powder): the content of Cu is 31.4wt.%; in region III (intermediate layer region formed by the second W-Cu mixed powder): the content of Cu is 46.5wt.%; in region IV (intermediate layer region formed by the third W-Cu mixed powder): the content of Cu is 68.3wt.%; in region V (intermediate layer region formed by the fourth W-Cu mixed powder): the content of Cu is 78.9wt.%; in region VI (region formed by CuCrZr powder): the content of Cu is 100wt.%. Since the addition amount of Y2O3 in ODS-W and Cr and Zr elements in CuCrZr is small, the spectrum peak of the spectrum is not detected. The above results are consistent with the composition and size structure of the ODS-W / CuCrZr Monoblock integral module designed in advance.

[0070] Figure 5 The EDS line scanning analysis of the cross section of the ODS-W / CuCrZr Monoblock integral module with four-layer W-Cu gradient intermediate layer prepared according to embodiment 1 of the application is shown in FIG. 6. Figure 5 It can be seen that the contents of W and Cu are gradually distributed, the combination between each layer is good, and the thickness of each layer basically meets the size of each layer designed in advance.

[0071] Figure 6 The microhardness distribution diagram of the ODS-W / CuCrZr Monoblock integral module with four-layer W-Cu gradient intermediate layer prepared according to embodiment 1 of the application along the cross section is shown in FIG. 7. Figure 6 It can be seen that the microhardness of the ODS-W / CuCrZr Monoblock integral module gradually changes along the direction from ODS-W to CuCrZr, the microhardness of the ODS-W layer is about 550HV, the microhardness of the first W-Cu layer is about 277HV, the microhardness of the second W-Cu layer is about 201HV, the microhardness of the third W-Cu layer is about 157HV, the microhardness of the fourth W-Cu layer is about 118HV, and the microhardness of the CuCrZr layer is about 56HV. The continuous change of the microhardness is conducive to relieving the residual stress of the Monoblock integral module, making the heterogeneous connection of ODS-W and CuCrZr more reliable, and prolonging the service life of the Monoblock module.

[0072] The room temperature tensile strength of the prepared ODS-W / CuCrZr Monoblock integral module with gradient interlayer is 307 MPa, the tensile strength at 600℃ is 257 MPa, and the overall average thermal conductivity is 284 W / (m·K) after testing.

[0073] Example 2

[0074] In addition to setting the SPS sintering condition in step seven as follows, the ODS-W / CuCrZr Monoblock integral module with gradient interlayer is prepared in the same steps as Example 1,

[0075] The SPS sintering condition in Example 2 is:

[0076] The sintering temperature is 1000℃, the pressure is 50MPa, the sintering time is 10min, and the heating rate is 100℃ / min.

[0077] The room temperature tensile strength of the prepared ODS-W / CuCrZr Monoblock integral module with gradient interlayer is 298 MPa, the tensile strength at 600℃ is 240 MPa, and the overall average thermal conductivity is 273 W / (m·K) after testing.

[0078] Example 3

[0079] In addition to setting the SPS sintering condition in step seven as follows, the ODS-W / CuCrZr Monoblock integral module with gradient interlayer is prepared in the same steps as Example 1, wherein the sintering condition is: sintering temperature 950℃, pressure 50MPa, sintering time 10min, heating rate 100℃ / min.

[0080] The room temperature tensile strength of the prepared ODS-W / CuCrZr Monoblock integral module with gradient interlayer is 273 MPa, the tensile strength at 600℃ is 225 MPa, and the overall average thermal conductivity is 252 W / (m·K) after testing.

[0081] Example 4

[0082] In addition to setting the SPS sintering condition in step seven as follows, the ODS-W / CuCrZr Monoblock integral module with gradient interlayer is prepared in the same steps as Example 1, wherein the sintering condition is: sintering temperature 1000℃, pressure 75MPa, sintering time 5min, heating rate 100℃ / min.

[0083] The ODS-W / CuCrZr Monoblock integral module prepared in this embodiment has a tensile strength of 285 MPa at room temperature, a tensile strength of 231 MPa at 600°C, and an average thermal conductivity of 260 W / (m·K).

[0084] Example 5

[0085] In this embodiment, the number of layers of the W-Cu intermediate layer is 3.

[0086] In addition to setting the outer diameter and inner diameter of the first annular gasket in step two to 23 mm and 19.8 mm respectively, the outer diameter and inner diameter of the second annular gasket to 19.8 mm and 17.4 mm respectively, the outer diameter and inner diameter of the third annular gasket to 17.4 mm and 15 mm respectively, and the outer diameter and inner diameter of the fourth annular gasket to 15 mm and 12 mm respectively, the outer diameter and inner diameter of the fifth annular gasket to 23 mm and 12 mm respectively, and setting the outer diameter of the first die to the third die in step three to 19.8 mm, 17.4 mm, 15 mm and 12 mm respectively, and the first W-Cu mixed powder being W-35wt.% Cu mixed powder (average particle size 756 nm), the second W-Cu mixed powder being W-55wt.% Cu mixed powder (average particle size 709 nm), and the third W-Cu mixed powder being W-75wt.% Cu mixed powder (average particle size 687 nm), and the sintering conditions being sintering temperature 1050°C, pressure 50 MPa, sintering time 10 min, and heating rate 100°C / min, the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer is prepared in the same manner as in Example 1.

[0087] The ODS-W / CuCrZr Monoblock integral module prepared in this embodiment has a tensile strength of 285 MPa at room temperature, a tensile strength of 231 MPa at 600°C, and an average thermal conductivity of 260 W / (m·K).

[0088] Example 6

[0089] In addition to setting the SPS sintering conditions as follows, the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer is prepared in the same steps as in Example 5, wherein the sintering conditions are: sintering temperature 950°C, pressure 75 MPa, sintering time 5 min, and heating rate 100°C / min.

[0090] The prepared ODS-W / Cu / CuCrZr Monoblock integral module has a room temperature tensile strength of 183 MPa, a tensile strength at 600°C of 145 MPa, and an overall average thermal conductivity of 197 W / (m·K).

[0091] Comparative Example 1

[0092] Currently, the divertor target plate for ITER and EAST mainly adopts W / Oxygen-free copper (OFCU) / CuCrZr Monoblock components. In this comparative example, the W-Cu intermediate layer is replaced by a single-layer Cu intermediate layer. Except that the through hole with an inner diameter of φ = 17 mm is machined on the ODS-W plate in step one, and the outer diameter and inner diameter of the first annular gasket are set to 17 mm and 15 mm respectively, the outer diameter and inner diameter of the second annular gasket are set to 15 mm and 12 mm respectively, and the outer diameter and inner diameter of the third annular gasket are set to 17 mm and 12 mm respectively in step two, and the outer diameter of the first die and the second die is set to 15 mm and 12 mm respectively in step three, and the sintering condition is sintering temperature 1050°C, pressure 50 MPa, sintering time 10 min, and heating rate 100°C / min, the ODS-W / Cu / CuCrZr Monoblock integral module is prepared in the same manner as in Example 1.

[0093] The prepared ODS-W / Cu / CuCrZr Monoblock integral module has a room temperature tensile strength of 183 MPa, a tensile strength at 600°C of 145 MPa, and an overall average thermal conductivity of 197 W / (m·K).

[0094] Figure 7 Figures (a) and (b) are stress distribution diagrams of the ODS-W / Cu / CuCrZr Monoblock integral module and the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer prepared according to Comparative Example 1 and Example 1 of the present application under a heat flux of 15 MW / m2, respectively. As can be seen from the figures, the thermal stress of the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer is significantly reduced. 2 Figures (a) and (b) are stress distribution diagrams of the ODS-W / Cu / CuCrZr Monoblock integral module and the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer prepared according to Comparative Example 1 and Example 1 of the present application under a heat flux of 15 MW / m2, respectively. As can be seen from the figures, the thermal stress of the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer is significantly reduced.

[0095] Figure 8 Figures (a) and (b) are stress distribution diagrams of the ODS-W / Cu / CuCrZr Monoblock integral module and the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer prepared according to Comparative Example 1 and Example 1 of the present application under a heat flux of 15 MW / m2, respectively. As can be seen from the figures, the thermal stress of the ODS-W / CuCrZr Monoblock integral module with a gradient intermediate layer is significantly reduced.

[0096] It can be seen by comparison that the ODS-W / Cu / CuCrZr Monoblock integrated module with gradient interlayer has higher mechanical properties and good thermal conductivity. The use of W-Cu gradient interlayer effectively improves the stress distribution of the module, greatly reduces the thermal stress during the service of the material.

Claims

1. A method for preparing an ODS-W / CuCrZr Monoblock integrated module with a gradient intermediate layer, comprising the following steps: Step 1: drilling a through hole in an ODS-W plate and cleaning the through hole; Step 2: preparing a first annular gasket to an n+2th annular gasket, wherein the first annular gasket to the n+1th annular gasket have different outer diameters and inner diameters, the outer diameters and the inner diameters of the first annular gasket to the n+1th annular gasket decrease in turn, the outer diameter of the first annular gasket is the same as the inner diameter of the through hole, the outer diameter of the second annular gasket is the same as the inner diameter of the first annular gasket, based on the same rule, the outer diameter of the n+1th annular gasket is the same as the inner diameter of the nth annular gasket, the outer diameter of the n+2th annular gasket is the same as the outer diameter of the first annular gasket, and the inner diameter of the n+2th annular gasket is the same as the inner diameter of the n+1th annular gasket; Step 3: preparing a first die to an n+1th die, wherein the outer diameters of the first die to the n+1th die are respectively the same as the inner diameters of the first annular gasket to the n+1th annular gasket, so that the die can be inserted into and fixed in the hole of the annular gasket; Step 4: placing two first annular gaskets at the bottom and the top of the through hole respectively, inserting the first die into the hole of the first annular gasket, and fixing the first die in the through hole by the first annular gaskets at the bottom and the top of the through hole respectively; adding a first W-Cu mixed powder into the space enclosed by the inner wall of the through hole, the outer surface of the first die, and the first annular gaskets at the bottom and the top of the through hole, removing the first annular gaskets at the bottom and the top of the through hole after compaction, adding the first W-Cu mixed powder at the top and the bottom again, compacting, and then removing the first die; Step 5: using a second annular gasket and a second die to fill a second W-Cu mixed powder in the same way as step 4, compacting, and removing the second annular gasket and the second die; and filling and compacting a third W-Cu mixed powder in the same way as step 4 until an n-th W-Cu mixed powder is filled and compacted; Step 6: using an n+1th annular gasket and an n+1th die to fill a CuCrZr powder in the same way as step 4, compacting, removing the n+1th annular gasket, not removing the n+1th die, filling a CuCrZr powder, compacting, and then inserting an n+2th annular gasket into the bottom and the top of the n+1th die respectively; Step 7: placing the ODS-W plate with a powder compact obtained in step 6, the n+2th annular gasket, and the n+1th die into a spark plasma sintering furnace for sintering treatment, and applying pressure to the compacted compact of the through hole by a pressure head during the sintering process, thereby obtaining an ODS-W / CuCrZr Monoblock integrated module with a gradient intermediate layer, the total thickness of the gradient intermediate layer ranges from 2 mm to 6 mm, wherein, n is 3 or 4; when n is 3, based on the total weight of the W-Cu mixed powder of 100 wt%, the Cu content of the first W-Cu layer is 25 wt% to 45 wt%. The Cu content of the second W-Cu layer is 45wt%-65wt%; The Cu content of the third W-Cu layer is 65wt%-85wt%; When n is 4, the total weight of the W-Cu mixed powder is 100wt%, and the Cu content of the first W-Cu layer is 20wt%-30wt%; The Cu content of the first W-Cu layer is 15wt%-35wt%; The Cu content of the second W-Cu layer is 35wt%-55wt%; The Cu content of the third W-Cu layer is 55wt%-70wt%; The Cu content of the fourth W-Cu layer is 70wt%-85wt%.

2. The method for preparing the oxidation dispersion strengthened tungsten / copper-chromium-zirconium penetrating structure integrated module with a gradient intermediate layer according to claim 1, wherein, The difference between the outer diameter and the inner diameter of each of the first annular gasket to the n-th annular gasket is in the range of 0.6mm-4mm, and the outer diameter and the inner diameter of the n+1-th annular gasket are fixed as 15mm and 12mm respectively.

3. The method for preparing the oxidation dispersion strengthened tungsten / copper-chromium-zirconium penetrating structure integrated module with a gradient intermediate layer according to claim 2, wherein, The difference between the outer diameter and the inner diameter of each of the first annular gasket to the n-th annular gasket is in the range of 1mm-3.5mm.

4. The method for preparing the oxidation dispersion strengthened tungsten / copper-chromium-zirconium penetrating structure integrated module with a gradient intermediate layer according to claim 1, wherein, n is 3 or 4; When n is 3, the total weight of the W-Cu mixed powder is 100wt%, and the Cu content of the first W-Cu layer is 20wt%-30wt%; The Cu content of the first W-Cu layer is 30wt%-40wt%; The Cu content of the second W-Cu layer is 50wt%-60wt%; The Cu content of the third W-Cu layer is 70wt%-80wt%; When n is 4, the total weight of the W-Cu mixed powder is 100wt%, and the Cu content of the first W-Cu layer is 20wt%-30wt%; The Cu content of the first W-Cu layer is 20wt%-30wt%; The Cu content of the second W-Cu layer is 40wt%-50wt%; The Cu content of the third W-Cu layer is 60wt%-70wt%; The Cu content of the fourth W-Cu layer is 75wt%-85wt%.

5. The method for preparing the oxidation dispersion strengthened tungsten / copper-chromium-zirconium penetrating structure integrated module with a gradient intermediate layer according to claim 1, wherein, When n=3, the radial thickness ratio of the first W-Cu layer, the second W-Cu layer and the third W-Cu layer formed by the first W-Cu mixed powder, the second W-Cu mixed powder and the third W-Cu mixed powder is 3-5:2-4:3; Or, when n=4, the radial thickness ratio of the first W-Cu layer, the second W-Cu layer, the third W-Cu layer and the fourth W-Cu layer formed by the first W-Cu mixed powder, the second W-Cu mixed powder, the third W-Cu mixed powder and the fourth W-Cu mixed powder is 2-4:2-4:1-3:

2.

6. The method for preparing the oxidation dispersion strengthened tungsten / copper-chromium-zirconium penetrating structure integrated module with a gradient intermediate layer according to claim 5, wherein, In the case of n=3, the radial thickness ratio of the first W-Cu layer, the second W-Cu layer and the third W-Cu layer formed by the first W-Cu mixed powder, the second W-Cu mixed powder and the third W-Cu mixed powder is 4:3:3; Or, in the case of n=4, the radial thickness ratio of the first W-Cu layer, the second W-Cu layer, the third W-Cu layer and the fourth W-Cu layer formed by the first W-Cu mixed powder, the second W-Cu mixed powder, the third W-Cu mixed powder and the fourth W-Cu mixed powder is 3:3:2:

2.

7. The method of claim 1, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: In step one, the ODS-W plate is processed by one or more of inner circle grinding, milling and wire cutting, and is polished; and the cleaning treatment is ultrasonic cleaning of the processed ODS-W plate in a solvent selected from acetone, ethanol or methanol.

8. The method of claim 1, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: In step one, the ODS-W plate has a density of ≥99%.

9. The method of claim 1, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: In step two, the first W-Cu mixed powder to the n-th W-Cu mixed powder are prepared by solution combustion synthesis-hydrogen reduction, and have an average particle size of 100 nm to 800 nm; and / or In steps four to six, the W-Cu mixed powder and the CuCrZr powder are added in multiple stages, i.e., after adding a portion of the W-Cu mixed powder or the CuCrZr powder, compaction is performed, and then after adding the W-Cu mixed powder or the CuCrZr powder, compaction is performed, until the space is filled.

10. The method of claim 1, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: The CuCrZr powder is a CuCrZr alloy powder, wherein the content of Cr is 0.05wt% to 0.9wt% and the content of Zr is 0.1wt% to 0.6wt% based on the weight of the CuCrZr alloy powder of 100wt%, and the balance is Cu.

11. The method of claim 10, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: The average particle size of the CuCrZr powder is 5 to 30 μm.

12. The method of claim 1, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: The first annular gasket to the n-th annular gasket are made of cemented carbide and have a thickness of 0.5 to 1.5 mm.

13. The method of claim 1, wherein the ODS-W / CuCrZr tube-structure integrated module with a gradient interlayer is prepared by the following steps: The annular gasket is movable along the vertical direction of the through hole; and / or In step seven, the SPS sintering temperature is 900-1050℃, the holding time is 5-20min, the pressure is 50-75MPa, and the heating rate is 50-150℃ / min, wherein the pressure is applied to the green body formed by the powder through the n+2 annular gasket.

14. A tungsten / copper-chromium-zirconium tube penetrating structure monolithic module with a gradient intermediate layer, which is prepared by the method for preparing a tungsten / copper-chromium-zirconium tube penetrating structure monolithic module with a gradient intermediate layer according to any one of claims 1 to 13.

15. The tungsten / copper-chromium-zirconium tube penetrating structure monolithic module with a gradient intermediate layer according to claim 14, wherein, the room temperature tensile strength of the tungsten / copper-chromium-zirconium tube penetrating structure monolithic module with a gradient intermediate layer is 270MPa or more, the tensile strength at 600℃ is 210MPa or more; and / or the average thermal conductivity of the tungsten / copper-chromium-zirconium tube penetrating structure monolithic module with a gradient intermediate layer is 245W / (m·K) or more.

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