CN110791674A - Preparation method of refractory carbide particle reinforced tungsten copper infiltrated composite material - Google Patents

Abstract

Translated fromChinese

本发明涉及一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，属于钨渗铜复合材料技术领域。本申请解决了现有过渡金属碳化物和硼化物之间具有较低的固溶度，很难制备得到过渡金属碳硼化物的问题。本发明将钨粉和过渡金属碳化物粉体配置成浆料，经过砂磨、喷雾干燥、射频等离子球化获得复合粉体。将复合粉体通过模压和冷等静压的方式获得多孔坯体，再经过排胶和高温烧结后获得多孔预制体，在1100℃～1400℃下渗入金属铜，制备出难熔碳化物颗粒增强钨渗铜复合材料。该复合材料在不降低钨渗铜材料耐烧蚀性能的基础上，进一步降低了材料的密度和热导率，同时力学性能大大提高。

The invention relates to a preparation method of a refractory carbide particle-reinforced tungsten-copper-infiltrated composite material, and belongs to the technical field of tungsten-copper-infiltrated composite materials. The present application solves the problem that the existing transition metal carbides and borides have low solid solubility, and it is difficult to prepare transition metal borides. In the present invention, tungsten powder and transition metal carbide powder are configured into slurry, and composite powder is obtained through sand grinding, spray drying and radio frequency plasma spheroidization. The composite powder is obtained by molding and cold isostatic pressing to obtain a porous body, and then a porous preform is obtained after debinding and high-temperature sintering, and metal copper is infiltrated at 1100 ° C ~ 1400 ° C to prepare refractory carbide particles reinforced Tungsten infiltrated copper composite material. The composite material further reduces the density and thermal conductivity of the material without reducing the ablation resistance of the tungsten-infiltrated copper material, and at the same time greatly improves the mechanical properties.

Description

Translated fromChinese

一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法A kind of preparation method of refractory carbide particle reinforced tungsten copper infiltration composite material

技术领域technical field

本发明涉及一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，属于钨渗铜复合材料技术领域。The invention relates to a preparation method of a refractory carbide particle-reinforced tungsten-copper-infiltrated composite material, and belongs to the technical field of tungsten-copper-infiltrated composite materials.

背景技术Background technique

钨渗铜材料是由高熔点、高强度的钨骨架熔渗金属铜所制备的复合材料，主要成分为钨，其含量在80％以上。渗入的铜在高温时会熔融挥发，起到发汗冷却的作用。钨渗铜材料具有高强度、高硬度、抗高温、耐烧蚀、低膨胀系数等优点，被广泛应用于航空航天(如火箭喷嘴、飞机喉衬等)、机械和电子等高温领域。The tungsten copper infiltration material is a composite material prepared by infiltrating metal copper with a high melting point and high strength tungsten skeleton. The main component is tungsten, and its content is more than 80%. The infiltrated copper will melt and volatilize at high temperature, and play the role of sweating and cooling. Tungsten infiltrated copper material has the advantages of high strength, high hardness, high temperature resistance, ablation resistance, low expansion coefficient, etc., and is widely used in high temperature fields such as aerospace (such as rocket nozzles, aircraft throat linings, etc.), machinery and electronics.

钨渗铜是应用于固体火箭发动机喉衬的最主要材料，钨渗铜喉衬性能稳定，耐烧蚀性能较好。但是钨渗铜材料密度大，热导率偏高，钨骨架在超高温烧蚀环境下强度偏低且尺寸稳定性较差，逐渐不适应航天领域轻质高效的要求。难熔金属碳化物增强钨基复合材料具有高强、高韧性、轻质耐烧蚀的优点，但是热压烧结成本高且难以实现构件的近净成型，限制了该材料的应用。因此，提供一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法是十分必要的。Tungsten-infiltrated copper is the most important material used in solid rocket motor throat linings. Tungsten-infiltrated copper throat linings have stable performance and good ablation resistance. However, the tungsten infiltrated copper material has high density and high thermal conductivity, and the tungsten skeleton has low strength and poor dimensional stability in the ultra-high temperature ablation environment, which gradually does not meet the requirements of lightweight and high efficiency in the aerospace field. Refractory metal carbide reinforced tungsten-based composites have the advantages of high strength, high toughness, light weight and ablation resistance, but the high cost of hot pressing sintering and the difficulty of achieving near-net shape of components limit the application of this material. Therefore, it is very necessary to provide a preparation method of refractory carbide particle reinforced tungsten copper-infiltrated composite material.

发明内容SUMMARY OF THE INVENTION

本发明为了解决现有过渡金属碳化物和硼化物之间具有较低的固溶度，很难制备得到过渡金属碳硼化物的问题，提供一种超硬单相的碳硼化物四元固溶体陶瓷材料的制备方法。In order to solve the problem that the existing transition metal carbides and borides have low solid solubility and it is difficult to prepare transition metal carbonborides, the present invention provides a superhard single-phase carbonboride quaternary solid solution ceramics Method of preparation of materials.

本发明的技术方案：Technical scheme of the present invention:

一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，该方法的操作步骤如下：A preparation method of a refractory carbide particle reinforced tungsten copper-infiltrated composite material, the operation steps of the method are as follows:

步骤一，将分散剂和粘结剂溶解在去离子水中，然后加入粉体，超声处理，获得浆料；Step 1, dissolving the dispersant and the binder in deionized water, then adding the powder, and ultrasonically treating it to obtain a slurry;

步骤二，对步骤一获得的浆料进行研磨；研磨后的浆料在惰性气氛下喷雾造粒，得到复合微粒；In step 2, the slurry obtained in step 1 is ground; the ground slurry is sprayed and granulated in an inert atmosphere to obtain composite particles;

步骤三，对复合微粒进行球化处理后，进行干压成型，制得生坯，然后将生坯进行冷等静压成型，煅烧，得到多孔预制体；Step 3: After spheroidizing the composite particles, dry pressing is performed to obtain a green body, and then the green body is subjected to cold isostatic pressing and calcination to obtain a porous preform;

步骤四，使用金属铜对多孔预制体进行熔渗，得到难熔碳化物颗粒增强钨渗铜复合材料。In step 4, metal copper is used to infiltrate the porous preform to obtain a refractory carbide particle reinforced tungsten copper-infiltrated composite material.

优选的：所述的步骤一中粉体为碳化物和钨粉，粉体中碳化物的质量为粉体总质量的1％～20％，余量为钨粉；所述的钨粉粒径为1μm～10μm。Preferably: the powder in the first step is carbide and tungsten powder, the mass of carbide in the powder is 1% to 20% of the total mass of the powder, and the balance is tungsten powder; the particle size of the tungsten powder is 1 μm to 10 μm.

最优选的：所述的步骤一中碳化物为碳化锆、碳化钛、碳化铌、碳化钽、碳化铬、碳化钒、碳化钼或碳化铪；所述的分散剂为聚乙烯醇脂，聚乙烯醇脂的质量为粉体总质量的1％～2％；所述的粘结剂为乙烯醇，乙烯醇的质量为粉体总质量的1％～2％；所述的浆料固体含量为30wt％～60wt％。Most preferably: in the step 1, the carbide is zirconium carbide, titanium carbide, niobium carbide, tantalum carbide, chromium carbide, vanadium carbide, molybdenum carbide or hafnium carbide; the dispersant is polyvinyl alcohol grease, polyethylene The quality of the alcohol fat is 1% to 2% of the total mass of the powder; the binder is vinyl alcohol, and the quality of the vinyl alcohol is 1% to 2% of the total mass of the powder; the solid content of the slurry is 30wt%～60wt%.

优选的：所述的步骤二中使用砂磨机对浆料进行研磨，研磨条件：转速为500r/min～3000r/min，研磨时间为5h～10h。Preferably: in the second step, a sand mill is used to grind the slurry, and the grinding conditions are: the rotation speed is 500r/min～3000r/min, and the grinding time is 5h～10h.

优选的：所述的步骤二中在在惰性气氛下使用喷雾干燥造粒机对研磨后的浆料进行喷雾造粒，喷雾造粒条件为：浆料泵输送浆料的压力为0.1MPa～0.5Mpa，离心转盘的转速为10000rpm～35000rpm，进口温度为200℃，出口温度为100℃。Preferably: in the second step, the ground slurry is spray-granulated using a spray-drying granulator under an inert atmosphere, and the spray-granulation conditions are: the pressure of the slurry pump to transport the slurry is 0.1 MPa to 0.5 Mpa, the rotational speed of the centrifugal turntable is 10000rpm to 35000rpm, the inlet temperature is 200°C, and the outlet temperature is 100°C.

优选的：所述的步骤三采用射频等离子球化设备对复合微粒进行球化处理，球化处理条件为：射频等离子球化输入功率为30KW～60KW，送粉速率为5g/min～50g/min，送粉气工作气流量为5L/min～20L/min，中气工作气流量为20L/min～50L/min，边气工作气流量为50L/min～100L/min。Preferably, in the third step, the composite particles are spheroidized by using radio frequency plasma spheroidization equipment, and the spheroidization treatment conditions are: the input power of the radio frequency plasma spheroidization is 30KW～60KW, and the powder feeding rate is 5g/min～50g/min , The working gas flow of powder gas is 5L/min～20L/min, the working gas flow of middle gas is 20L/min～50L/min, and the working gas flow of side gas is 50L/min～100L/min.

优选的：所述的步骤三将球化处理后的复合微粒放入钢模中干压成型得到生坯，干压成型条件为：压力为10MPa～50MPa，保压时间为1min～5min。Preferably: in the step 3, the spheroidized composite particles are put into a steel mold for dry pressing to obtain a green body.

优选的：所述的步骤三将生坯进行冷等静压成型的条件为：压力为50MPa～200Mpa，保压时间为1min～3min。Preferably, in the third step, the conditions for cold isostatic pressing of the green body are as follows: the pressure is 50MPa-200Mpa, and the pressure holding time is 1min-3min.

优选的：所述的步骤三中煅烧的条件为：在氩气流中，以0.5℃/min～2℃/min的速度升温到500℃～600℃后煅烧1h～4h，然后以20℃/min的速度升温到2000℃～2300℃后烧结2h～4h。Preferably: the conditions for calcination in the third step are: in an argon flow, the temperature is raised to 500°C to 600°C at a rate of 0.5°C/min to 2°C/min, followed by calcination for 1h to 4h, and then to 20°C/min. The speed of heating to 2000 ℃ ~ 2300 ℃ and then sintering for 2h ~ 4h.

优选的：所述的步骤四为在1100℃～1400℃下使用金属铜对多孔预制体进行熔渗，熔渗时间为0.5h～2h。Preferably: the fourth step is to use metal copper to infiltrate the porous preform at 1100°C to 1400°C, and the infiltration time is 0.5h to 2h.

本发明具有以下有益效果：本发明采用难熔金属碳化物颗粒增强钨渗铜制备复合材料，在保留钨渗铜材料耐烧蚀性能的基础上，轻质碳化物颗粒能够使复合材料的密度降低，复合材料密度不超过16.0g/cm³。同时提高了复合材料的力学性能，复合材料抗弯强度达800MPa～1300MPa，断裂韧性达11MPa·m^1/2～18MPa·m^1/2，热导率不高于160W/(m·K)。本发明在制备过程中采用砂磨机研磨浆料有效降低碳化物和钨粉的粒度，使两者混合更加均匀；采用射频等离子球化工艺可以得到球化率高、球形度好的复合微粒，高度球化的原始粉体提高了多孔骨架强度，改善了骨架与铜的润湿性；通过控制干压成型和冷等静压的压力和保压时间可以实现对多孔预制体孔结构和孔径大小调控。The invention has the following beneficial effects: the invention adopts the refractory metal carbide particles to strengthen the tungsten copper infiltration to prepare the composite material, and on the basis of retaining the ablation resistance of the tungsten copper infiltration material, the light carbide particles can reduce the density of the composite material , the density of the composite material does not exceed 16.0g/cm³ . At the same time, the mechanical properties of the composite material are improved. The flexural strength of the composite material reaches 800MPa to 1300MPa, the fracture toughness reaches 11MPa·m^1/2 to 18MPa·m^1/2 , and the thermal conductivity is not higher than 160W/(m·K). In the preparation process of the invention, a sand mill is used to grind the slurry to effectively reduce the particle size of the carbide and the tungsten powder, so that the two are mixed more uniformly; the radio frequency plasma spheroidization process can be used to obtain composite particles with high spheroidization rate and good sphericity. The highly spheroidized original powder increases the strength of the porous skeleton and improves the wettability of the skeleton and copper; the pore structure and pore size of the porous preform can be realized by controlling the pressure and holding time of dry pressing and cold isostatic pressing. regulation.

附图说明Description of drawings

图1为具体实施方式3制备的多孔预制体的表面SEM照片；1 is a surface SEM photo of the porous preform prepared in Embodiment 3;

图2为具体实施方式3制备的难熔碳化物颗粒增强钨渗铜复合材料的表面SEM照片。FIG. 2 is a surface SEM photograph of the refractory carbide particle-reinforced tungsten-copper-infiltrated composite material prepared in Embodiment 3. FIG.

具体实施方式Detailed ways

下述实施例中所使用的实验方法如无特殊说明均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.

具体实施方式1：Specific implementation 1:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化锆和钨粉组成，粉体中碳化锆和钨粉的质量比为5:95，碳化锆和钨粉体的纯度＞99％，碳化锆和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of zirconium carbide and tungsten powder, the mass ratio of zirconium carbide and tungsten powder in the powder is 5:95, the purity of zirconium carbide and tungsten powder is more than 99%, and the particle size of zirconium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化；然后喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化锆/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry configured in step 1 at a rotational speed of 2000 rpm for 10 hours, so that the slurry is more uniform and stable and the particle size of the carbide and tungsten powder is refined; then the spray drying granulator will mix the slurry The material is sprayed and granulated to obtain zirconium carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the pressure of the slurry pump of the spray drying granulator to deliver the slurry is 0.15MPa, and the rotational speed of the centrifugal turntable is 25000rpm. The inlet temperature of the dry granulator was 200°C and the outlet temperature was 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化锆/钨复合微粒球化，射频等离子球化输入功率为50KW，送粉速率为20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径30μm。然后将碳化锆/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The zirconium carbide/tungsten composite particles obtained in step 3 were spheroidized by radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20 g/min, and the working gas flow rate of powder feeding gas was 6L/min. min, the working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 30 μm. Then, the zirconium carbide/tungsten composite particles were put into a steel mold for dry pressing with a pressure of 20 MPa and a holding time of 3 minutes; the green body was then cold isostatically pressed with a pressure of 200 MPa and a holding time of 2 minutes.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化锆增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化锆增强钨多孔预制体，该孔预制体的室温压缩强度为1261MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body was heated to 500 °C at 1 °C/min, fired for 2 h, and then cooled to room temperature at 5 °C/min to prepare a zirconium carbide reinforced tungsten porous green body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a zirconium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1261 MPa.

(6)将多孔预制体用金属铜在1200℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化锆颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1200° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the zirconium carbide particle reinforced tungsten copper infiltration composite material.

对本具体实施例的到的碳化锆增强钨渗铜复合材料进行检测，可知该复合材料的密度为15.89g/cm³；抗弯强度为1243MPa；断裂韧性为17.5MPa·m^1/2；热导率为158.2W/(m·K)。The zirconium carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example is detected, and it is known that the density of the composite material is 15.89 g/cm³ ; the flexural strength is 1243 MPa; the fracture toughness is 17.5 MPa·m^1/2 ; The rate is 158.2W/(m·K).

具体实施方式二：Specific implementation two:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化锆和钨粉组成，粉体中碳化锆和钨粉的质量比为10:90，碳化锆和钨粉体的纯度＞99％，碳化锆和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of zirconium carbide and tungsten powder, the mass ratio of zirconium carbide and tungsten powder in the powder is 10:90, the purity of zirconium carbide and tungsten powder is more than 99%, and the particle size of zirconium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为132nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化锆/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours to make the slurry more uniform and stable and to refine the particle size of carbide and tungsten powder. Use a laser particle size analyzer to measure the slurry after mixing The particle size D90 of the medium powder particles is 132 nm; then the mixed slurry is spray granulated by a spray drying granulator to obtain zirconium carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the spray drying granulator The pressure of the slurry pump conveying the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化锆/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径28μm。然后将碳化锆/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The zirconium carbide/tungsten composite particles obtained in step 3 were spheroidized by radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20 g/min, and the working air flow rate of powder feeding gas was 6L/min, The working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 28 μm. Then, the zirconium carbide/tungsten composite particles were put into a steel mold for dry pressing with a pressure of 20 MPa and a holding time of 3 minutes; the green body was then cold isostatically pressed with a pressure of 200 MPa and a holding time of 2 minutes.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化锆增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化锆增强钨多孔预制体，该孔预制体的室温压缩强度为1296MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body was heated to 500 °C at 1 °C/min, fired for 2 h, and then cooled to room temperature at 5 °C/min to prepare a zirconium carbide reinforced tungsten porous green body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a zirconium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1296 MPa.

(6)将多孔预制体用金属铜在1200℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化锆颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1200° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the zirconium carbide particle reinforced tungsten copper infiltration composite material.

对本具体实施例的到的碳化锆增强钨渗铜复合材料进行检测，可知该复合材料的密度为15.3g/cm³；抗弯强度为1022MPa；断裂韧性为17.4MPa·m^1/2；热导率为143W/(m·K)。The zirconium carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example is tested, and it is known that the density of the composite material is 15.3 g/cm³ ; the flexural strength is 1022 MPa; the fracture toughness is 17.4 MPa·m^1/2 ; The rate is 143W/(m·K).

具体实施方式三：Specific implementation three:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化锆和钨粉组成，粉体中碳化锆和钨粉的质量比为15:85，碳化锆和钨粉体的纯度＞99％，碳化锆和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of zirconium carbide and tungsten powder, the mass ratio of zirconium carbide and tungsten powder in the powder is 15:85, the purity of zirconium carbide and tungsten powder is more than 99%, and the particle size of zirconium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为107nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化锆/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours to make the slurry more uniform and stable and to refine the particle size of carbide and tungsten powder. Use a laser particle size analyzer to measure the slurry after mixing The particle size D90 of the medium powder particles is 107 nm; then the mixed slurry is spray granulated by a spray drying granulator to obtain zirconium carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the spray drying granulator The pressure of the slurry pump conveying the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化锆/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径25μm。然后将碳化锆/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The zirconium carbide/tungsten composite particles obtained in step 3 were spheroidized by radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20 g/min, and the working air flow rate of powder feeding gas was 6L/min, The working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 25 μm. Then, the zirconium carbide/tungsten composite particles were put into a steel mold for dry pressing with a pressure of 20 MPa and a holding time of 3 minutes; the green body was then cold isostatically pressed with a pressure of 200 MPa and a holding time of 2 minutes.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化锆增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化锆增强钨多孔预制体，该孔预制体的室温压缩强度为1344MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, and pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body was heated to 500 °C at 1 °C/min, fired for 2 h, and then cooled to room temperature at 5 °C/min to prepare a zirconium carbide reinforced tungsten porous green body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a zirconium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1344 MPa.

(6)将多孔预制体用金属铜在1200℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化锆颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1200° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the zirconium carbide particle reinforced tungsten copper infiltration composite material.

对本具体实施例的到的碳化锆增强钨渗铜复合材料进行检测，可知该复合材料的密度为15.0g/cm³；抗弯强度为930MPa；断裂韧性为17.9MPa·m^1/2；热导率为151W/(m·K)。The zirconium carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example is tested, and it is known that the density of the composite material is 15.0 g/cm³ ; the flexural strength is 930 MPa; the fracture toughness is 17.9 MPa·m^1/2 ; The rate is 151W/(m·K).

具体实施方式4：Specific implementation 4:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化锆和钨粉组成，粉体中碳化锆和钨粉的质量比为20:80，碳化锆和钨粉体的纯度＞99％，碳化锆和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of zirconium carbide and tungsten powder, the mass ratio of zirconium carbide and tungsten powder in the powder is 20:80, the purity of zirconium carbide and tungsten powder is more than 99%, and the particle size of zirconium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为144nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化锆/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours to make the slurry more uniform and stable and to refine the particle size of carbide and tungsten powder. Use a laser particle size analyzer to measure the slurry after mixing The particle size D90 of the medium powder particles is 144 nm; then the mixed slurry is spray granulated by a spray drying granulator to obtain zirconium carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the spray drying granulator The pressure of the slurry pump conveying the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化锆/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径33μm。然后将碳化锆/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The zirconium carbide/tungsten composite particles obtained in step 3 were spheroidized by radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20 g/min, and the working air flow rate of powder feeding gas was 6L/min, The working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 33 μm. Then, the zirconium carbide/tungsten composite particles were put into a steel mold for dry pressing with a pressure of 20 MPa and a holding time of 3 minutes; the green body was then cold isostatically pressed with a pressure of 200 MPa and a holding time of 2 minutes.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化锆增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化锆增强钨多孔预制体，该孔预制体的室温压缩强度为1420MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body was heated to 500 °C at 1 °C/min, fired for 2 h, and then cooled to room temperature at 5 °C/min to prepare a zirconium carbide reinforced tungsten porous green body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a zirconium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1420 MPa.

(6)将多孔预制体用金属铜在1300℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化锆颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1300° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the zirconium carbide particle reinforced tungsten copper infiltration composite material.

对本具体实施例的到的碳化锆增强钨渗铜复合材料进行检测，可知该复合材料的密度为14.3g/cm³；抗弯强度为1053MPa；断裂韧性为15.4MPa·m^1/2；热导率为128W/(m·K)。The zirconium carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example is detected, and it is known that the density of the composite material is 14.3 g/cm³ ; the flexural strength is 1053 MPa; the fracture toughness is 15.4 MPa·m^1/2 ; The rate is 128W/(m·K).

具体实施方式5：Specific implementation 5:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化钛和钨粉组成，粉体中碳化钛和钨粉的质量比为20:80，碳化钛和钨粉体的纯度＞99％，碳化钛和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of titanium carbide and tungsten powder. The mass ratio of titanium carbide and tungsten powder in the powder is 20:80, the purity of titanium carbide and tungsten powder is more than 99%, and the particle size of titanium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为121nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化钛/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours to make the slurry more uniform and stable and to refine the particle size of carbide and tungsten powder. Use a laser particle size analyzer to measure the slurry after mixing The particle size D90 of the medium powder particles is 121 nm; then the mixed slurry is spray granulated by a spray drying granulator to obtain titanium carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the spray drying granulator The pressure of the slurry pump conveying the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化钛/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径30μm。然后将碳化钛/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The titanium carbide/tungsten composite particles obtained in step 3 were spheroidized by using radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20g/min, and the working air flow rate of powder feeding gas was 6L/min, The working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 30 μm. Then, the titanium carbide/tungsten composite particles are put into a steel mold for dry pressing with a pressure of 20 MPa and a holding time of 3 minutes; the green body is then cold isostatically pressed with a pressure of 200 MPa and a holding time of 2 minutes.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化钛增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化钛增强钨多孔预制体，该孔预制体的室温压缩强度为1008MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body was heated to 500 °C at 1 °C/min, fired for 2 h, and then cooled to room temperature at 5 °C/min to prepare a titanium carbide reinforced tungsten porous body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a titanium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1008 MPa.

(6)将多孔预制体用金属铜在1200℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化钛颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1200° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the titanium carbide particle reinforced tungsten copper infiltration composite material.

对本具体实施例的到的碳化钛增强钨渗铜复合材料进行检测，可知该复合材料的密度为14.2g/cm³；抗弯强度为811MPa；断裂韧性为14.6MPa·m^1/2；热导率为143W/(m·K)。The titanium carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example is tested, and it is known that the density of the composite material is 14.2 g/cm³ ; the flexural strength is 811 MPa; the fracture toughness is 14.6 MPa·m^1/2 ; The rate is 143W/(m·K).

具体实施方式6：Specific implementation 6:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化铌和钨粉组成，粉体中碳化铌和钨粉的质量比为20:80，碳化铌和钨粉体的纯度＞99％，碳化铌和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of niobium carbide and tungsten powder. The mass ratio of niobium carbide and tungsten powder in the powder is 20:80. The purity of niobium carbide and tungsten powder is more than 99%. The particle size of niobium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为173nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化铌/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours to make the slurry more uniform and stable and to refine the particle size of carbide and tungsten powder. Use a laser particle size analyzer to measure the slurry after mixing The particle size D90 of the medium powder particles is 173 nm; then the mixed slurry is spray granulated by a spray drying granulator to obtain niobium carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the spray drying granulator The pressure of the slurry pump conveying the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化铌/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率为20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径37μm。然后将碳化铌/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The niobium carbide/tungsten composite particles obtained in step 3 were spheroidized by radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20 g/min, and the working gas flow rate of powder feeding gas was 6L/min , the working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 37 μm. Then, the niobium carbide/tungsten composite particles are put into a steel mold for dry pressing, the pressure is 20MPa, and the pressure holding time is 3min; and then the green body is cold isostatically pressed, the pressure is 200MPa, and the pressure holding time is 2min.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化铌增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化铌增强钨多孔预制体，该孔预制体的室温压缩强度为975MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body was heated to 500 °C at 1 °C/min, fired for 2 h, and then cooled to room temperature at 5 °C/min to prepare a niobium carbide reinforced tungsten porous body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a niobium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 975 MPa.

(6)将多孔预制体用金属铜在1200℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化铌颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1200° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the niobium carbide particle reinforced tungsten infiltrated copper composite material.

对本具体实施例的到的碳化铌增强钨渗铜复合材料进行检测，可知该复合材料的密度为14.6g/cm³；抗弯强度为847MPa；断裂韧性为13.8MPa·m^1/2；热导率为155W/(m·K)。The niobium carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example is detected, and it is known that the density of the composite material is 14.6 g/cm³ ; the flexural strength is 847 MPa; the fracture toughness is 13.8 MPa·m^1/2 ; The rate is 155W/(m·K).

具体实施方式7：Specific implementation 7:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化铪和钨粉组成，粉体中碳化铪和钨粉的质量比为20:80，碳化铪和钨粉体的纯度＞99％，碳化铪和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of hafnium carbide and tungsten powder, the mass ratio of hafnium carbide and tungsten powder in the powder is 20:80, the purity of hafnium carbide and tungsten powder is more than 99%, and the particle size of hafnium carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化物和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为103nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化铪钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours to make the slurry more uniform and stable and to refine the particle size of carbide and tungsten powder. Use a laser particle size analyzer to measure the slurry after mixing The particle size D90 of the medium powder particles is 103 nm; then the mixed slurry is spray-granulated by a spray-drying granulator to obtain hafnium-tungsten carbide composite powder particles with a particle size of 20 μm to 30 μm. The pressure of the slurry pump to transport the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化铪/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率为20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径22μm。然后将碳化铪/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The hafnium carbide/tungsten composite particles obtained in step 3 are spheroidized by using radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization is 50KW, the powder feeding rate is 20g/min, and the working gas flow rate of powder feeding gas is 6L/min , the working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 22 μm. Then, the hafnium carbide/tungsten composite particles are put into a steel mold for dry pressing with a pressure of 20 MPa and a holding time of 3 minutes; the green body is then cold isostatically pressed with a pressure of 200 MPa and a holding time of 2 minutes.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化铪增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化铪增强钨多孔预制体，该孔预制体的室温压缩强度为1237MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body is heated to 500°C at 1°C/min, fired for 2 hours, and then cooled to room temperature at 5°C/min to prepare a hafnium carbide reinforced tungsten porous blank. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a hafnium carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1237 MPa.

(6)将多孔预制体用金属铜在1300℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化铪颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1300° C. under vacuum conditions, and the infiltration time is 0.5 h to complete the preparation of the hafnium carbide particle reinforced tungsten infiltrated copper composite material.

对本具体实施例的到的碳化铪增强钨渗铜复合材料进行检测，可知该复合材料的密度为15.3g/cm³；抗弯强度为1026MPa；断裂韧性为14.4MPa·m^1/2；热导率为151W/(m·K)。Detecting the hafnium carbide reinforced tungsten copper-infiltrated composite material obtained in this specific embodiment, it is known that the density of the composite material is 15.3 g/cm³ ; the flexural strength is 1026 MPa; the fracture toughness is 14.4 MPa·m^1/2 ; The rate is 151W/(m·K).

具体实施方式8：Specific implementation 8:

(1)以200mL去离子水为分散介质，先加入1mL聚乙烯醇脂分散剂和1mL聚乙烯醇粘结剂，待分散剂和粘结剂完全溶于分散介质，然后加入100g粉体，其中粉体由碳化钽和钨粉组成，粉体中碳化钽和钨粉的质量比为20:80，碳化钽和钨粉体的纯度＞99％，碳化钽和钨粉的粒径为1μm～2μm，超声处理30min后，得到浆料。(1) Take 200 mL of deionized water as the dispersion medium, first add 1 mL of polyvinyl alcohol fat dispersant and 1 mL of polyvinyl alcohol binder, wait until the dispersant and the binder are completely dissolved in the dispersion medium, and then add 100 g of powder, wherein The powder is composed of tantalum carbide and tungsten powder. The mass ratio of tantalum carbide and tungsten powder in the powder is 20:80, the purity of tantalum carbide and tungsten powder is more than 99%, and the particle size of tantalum carbide and tungsten powder is 1μm～2μm , and after ultrasonic treatment for 30 min, a slurry was obtained.

(2)使用砂磨机将步骤一中配置的浆料以转速2000rpm研磨10h，使浆料更加均匀稳定且碳化钽和钨粉的粒径细化，使用激光粒度仪测得混匀后浆料中粉体颗粒的粒径D90为150nm；然后使用喷雾干燥造粒机将混匀后浆料喷雾造粒，得到粒径为20μm～30μm的碳化钽/钨复合粉末微粒，其中喷雾干燥造粒机的浆料泵输送浆料的压力为0.15MPa，离心转盘的转速为25000rpm，所述喷雾干燥造粒机的进口温度为200℃，出口温度为100℃。(2) Use a sand mill to grind the slurry prepared in step 1 at a speed of 2000 rpm for 10 hours, so that the slurry is more uniform and stable and the particle size of the tantalum carbide and tungsten powders is refined, and the slurry after mixing is measured by a laser particle sizer. The particle size D90 of the medium powder particles is 150 nm; then the mixed slurry is spray granulated by a spray drying granulator to obtain tantalum carbide/tungsten composite powder particles with a particle size of 20 μm to 30 μm, wherein the spray drying granulator The pressure of the slurry pump conveying the slurry is 0.15MPa, the rotational speed of the centrifugal turntable is 25000rpm, the inlet temperature of the spray drying granulator is 200°C, and the outlet temperature is 100°C.

(4)采用射频等离子球化设备将步骤三中得到的碳化钽/钨复合微粒球化，射频等离子球化输入功率50KW，送粉速率20g/min，送粉气工作气流量为6L/min，中气工作气流量为30L/min，边气工作气流量为80L/min。球化后复合微粒的粒径44μm。然后将碳化钽/钨复合微粒放入钢模中干压成型，压力大小为20MPa，保压时间为3min；再将生坯冷等静压成型，压力大小为200MPa，保压时间为2min。(4) The tantalum carbide/tungsten composite particles obtained in step 3 were spheroidized by using radio frequency plasma spheroidization equipment, the input power of radio frequency plasma spheroidization was 50KW, the powder feeding rate was 20 g/min, and the working air flow rate of powder feeding gas was 6L/min, The working gas flow of the middle gas is 30L/min, and the working gas flow of the side gas is 80L/min. The particle size of the composite particles after spheroidization was 44 μm. Then, the tantalum carbide/tungsten composite particles are put into a steel mold for dry pressing, the pressure is 20MPa, and the pressure holding time is 3min; then the green body is cold isostatically pressed, the pressure is 200MPa, and the pressure holding time is 2min.

(5)将冷等静压之后的坯体放入低温烧结炉，通入流动氩气，氩气流量为0.2L/min。将坯体以1℃/min升温到500℃，灼烧2h，然后以5℃/min降温到室温，制备得到碳化钽增强钨多孔坯体。然后将多孔坯体在高温烧结炉中以20℃/min升温到2000℃，并于氩气流中保温2h，然后以20℃/min降温到室温，获得碳化钽增强钨多孔预制体，该孔预制体的室温压缩强度为1332MPa。(5) Put the green body after cold isostatic pressing into a low-temperature sintering furnace, pass flowing argon gas, and the flow rate of argon gas is 0.2L/min. The green body is heated to 500° C. at 1° C./min, fired for 2 hours, and then cooled to room temperature at 5° C./min to prepare a tantalum carbide-reinforced tungsten porous body. Then, the porous body was heated to 2000°C at 20°C/min in a high-temperature sintering furnace, kept in an argon flow for 2 hours, and then cooled to room temperature at 20°C/min to obtain a tantalum carbide reinforced tungsten porous preform. The room temperature compressive strength of the body is 1332 MPa.

(6)将多孔预制体用金属铜在1400℃，真空条件下进行熔渗，熔渗时间为0.5h，完成碳化钽颗粒增强钨渗铜复合材料的制备。(6) The porous preform is infiltrated with metallic copper at 1400° C. under vacuum conditions, and the infiltration time is 0.5 h, to complete the preparation of the tantalum carbide particle reinforced tungsten-infiltrated copper composite material.

对本具体实施例的到的碳化钽增强钨渗铜复合材料进行检测，可知该复合材料的密度为15.5g/cm³；抗弯强度为951MPa；断裂韧性为12.1MPa·m^1/2；热导率为138W/(m·K)。Detecting the tantalum carbide reinforced tungsten-infiltrated copper composite material obtained in this specific example, it is known that the density of the composite material is 15.5g/cm³ ; the flexural strength is 951MPa; the fracture toughness is 12.1MPa·m^1/2 ; The rate is 138W/(m·K).

Claims (10)

Translated fromChinese

1.一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：该方法的操作步骤如下：1. a preparation method of refractory carbide particle reinforced tungsten copper-infiltrating composite material, is characterized in that: the operation steps of this method are as follows:步骤一，将分散剂和粘结剂溶解在去离子水中，然后加入粉体，超声处理，获得浆料；Step 1, dissolving the dispersant and the binder in deionized water, then adding the powder, and ultrasonically treating it to obtain a slurry;步骤二，对步骤一获得的浆料进行研磨；研磨后的浆料在惰性气氛下喷雾造粒，得到复合微粒；In step 2, the slurry obtained in step 1 is ground; the ground slurry is sprayed and granulated in an inert atmosphere to obtain composite particles;步骤三，对复合微粒进行球化处理后，进行干压成型，制得生坯，然后将生坯进行冷等静压成型，煅烧得到多孔坯体后冷却，对多孔坯体煅烧，得到多孔预制体；Step 3: After spheroidizing the composite particles, dry pressing is performed to obtain a green body, and then the green body is subjected to cold isostatic pressing, calcined to obtain a porous body, and then cooled, and the porous body is calcined to obtain a porous prefabricated body. body;步骤四，使用金属铜对多孔预制体进行熔渗，得到难熔碳化物颗粒增强钨渗铜复合材料。In step 4, metal copper is used to infiltrate the porous preform to obtain a refractory carbide particle reinforced tungsten copper-infiltrated composite material.2.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤一中粉体为碳化物和钨粉，粉体中碳化物的质量为粉体总质量的1％～20％，余量为钨粉；所述的钨粉粒径为1μm～10μm。2. the preparation method of a kind of refractory carbide particle reinforced tungsten copper infiltration composite material according to claim 1, is characterized in that: in the described step 1, the powder is carbide and tungsten powder, and the powder is carbonized The mass of the powder is 1% to 20% of the total mass of the powder, and the balance is tungsten powder; the particle size of the tungsten powder is 1 μm to 10 μm.3.根据权利要球2所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤一中碳化物为碳化锆、碳化钛、碳化铌、碳化钽、碳化铬、碳化钒、碳化钼或碳化铪；所述的分散剂为聚乙烯醇脂，聚乙烯醇脂的质量为粉体总质量的1％～2％；所述的粘结剂为乙烯醇，乙烯醇的质量为粉体总质量的1％～2％；所述的浆料固体含量为30wt％～60wt％。3. the preparation method of a kind of refractory carbide particle reinforced tungsten copper infiltration composite material according to claim 2, is characterized in that: in described step 1, carbide is zirconium carbide, titanium carbide, niobium carbide, carbide Tantalum, chromium carbide, vanadium carbide, molybdenum carbide or hafnium carbide; the dispersant is polyvinyl alcohol grease, and the mass of the polyvinyl alcohol grease is 1% to 2% of the total mass of the powder; the binder is Vinyl alcohol, the mass of vinyl alcohol is 1% to 2% of the total mass of the powder; the solid content of the slurry is 30% to 60% by weight.4.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤二中使用砂磨机对浆料进行研磨，研磨条件：转速为500r/min～3000r/min，研磨时间为5h～10h。4. the preparation method of a kind of refractory carbide particle reinforced tungsten copper-infiltrating composite material according to claim 1, is characterized in that: in the described step 2, use a sand mill to grind the slurry, and the grinding conditions are: The rotating speed is 500r/min～3000r/min, and the grinding time is 5h～10h.5.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤二中在在惰性气氛下使用喷雾干燥造粒机对研磨后的浆料进行喷雾造粒，喷雾造粒条件为：浆料泵输送浆料的压力为0.1MPa～0.5Mpa，离心转盘的转速为10000rpm～35000rpm，进口温度为200℃，出口温度为100℃。5. the preparation method of a kind of refractory carbide particle reinforced tungsten copper-infiltrating composite material according to claim 1, is characterized in that: in described step 2, use spray drying granulator to grind under inert atmosphere The slurry is sprayed and granulated. The spray granulation conditions are: the pressure of the slurry pump to transport the slurry is 0.1MPa～0.5Mpa, the rotational speed of the centrifugal turntable is 10000rpm～35000rpm, the inlet temperature is 200℃, and the outlet temperature is 100℃ .6.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤三采用射频等离子球化设备对复合微粒进行球化处理，球化处理条件为：射频等离子球化输入功率为30KW～60KW，送粉速率为5g/min～50g/min，送粉气工作气流量为5L/min～20L/min，中气工作气流量为20L/min～50L/min，边气工作气流量为50L/min～100L/min。6. the preparation method of a kind of refractory carbide particle reinforced tungsten copper infiltration composite material according to claim 1, is characterized in that: described step 3 adopts radio frequency plasma spheroidizing equipment to carry out spheroidizing treatment to the composite particles, The spheroidizing treatment conditions are as follows: the input power of radio frequency plasma spheroidization is 30KW~60KW, the powder feeding rate is 5g/min~50g/min, the working air flow rate of powder feeding gas is 5L/min~20L/min, and the working air flow rate of medium gas is 20L/min～50L/min, the working air flow of side gas is 50L/min～100L/min.7.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤三将球化处理后的复合微粒放入钢模中干压成型得到生坯，干压成型条件为：压力为10MPa～50MPa，保压时间为1min～5min。7. the preparation method of a kind of refractory carbide particle reinforced tungsten copper-infiltrating composite material according to claim 1, is characterized in that: described step 3 puts the composite particle after spheroidizing treatment into the steel mold to dry Press molding to obtain a green body, and the dry pressing molding conditions are as follows: the pressure is 10 MPa to 50 MPa, and the pressure holding time is 1 min to 5 min.8.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤三将生坯进行冷等静压成型的条件为：压力为50MPa～200Mpa，保压时间为1min～3min。8. the preparation method of a kind of refractory carbide particle reinforced tungsten copper-infiltrating composite material according to claim 1, is characterized in that: the condition that described step 3 carries out cold isostatic pressing to green body is: pressure It is 50MPa～200Mpa, and the pressure holding time is 1min～3min.9.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤三中煅烧的条件为：在氩气流中，以0.5℃/min～2℃/min的速度升温到500℃～600℃后煅烧1h～4h后冷却，得到多孔坯体；然后在氩气流中以20℃/min的速度升温到2000℃～2300℃后烧结2h～4h，得到多孔预制体。9 . The method for preparing a refractory carbide particle-reinforced tungsten-copper-infiltrated composite material according to claim 1 , wherein the calcination condition in the third step is: in an argon flow, at a temperature of 0.5° C. The temperature is increased to 500℃～600℃ at the speed of /min～2℃/min, then calcined for 1h～4h, and then cooled to obtain a porous body; then it is heated to 2000℃～2300℃ at the speed of 20℃/min in an argon flow, and then sintered 2h to 4h to obtain a porous preform.10.根据权利要球1所述的一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法，其特征在于：所述的步骤四为在1100℃～1400℃下使用金属铜对多孔预制体进行熔渗，熔渗时间为0.5h～2h。10. The method for preparing a refractory carbide particle reinforced tungsten copper-infiltrated composite material according to claim 1, wherein the step 4 is to use metallic copper to prefabricate the porous The body is infiltrated, and the infiltration time is 0.5h to 2h.

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