A method for preparing a net-fiber toughened tungsten-based composite material

Abstract

This invention discloses a method for preparing a reticulated fiber-reinforced tungsten-based composite material, relating to the field of tungsten-based material preparation technology. First, long fibers are woven into a mesh and coated with a functional interface layer. Then, the fiber mesh and slurry are alternately laid using an indirect 3D printing method to obtain a green body of the reticulated fiber-reinforced tungsten-based composite material. Next, the binder components in the green body are removed using a hydrothermal method and a thermal stripping method. Finally, pre-sintering is performed using a hydrogen reduction sintering method to obtain a reticulated fiber-reinforced tungsten-based composite material with a certain structural strength. Then, a bulk composite material is obtained using an ultra-high pressure high temperature sintering method. The tungsten-based composite material prepared by this process is nearly fully dense, exhibiting high toughness at room temperature while ensuring high strength. Furthermore, the combination of hot pressing sintering and ultra-high pressure high temperature sintering methods allows the final composite material bulk to achieve a density of over 99%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tungsten-based material preparation, and particularly relates to a preparation method of a reticular fiber tough tungsten-based composite material. BACKGROUND

[0002] Controllable nuclear fusion reactor has the characteristics of safety and high efficiency, and is the ultimate goal of China's nuclear energy development "three-step" strategy. The magnetic confinement controllable nuclear fusion (tokamak) device needs to withstand the synergistic effects of plasma erosion, high-energy neutron impact and extremely high environmental temperature, and has not yet found the optimal choice. Tungsten, as the metal with the highest melting point (3410℃), has high thermal conductivity, low sputtering rate and fuel retention, and is a highly respected plasma-facing material. However, as a body-centered cubic (BCC) metal, its room temperature brittleness and recrystallization brittleness are the main factors limiting its processing and application. Moreover, in future nuclear fusion reactors, high-energy neutron irradiation will inevitably lead to irradiation embrittlement of the material, which makes tungsten materials face the problem of insufficient toughness in the engineering practice of nuclear fusion energy.

[0003] At present, there are mainly two ways to improve the strength and toughness of tungsten materials: intrinsic toughening means and extrinsic toughening means (using the pseudo-plasticity of composite materials, also known as pseudo-toughness or pseudo-toughness). Among them, the intrinsic toughening means to improve the plasticity of tungsten mainly through alloying, large deformation or refining the grains of tungsten. However, due to the high strength of tungsten itself and its sensitivity to impurities, the effect of these methods is not obvious. The extrinsic toughening means is mainly to prepare tungsten-based composite materials to improve the strength and toughness of tungsten. According to the type of added reinforcing body, it can also be divided into second phase particle toughening and fiber toughening.

[0004] The invention patent with publication number CN112442643B discloses a layered fiber tough tungsten-based composite material and a preparation method thereof. The composite material includes tungsten matrix layers and tungsten fiber net toughening layers which are alternately stacked with each other. The layered fiber tough tungsten-based composite material is prepared after discharge plasma sintering under vacuum conditions. However, the composite material obtained by this method lacks an interface between the matrix and the reinforcing body, which is not conducive to improving the fracture dissipation energy.

[0005] The invention patent with publication number CN114959518A discloses a tungsten fiber and Y2O3 nanoparticle synergistic tough tungsten-based composite material. Y2O3 nanoparticles are used to block the complete connection of tungsten fibers and tungsten matrix at high temperature, and to weaken the bonding strength between the tungsten matrix and the tungsten fibers. However, the fibers belong to the category of short fibers, and their reinforcing and toughening effect cannot reach the level of long fibers.

[0006] The invention patent with publication number CN114717491B discloses a strong and tough Wf / W composite material, the raw materials of which include Wf, W powder and plated Wf, the Wf capable of producing a strong interface and the plated Wf capable of producing a weak interface are used to jointly composite the W matrix, thereby improving the strength and toughness simultaneously. However, the invention patent with publication number CN114959518A discloses a tungsten fiber and Y2O3 nanoparticle synergistic toughening tungsten-based composite material, and the fibers used in the patent belong to the category of short fibers, and the reinforcing and toughening effect cannot reach the level of long fibers.

[0007] Therefore, the current tungsten-based composite material still has the problems of insufficient strength and toughness. SUMMARY

[0008] The technical problem to be solved by the present application is the problem of insufficient strength and toughness of the current tungsten-based composite material, and the purpose is to provide a preparation method of a net-shaped fiber strong and tough tungsten-based composite material, to solve the problem of insufficient strength and toughness of the current tungsten-based composite material, and to obtain an almost fully dense engineering application material.

[0009] The present application is realized by the following technical scheme:

[0010] A preparation method of a net-shaped fiber strong and tough tungsten-based composite material, comprising the following steps:

[0011] Step 1: weaving long fibers into a net;

[0012] Step 2: plating a functional interface layer on the woven net;

[0013] Step 3: using an indirect 3D printing method to alternately lay the fiber net and the tungsten matrix slurry to obtain a net-shaped fiber strong and tough tungsten-based composite material green body;

[0014] Step 4: removing the binder components in the green body by using a hydrothermal method and a thermal decomposition method;

[0015] Step 5: pre-sintering by using a hydrogen reduction sintering method to obtain a net-shaped fiber strong and tough tungsten-based composite material with a certain structural strength, and then using an ultrahigh pressure and high temperature sintering method to obtain a composite material block.

[0016] The indirect 3D printing method is a powder extrusion method.

[0017] The toughening mechanism of the tungsten-based composite material in the present application is to consume energy by interface cracking, fiber pull-out and sliding when the tungsten matrix material is fractured, to inhibit brittle fracture of the material, thereby achieving the effect of material plasticity. This method is based on energy dissipation in structural mechanics, and can effectively avoid the problem of temperature working condition restriction based on the composition toughening mechanism.

[0018] In the preparation method of the present application, long fibers are woven into a net, and an interface plating layer is added. An indirect 3D printing method is used to build a net-shaped fiber-tough tungsten-based composite green body with super-high precision (for example, the thickness of the slurry layer containing tungsten powder can be as thin as microns in PEP printing) by layer-by-layer stacking of the fiber net and tungsten matrix. Through debinding and hydrogen reduction sintering, the density of the composite material is improved to nearly 90%. Finally, an ultra-high pressure and high temperature press is used to complete the densification of the material. The tungsten-based composite material prepared by this process is nearly fully dense, and also exhibits high toughness at room temperature while ensuring high strength.

[0019] The present application combines hydrogen reduction sintering method and ultra-high pressure and high temperature sintering method. First, preliminary sintering is carried out by hydrogen reduction sintering method. After preliminary sintering, the density of the composite material is close to 90%. Then, ultra-high pressure and high temperature sintering is carried out. As a result, the density of the final composite block can reach more than 99%.

[0020] Preferably, the long fibers in step 1 include metal long fibers or non-metal long fibers.

[0021] Preferably, the metal long fibers include pure tungsten, tungsten alloy or tungsten wire containing reinforcing phase; and the non-metal long fibers include carbon fiber or silicon carbide fiber.

[0022] The tungsten alloy includes tungsten-rhenium wire, and the tungsten wire containing reinforcing phase includes potassium bubble reinforced tungsten wire.

[0023] The long tungsten fibers are commercial or research tungsten wires.

[0024] Preferably, the diameter of the long fibers is 10-500 μm, and the specification of the woven net is 20-300 mesh.

[0025] Preferably, the material of the functional interface layer in step 2 includes any one or more of oxides, metals and intermetallic compounds, and the thickness of the plating layer is 0.1 μm-2 mm.

[0026] The oxides include YO x , ZrO x , ErO x , etc.; and the metals include Ti, Ta, Re, etc.

[0027] Preferably, the plating method in step 2 includes magnetron sputtering method, chemical vapor deposition method and sol-gel method.

[0028] Preferably, the slurry in step 3 includes tungsten-based material powder and binder; the purity of the tungsten-based material powder is greater than 99%, and the particle size is 0.05-5 um; the tungsten-based material powder also includes tungsten-based material powder doped with any one or more of Y2O3, ZrC, Ta, K reinforcing phase.

[0029] Preferably, the binder comprises a mixture of any one or more of paraffin wax, PP, PE, stearic acid, and the volume ratio of the tungsten-based material powder to the binder is 1 / 3-3.

[0030] Preferably, the hydrothermal temperature in the hydrothermal method in step 4 is 40-90℃, and the hydrothermal time is 12-48 h; during thermal desorption, the protective atmosphere is hydrogen, the flow rate is 0.5-1.5 m 3 / h, the thermal desorption temperature is 800-1200℃, and the holding time is greater than 240 min.

[0031] Preferably, the sintering temperature of the preheating sintering in step 5 is 1200-2300℃, the protective atmosphere is hydrogen, the flow rate is 0.5-1.5 m 3 / h, the heating rate is 1-6℃ / min, the sintering time is 3050-4800 min, and the sintered body density is 70%-96%; the sintering temperature of the ultra-high pressure and high temperature sintering is 1200-1800℃, the pressure is 1 GPa-10 GPa, and the sintering time is 5-60 min.

[0032] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0033] (1) The toughening mechanism of the tungsten-based composite material in the present application is to consume energy by interface cracking, fiber pull-out and sliding when the tungsten matrix material is fractured, to inhibit brittle fracture of the material, so as to make the material exhibit plasticity. This method is based on energy dissipation in structural mechanics, and can effectively avoid the problem of temperature working condition restriction based on composition toughening mechanism.

[0034] (2) In the preparation method of the present application, long fibers are woven into a net, an interface plating layer is added, and an indirect 3D printing method is used to construct a net-shaped fiber tough tungsten-based composite material green body by layer-by-layer super-precision stacking of the fiber net and the tungsten matrix. Through debinding and hydrogen reduction sintering, the density of the composite material is further improved to nearly 90%, and finally the densification of the material is completed using an ultra-high pressure and high temperature press. The tungsten-based composite material prepared by this process is nearly fully dense, and exhibits high toughness at room temperature while ensuring high strength.

[0035] (3) The present application combines the hydrogen reduction sintering method with the ultra-high pressure and high temperature sintering method. After preliminary sintering by the hydrogen reduction sintering method, the density of the sample after preliminary sintering can reach more than 80%. After preliminary hydrogen reduction sintering, the ultra-high pressure and high temperature sintering is performed, so that the density of the final composite material block can reach more than 99%. BRIEF DESCRIPTION OF DRAWINGS

[0036] In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some of the embodiments of the present application, and therefore should not be considered as a limitation to the scope. For those skilled in the art, other related drawings can also be obtained without creative effort. In the drawings:

[0037] Figure 1 Preparation flow chart of the preparation method of the reticular fiber strong tungsten-based composite material in the present application;

[0038] Figure 2 Structure schematic diagram of the reticular fiber strong tungsten-based composite material in the present application;

[0039] Figure 3 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 1 of the present application;

[0040] Figure 4 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 2 of the present application;

[0041] Figure 5 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 3 of the present application;

[0042] Figure 6 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 4 of the present application;

[0043] Figure 7 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 5 of the present application;

[0044] Figure 8 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 6 of the present application;

[0045] Figure 9 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 7 of the present application;

[0046] Figure 10 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 8 of the present application;

[0047] Figure 11 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 9 of the present application;

[0048] Figure 12 Compression curve diagram of the reticular fiber strong tungsten-based composite material in Example 10 of the present application;

[0049] Figure 13Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 11 of the present application;

[0050] Figure 14 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 12 of the present application;

[0051] Figure 15 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 13 of the present application;

[0052] Figure 16 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 14 of the present application;

[0053] Figure 17 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 15 of the present application;

[0054] Figure 18 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 16 of the present application;

[0055] Figure 19 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 17 of the present application;

[0056] Figure 20 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 18 of the present application;

[0057] Figure 21 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 19 of the present application;

[0058] Figure 22 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 20 of the present application;

[0059] Figure 23 Compression curve diagram of the reticular fiber reinforced tungsten-based composite material in the embodiment 21 of the present application. DETAILED DESCRIPTION

[0060] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application.

[0061] The following detailed description of embodiments of the application provided in the accompanying drawings is not intended to limit the scope of the application as claimed, but merely represents selected embodiments of the application. All other embodiments falling within the scope of the application as claimed are intended to be embraced by the application based on the embodiments in the application, without requiring inventive effort.

[0062] It should be noted that like numerals and letters refer to like items throughout the drawings, and therefore, once an item is defined in one drawing, it need not be further defined and explained in subsequent drawings.

[0063] Example 1

[0064] The long fibers of this example use carbon fibers, such as Figure 1 and Figure 2 The specific preparation method is as follows:

[0065] Step 1: Use a braiding machine to braid a carbon fiber bundle with a diameter of about 50 μm (about 9 T700 carbon fibers on the market) into a 30-denier carbon fiber net by plain weave method.

[0066] Step 2: The carbon fiber net braided in step 1 is clamped using a tool, then placed and fixed in the inner cavity of a magnetron sputtering for deposition of a Y2O3 functional interface layer. The deposition thickness of Y2O3 is 1 μm. After the plating is completed, the tool is removed, and the carbon fiber net with the functional interface is cut according to the required size for subsequent production.

[0067] Step 3: Prepare a net-shaped fiber-toughened tungsten-based composite green body.

[0068] 1) Configure the required tungsten matrix slurry: the slurry composition is a mixture of pure tungsten powder and a binder; the purity of the tungsten powder is 99.95%, and the powder D50 is 3 μm; the binder is a mixture of paraffin, PP, PE and stearic acid; the mass ratio of paraffin, PP, PE and stearic acid is 10.0:6.0:3.9:0.1; the volume ratio of tungsten powder to forming agent in the slurry is 1:1.

[0069] 2) Use a PEP 3D printer to process the net-shaped fiber-toughened tungsten-based composite green body layer by layer, with a composite length of 50 mm, a width of 50 mm, a single layer of slurry thickness of 0.3 mm, and a functional interface carbon fiber net with a size of 30*30 mm laid every 20 layers of slurry, with the laying position being the center; each green body contains 10 pieces of carbon fiber net and 11 layers of tungsten slurry; after printing, wait for 10 min to ensure that the green body is solidified, and then place the completely solidified green body in a 40°C water bath for 24 h to remove the solvent.

[0070] Step 4: Put the green body of step 3 into the sintering furnace for thermal desorption. The parameters in the process steps of thermal desorption are shown in Table 1.

[0071] Table 1

[0072]

[0073] Step 5: Sinter the green body of the composite material by using hydrogen reduction sintering method and ultra-high pressure high temperature sintering method.

[0074] 1) Sinter the green body of the composite material by using hydrogen reduction sintering method.

[0075] The obtained composite material is subjected to hydrogen reduction sintering. The process steps of hydrogen reduction sintering are shown in Table 2.

[0076] Table 2

[0077]

[0078] 2) Cut the sintered body with a certain strength by using an electric spark cutting machine to adapt to the mold of the ultra-high pressure high temperature sintering device. In this embodiment, a 650 type hinge six-surface press is used as a high pressure high temperature generating device, and the mold size is Φ6x6mm. The parameters of ultra-high pressure high temperature sintering are sintering temperature of 1400℃, sintering pressure of 5GPa, and holding time of 30min.

[0079] Performance test

[0080] The density of the finished reticular fiber tough tungsten-based composite material prepared by the preparation method of embodiment 1 is tested by the drainage method, and the density is 99.6%.

[0081] The reticular fiber tough tungsten-based composite material sample prepared by the preparation method of embodiment 1 is subjected to room temperature compression experiment, and the compression strength is 1550MPa and the plastic deformation deformation is 4.7% as shown in Table 3. Figure 3

[0082] Embodiment 2

[0083] The difference between this embodiment and embodiment 1 is that the long fibers of embodiment 2 are silicon carbide fibers, and other technical features are the same as embodiment 1.

[0084] Performance test

[0085] The density of the finished reticular fiber tough tungsten-based composite material prepared by the preparation method of embodiment 2 is tested by the drainage method, and the density is 99.5%.

[0086] The reticular fiber tough tungsten-based composite material sample prepared by the preparation method of embodiment 2 is subjected to room temperature compression experiment, and the compression strength is 1550MPa and the plastic deformation deformation is 4.7% as shown in Table 3. Figure 4 ​As shown, the compressive strength is measured to be 1590 MPa, and the plastic deformation is 4.9%.

[0087] Example 3

[0088] The difference between this example and Example 1 is that the long fibers of Example 3 are pure tungsten wires, and other technical features are completely the same as Example 1.

[0089] Performance detection

[0090] The density of the finished reticular fiber tough tungsten-based composite material prepared by the preparation method of Example 3 is tested by the drainage method, and the density is 99.5%.

[0091] The reticular fiber tough tungsten-based composite material sample prepared by the preparation method of Example 3 is subjected to room temperature compression test, as shown in Figure 5 The compressive strength is measured to be 1650 MPa, and the plastic deformation is 19.8%.

[0092] Example 4

[0093] The difference between this example and Example 1 is that the long fibers of Example 4 are tungsten-rhenium wires, and other technical features are completely the same as Example 1.

[0094] Performance detection

[0095] The density of the finished reticular fiber tough tungsten-based composite material prepared by the preparation method of Example 4 is tested by the drainage method, and the density is 99.7%.

[0096] The reticular fiber tough tungsten-based composite material sample prepared by the preparation method of Example 4 is subjected to room temperature compression test, as shown in Figure 6 The compressive strength is measured to be 1775 MPa, and the plastic deformation is 26.3%.

[0097] Example 5

[0098] The difference between this example and Example 1 is that the long fibers of Example 5 are potassium bubble enhanced tungsten wires, and other technical features are completely the same as Example 1.

[0099] Performance detection

[0100] The density of the finished reticular fiber tough tungsten-based composite material prepared by the preparation method of Example 5 is tested by the drainage method, and the density is 99.8%.

[0101] The reticular fiber tough tungsten-based composite material sample prepared by the preparation method of Example 5 is subjected to room temperature compression test, as shown in Figure 7 The compressive strength is measured to be 1880 MPa, and the plastic deformation is 27.5%.

[0102] Example 6

[0103] The difference between this example and Example 1 is that the long fibers used in Example 6 have a diameter of 10 μm, and the specifications of the woven mesh are 20 mesh, and other technical features are exactly the same as those of Example 1.

[0104] Performance test

[0105] The density of the finished mesh-like fiber toughened tungsten-based composite material prepared by using the preparation method of Example 6 is tested by the drainage method, and the density is 99.2%.

[0106] The mesh-like fiber toughened tungsten-based composite material sample prepared by using the preparation method of Example 6 is subjected to a room temperature compression test, and as shown in FIG. 6, the compression strength is measured to be 1520 MPa, and the plastic deformation deformation is 4.2%. Figure 8

[0107] Example 7

[0108] The difference between this example and Example 1 is that the long fibers used in Example 7 have a diameter of 500 μm, and the specifications of the woven mesh are 300 mesh, and other technical features are exactly the same as those of Example 1.

[0109] Performance test

[0110] The density of the finished mesh-like fiber toughened tungsten-based composite material prepared by using the preparation method of Example 7 is tested by the drainage method, and the density is 99.6%.

[0111] The mesh-like fiber toughened tungsten-based composite material sample prepared by using the preparation method of Example 7 is subjected to a room temperature compression test, and as shown in FIG. 7, the compression strength is measured to be 1850 MPa, and the plastic deformation deformation is 28.5%. Figure 9

[0112] Example 8

[0113] The difference between this example and Example 1 is that the material of the functional interface layer in Example 8 is ZrO2, and other technical features are exactly the same as those of Example 1.

[0114] Performance test

[0115] The density of the finished mesh-like fiber toughened tungsten-based composite material prepared by using the preparation method of Example 8 is tested by the drainage method, and the density is 99.3%.

[0116] The mesh-like fiber toughened tungsten-based composite material sample prepared by using the preparation method of Example 8 is subjected to a room temperature compression test, and as shown in FIG. 8, the compression strength is measured to be 1590 MPa, and the plastic deformation deformation is 5.1%. Figure 10

[0117] Example 9​​​

[0118] The difference between this embodiment and embodiment 1 is that the material of the functional interface layer in embodiment 9 is ErO x , and other technical features are completely the same as those of embodiment 1.

[0119] Performance detection

[0120] The density of the finished reticular fiber toughened tungsten-based composite material prepared by the preparation method of embodiment 9 is tested by the drainage method, and the density is 99.6%.

[0121] The reticular fiber toughened tungsten-based composite material sample prepared by the preparation method of embodiment 9 is subjected to room temperature compression test, and the compression strength is 1584 MPa and the plastic deformation variable is 5.2% as shown in the table. Figure 11

[0122] Embodiment 10

[0123] The difference between this embodiment and embodiment 1 is that the material of the functional interface layer in embodiment 10 is Ti, and other technical features are completely the same as those of embodiment 1.

[0124] Performance detection

[0125] The density of the finished reticular fiber toughened tungsten-based composite material prepared by the preparation method of embodiment 10 is tested by the drainage method, and the density is 99.5%.

[0126] The reticular fiber toughened tungsten-based composite material sample prepared by the preparation method of embodiment 10 is subjected to room temperature compression test, and the compression strength is 1600 MPa and the plastic deformation variable is 4.7% as shown in the table. Figure 12

[0127] Embodiment 11

[0128] The difference between this embodiment and embodiment 1 is that the material of the functional interface layer in embodiment 11 is Ta, and other technical features are completely the same as those of embodiment 1.

[0129] Performance detection

[0130] The density of the finished reticular fiber toughened tungsten-based composite material prepared by the preparation method of embodiment 11 is tested by the drainage method, and the density is 99.6%.

[0131] The reticular fiber toughened tungsten-based composite material sample prepared by the preparation method of embodiment 11 is subjected to room temperature compression test, and the compression strength is 1610 MPa and the plastic deformation variable is 4.8% as shown in the table. Figure 13

[0132] Embodiment 12

[0133] ​​​The difference between this embodiment and embodiment 1 is that the plating method in embodiment 12 is chemical vapor deposition, and other technical features are completely the same as those in embodiment 1.

[0134] Performance detection

[0135] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by using the preparation method in embodiment 12 is tested by the drainage method, and the density is 99.5%.

[0136] The room temperature compression experiment is performed on the reticular fiber reinforced tungsten-based composite material sample prepared by using the preparation method in embodiment 12, and as shown in the table, the compression strength is 1560 MPa, and the plastic deformation variable is 4.9%. Figure 14

[0137] Embodiment 13

[0138] The difference between this embodiment and embodiment 1 is that the plating method in embodiment 13 is sol-gel method, and other technical features are completely the same as those in embodiment 1.

[0139] Performance detection

[0140] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by using the preparation method in embodiment 13 is tested by the drainage method, and the density is 99.6%.

[0141] The room temperature compression experiment is performed on the reticular fiber reinforced tungsten-based composite material sample prepared by using the preparation method in embodiment 13, and as shown in the table, the compression strength is 1590 MPa, and the plastic deformation variable is 4.7%. Figure 15

[0142] Embodiment 14

[0143] The difference between this embodiment and embodiment 1 is that the tungsten-based material powder in the slurry in embodiment 14 is doped with Y2O 3， The particle size of the tungsten-based material powder is 0.05 um, and other technical features are completely the same as those in embodiment 1.

[0144] Performance detection

[0145] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by using the preparation method in embodiment 14 is tested by the drainage method, and the density is 99.8%.

[0146] The room temperature compression experiment is performed on the reticular fiber reinforced tungsten-based composite material sample prepared by using the preparation method in embodiment 14, and as shown in the table, the compression strength is 1650 MPa, and the plastic deformation variable is 21%. Figure 16

[0147] Embodiment 15

[0148] ​​​The difference between this embodiment and embodiment 1 is that the tungsten-based material powder in the slurry in embodiment 15 is doped with ZrC ， The particle size of the tungsten-based material powder is 5um, and other technical features are completely the same as those of embodiment 1.

[0149] Performance detection

[0150] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by the preparation method of embodiment 15 is tested by the drainage method, and the density is 99.6%.

[0151] The reticular fiber reinforced tungsten-based composite material sample prepared by the preparation method of embodiment 15 is subjected to room temperature compression test, and the compression strength is 1580MPa and the plastic deformation deformation is 20.5% as shown in the following table. Figure 17

[0152] Embodiment 16

[0153] The difference between this embodiment and embodiment 1 is that the tungsten-based material powder in the slurry in embodiment 16 is doped with Ta ， The particle size of the tungsten-based material powder is 5um, and other technical features are completely the same as those of embodiment 1.

[0154] Performance detection

[0155] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by the preparation method of embodiment 16 is tested by the drainage method, and the density is 99.4%.

[0156] The reticular fiber reinforced tungsten-based composite material sample prepared by the preparation method of embodiment 16 is subjected to room temperature compression test, and the compression strength is 1550MPa and the plastic deformation deformation is 18.5% as shown in the following table. Figure 18

[0157] Embodiment 17

[0158] The difference between this embodiment and embodiment 1 is that the tungsten-based material powder in the slurry in embodiment 17 is doped with K ， The particle size of the tungsten-based material powder is 5um, and other technical features are completely the same as those of embodiment 1.

[0159] Performance detection

[0160] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by the preparation method of embodiment 17 is tested by the drainage method, and the density is 99.5%.

[0161] The reticular fiber reinforced tungsten-based composite material sample prepared by the preparation method of embodiment 18 is subjected to room temperature compression test, and the compression strength is 1550MPa and the plastic deformation deformation is 18.5% as shown in the following table. Figure 19 ​​The compressive strength is measured to be 1580 MPa and the plastic deformation is 21%.

[0162] Example 18

[0163] The difference between this example and Example 1 is that the volume ratio of the tungsten-based material powder to the binder in Example 18 is 1 / 3, and other technical features are completely the same as those of Example 1.

[0164] Performance detection

[0165] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by using the preparation method of Example 18 is tested by the drainage method, and the density is 99.6%.

[0166] The reticular fiber reinforced tungsten-based composite material sample prepared by using the preparation method of Example 18 is subjected to a room temperature compression experiment, as shown in Figure 20 The compressive strength is measured to be 1570 MPa and the plastic deformation is 4.7%.

[0167] Example 19

[0168] The difference between this example and Example 1 is that the volume ratio of the tungsten-based material powder to the binder in Example 19 is 3, and other technical features are completely the same as those of Example 1.

[0169] Performance detection

[0170] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by using the preparation method of Example 19 is tested by the drainage method, and the density is 99.4%.

[0171] The reticular fiber reinforced tungsten-based composite material sample prepared by using the preparation method of Example 19 is subjected to a room temperature compression experiment, as shown in Figure 21 The compressive strength is measured to be 1550 MPa and the plastic deformation is 4.8%.

[0172] Example 20

[0173] The difference between this example and Example 1 is that the plating thickness of the functional interface layer in Example 20 is 0.1 μm, and other technical features are completely the same as those of Example 1.

[0174] Performance detection

[0175] The density of the finished reticular fiber reinforced tungsten-based composite material prepared by using the preparation method of Example 20 is tested by the drainage method, and the density is 99.8%.

[0176] The reticular fiber reinforced tungsten-based composite material sample prepared by using the preparation method of Example 20 is subjected to a room temperature compression experiment, as shown in Figure 22As shown, the compressive strength is measured to be 1535 MPa, and the plastic deformation is 3.9%.

[0177] Example 21

[0178] The difference between this example and Example 1 is that the plating thickness of the functional interface layer in Example 21 is 2 mm, and other technical features are completely the same as those of Example 1.

[0179] Performance detection

[0180] The density of the finished reticular fiber toughened tungsten-based composite material prepared by using the preparation method of Example 21 is tested by the drainage method, and the density is 99.6%.

[0181] The reticular fiber toughened tungsten-based composite material sample prepared by using the preparation method of Example 21 is subjected to a room temperature compression experiment, and the stress-strain curve is shown in Figure 23 As shown, the compressive strength is measured to be 1550 MPa, and the plastic deformation is 15.5%.

[0182] The above specific embodiments further illustrate the purposes, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method of producing a net-shaped, fiber-reinforced tungsten-based composite material, characterized by, The method comprises the following steps: Step 1: weaving long fibers into a net; Step 2: plating a functional interface layer on the net obtained in step 1; Step 3: alternately laying a slurry and the net obtained in step 2 by using an indirect 3D printing method to obtain a net-shaped fiber-reinforced tungsten-based composite green body; Step 4: removing the binder component in the green body by using a hydrothermal method and a thermal decomposition method; Step 5: pre-sintering by using a hydrogen reduction sintering method to obtain a net-shaped fiber-reinforced tungsten-based composite material with a certain structural strength, and then using an ultra-high pressure and high temperature sintering method to obtain a composite material block; The material of the functional interface layer in step 2 comprises any one or more of oxides, metals, and intermetallic compounds, and the thickness of the plating layer is 0.1 μm to 2 mm.

2. The method for preparing a reticulated fiber reinforced tungsten-based composite material according to claim 1, characterized in that, The long fibers in step 1 comprise metal long fibers or non-metal long fibers.

3. The method of claim 2, wherein the method further comprises the step of: The metal long fibers comprise pure tungsten, tungsten alloy, or tungsten wire containing a reinforcing phase; and the non-metal long fibers comprise carbon fibers or silicon carbide fibers.

4. The method for preparing a reticulated fiber reinforced tungsten-based composite material according to claim 1, characterized in that, The diameter of the long fibers is 10-500 μm, and the specification of the woven net is 20-300 mesh.

5. The method for preparing a reticulated fiber reinforced tungsten-based composite material according to claim 1, characterized in that, The plating method in step 2 comprises a magnetron sputtering method, a chemical vapor deposition method, or a sol-gel method.

6. The method for preparing a reticulated fiber reinforced tungsten-based composite material according to claim 1, characterized in that, The slurry in step 3 comprises tungsten-based material powder and a binder; the purity of the tungsten-based material powder is greater than 99%, and the particle size is 0.05-5 μm; the tungsten-based material powder further comprises any one or more of Y2O3, ZrC, Ta, and K.

7. The method of claim 6, wherein the method further comprises the step of: The binder comprises a mixture of any one or more of paraffin, PP, PE, and stearic acid, and the volume ratio of the tungsten-based material powder to the binder is 1 / 3 to 3.

8. The method for preparing a reticulated fiber reinforced tungsten-based composite material according to claim 1, characterized in that, The hydrothermal temperature in the hydrothermal method described in step 4 is 40-90℃, and the hydrothermal time is 12-48 h; in the thermal decomposition, the protective atmosphere is hydrogen, the flow rate is 0.5-1.5 m 3 / h, the thermal decomposition temperature is 800-1200℃, and the holding time is greater than 240 min.

9. The method for preparing a reticulated fiber reinforced tungsten-based composite material according to claim 1, characterized in that, The sintering temperature of the pre-sintering in step 5 is 1200-2300℃, the protective atmosphere is hydrogen, the flow rate is 0.5-1.5m 3 / h, the heating rate is 1-6℃ / min, the sintering time is 3050-4800 min, and the sintered body density is 70%-96%; the sintering temperature of the ultra-high pressure high temperature sintering is 1200-1800℃, the pressure is 1 GPa-10 GPa, and the sintering time is 5-60 min.

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