阅读说明：本技术 一种难熔碳化物颗粒增强钨渗铜复合材料的制备方法 (Preparation method of refractory carbide particle reinforced tungsten copper infiltrated composite material ) 是由 王玉金 陈磊 霍思嘉 周玉 于 2019-11-13 设计创作，主要内容包括：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, belonging to the technical field of tungsten copper infiltrated composite materials. The application solves the problems that the prior transition metal carbide and boride have lower solid solubility and are difficult to prepare and obtain the transition metal carbide and boride. The invention prepares tungsten powder and transition metal carbide powder into slurry, and obtains composite powder through sanding, spray drying and radio frequency plasma spheroidization. And (3) obtaining a porous blank by carrying out die pressing and cold isostatic pressing on the composite powder, then carrying out gel discharging and high-temperature sintering to obtain a porous preform, and infiltrating metallic copper at the temperature of 1100-1400 ℃ to prepare the refractory carbide particle reinforced tungsten-copper infiltrated composite material. The composite material further reduces the density and the heat conductivity of the material on the basis of not reducing the ablation resistance of the tungsten copper infiltrated material, and simultaneously greatly improves the mechanical property.)

1. A method for preparing a refractory carbide particle reinforced tungsten copper infiltrated composite material is characterized by comprising the following steps: the method comprises the following operation steps:

dissolving a dispersing agent and a binder in deionized water, adding powder, and performing ultrasonic treatment to obtain slurry;

step two, grinding the slurry obtained in the step one; spraying and granulating the ground slurry in an inert atmosphere to obtain composite particles;

step three, after spheroidizing the composite particles, carrying out dry pressing forming to obtain a green body, then carrying out cold isostatic pressing forming on the green body, cooling after calcining to obtain a porous green body, and calcining the porous green body to obtain a porous prefabricated body;

and step four, infiltrating the porous preform by using metal copper to obtain the refractory carbide particle reinforced tungsten-infiltrated copper composite material.

2. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: in the first step, the powder is carbide and tungsten powder, the mass of the carbide in the powder is 1% -20% of the total mass of the powder, and the balance is tungsten powder; the particle size of the tungsten powder is 1-10 mu m.

3. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 2, wherein: the carbide in the first step is zirconium carbide, titanium carbide, niobium carbide, tantalum carbide, chromium carbide, vanadium carbide, molybdenum carbide or hafnium carbide; the dispersing agent is polyvinyl alcohol ester, and the mass of the polyvinyl alcohol ester is 1-2% of the total mass of the powder; the adhesive is vinyl alcohol, and the mass of the vinyl alcohol is 1-2% of the total mass of the powder; the solid content of the slurry is 30-60 wt%.

4. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: and grinding the slurry by using a sand mill in the second step, wherein the grinding conditions are as follows: the rotating speed is 500r/min to 3000r/min, and the grinding time is 5h to 10 h.

5. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: in the second step, a spray drying granulator is used for spray granulation of the ground slurry under an inert atmosphere, and the spray granulation conditions are as follows: the pressure of the slurry pump for conveying the slurry is 0.1 MPa-0.5 MPa, the rotating speed of the centrifugal turntable is 10000 rpm-35000 rpm, the inlet temperature is 200 ℃, and the outlet temperature is 100 ℃.

6. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: and step three, spheroidizing the composite particles by adopting radio frequency plasma spheroidizing equipment, wherein the spheroidizing conditions are as follows: the input power of the radio frequency plasma spheroidization is 30 KW-60 KW, the powder feeding speed is 5 g/min-50 g/min, the working gas flow of the powder feeding gas is 5L/min-20L/min, the working gas flow of the middle gas is 20L/min-50L/min, and the working gas flow of the side gas is 50L/min-100L/min.

7. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: and step three, putting the spheroidized composite particles into a steel die for dry pressing and forming to obtain a green body, wherein the dry pressing and forming conditions are as follows: the pressure is 10MPa to 50MPa, and the pressure maintaining time is 1min to 5 min.

8. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: and step three, carrying out cold isostatic pressing on the green body under the following conditions: the pressure is 50 MPa-200 MPa, and the pressure maintaining time is 1 min-3 min.

9. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: the calcining conditions in the third step are as follows: heating to 500-600 ℃ at the speed of 0.5-2 ℃/min in argon flow, calcining for 1-4 h, and cooling to obtain a porous blank; then heating to 2000-2300 ℃ in argon flow at the speed of 20 ℃/min, and sintering for 2-4 h to obtain the porous preform.

10. The method for preparing the refractory carbide particle reinforced tungsten-copper infiltrated composite material according to claim 1, wherein the method comprises the following steps: and step four, infiltrating the porous preform by using metal copper at the temperature of 1100-1400 ℃, wherein the infiltration time is 0.5-2 h.

Technical Field

The invention relates to a preparation method of a refractory carbide particle reinforced tungsten copper infiltrated composite material, belonging to the technical field of tungsten copper infiltrated composite materials.

Background

The tungsten copper infiltration material is a composite material prepared by infiltrating metal copper into a high-melting-point and high-strength tungsten framework, and the main component of the tungsten copper infiltration material is tungsten, and the content of the tungsten copper infiltration material is more than 80 percent. The infiltrated copper can be melted and volatilized at high temperature, and the sweating and cooling effects are realized. The tungsten copper infiltrated material has the advantages of high strength, high hardness, high temperature resistance, ablation resistance, low expansion coefficient and the like, and is widely applied to the high-temperature fields of aerospace (such as rocket nozzles, airplane throat linings and the like), machinery, electronics and the like.

The tungsten copper infiltration is the most main material applied to the throat insert of the solid rocket engine, and the tungsten copper infiltration throat insert has stable performance and better ablation resistance. However, the tungsten copper infiltrated material has high density and high thermal conductivity, and the tungsten skeleton has low strength and poor dimensional stability in an ultra-high temperature ablation environment, so that the tungsten copper infiltrated material is gradually not suitable for the requirements of light weight and high efficiency in the aerospace field. The refractory metal carbide reinforced tungsten-based composite material has the advantages of high strength, high toughness, light weight and ablation resistance, but the hot-pressing sintering cost is high, the near net shape of a component is difficult to realize, and the application of the material is limited. Therefore, it is necessary to provide a method for preparing a refractory carbide particle reinforced copper tungsten infiltrated composite material.

Disclosure of Invention

The invention provides a preparation method of a superhard single-phase carborundum quaternary solid solution ceramic material, aiming at solving the problems that the existing transition metal carbide and boride have lower solid solubility and are difficult to prepare and obtain the transition metal carborundum.

The technical scheme of the invention is as follows:

a method for preparing a refractory carbide particle reinforced tungsten copper infiltrated composite material comprises the following operation steps:

dissolving a dispersing agent and a binder in deionized water, adding powder, and performing ultrasonic treatment to obtain slurry;

step two, grinding the slurry obtained in the step one; spraying and granulating the ground slurry in an inert atmosphere to obtain composite particles;

step three, after spheroidizing the composite particles, carrying out dry pressing forming to prepare a green body, and then carrying out cold isostatic pressing forming and calcining on the green body to obtain a porous prefabricated body;

and step four, infiltrating the porous preform by using metal copper to obtain the refractory carbide particle reinforced tungsten-infiltrated copper composite material.

Preferably: in the first step, the powder is carbide and tungsten powder, the mass of the carbide in the powder is 1% -20% of the total mass of the powder, and the balance is tungsten powder; the particle size of the tungsten powder is 1-10 mu m.

Most preferably: the carbide in the first step is zirconium carbide, titanium carbide, niobium carbide, tantalum carbide, chromium carbide, vanadium carbide, molybdenum carbide or hafnium carbide; the dispersing agent is polyvinyl alcohol ester, and the mass of the polyvinyl alcohol ester is 1-2% of the total mass of the powder; the adhesive is vinyl alcohol, and the mass of the vinyl alcohol is 1-2% of the total mass of the powder; the solid content of the slurry is 30-60 wt%.

Preferably: and grinding the slurry by using a sand mill in the second step, wherein the grinding conditions are as follows: the rotating speed is 500r/min to 3000r/min, and the grinding time is 5h to 10 h.

Preferably: in the second step, a spray drying granulator is used for spray granulation of the ground slurry under an inert atmosphere, and the spray granulation conditions are as follows: the pressure of the slurry pump for conveying the slurry is 0.1 MPa-0.5 MPa, the rotating speed of the centrifugal turntable is 10000 rpm-35000 rpm, the inlet temperature is 200 ℃, and the outlet temperature is 100 ℃.

Preferably: and step three, spheroidizing the composite particles by adopting radio frequency plasma spheroidizing equipment, wherein the spheroidizing conditions are as follows: the input power of the radio frequency plasma spheroidization is 30 KW-60 KW, the powder feeding speed is 5 g/min-50 g/min, the working gas flow of the powder feeding gas is 5L/min-20L/min, the working gas flow of the middle gas is 20L/min-50L/min, and the working gas flow of the side gas is 50L/min-100L/min.

Preferably: and step three, putting the spheroidized composite particles into a steel die for dry pressing and forming to obtain a green body, wherein the dry pressing and forming conditions are as follows: the pressure is 10MPa to 50MPa, and the pressure maintaining time is 1min to 5 min.

Preferably: and step three, carrying out cold isostatic pressing on the green body under the following conditions: the pressure is 50 MPa-200 MPa, and the pressure maintaining time is 1 min-3 min.

Preferably: the calcining conditions in the third step are as follows: in argon flow, the temperature is raised to 500-600 ℃ at the speed of 0.5-2 ℃/min, then the calcination is carried out for 1-4 h, and then the temperature is raised to 2000-2300 ℃ at the speed of 20 ℃/min, and then the sintering is carried out for 2-4 h.

Preferably: and step four, infiltrating the porous preform by using metal copper at the temperature of 1100-1400 ℃, wherein the infiltration time is 0.5-2 h.

The invention has the following beneficial effects: the invention adopts refractory metal carbide particles to reinforce the tungsten copper infiltration to prepare the composite material, and on the basis of keeping the ablation resistance of the tungsten copper infiltration material, the light carbide particles can reduce the density of the composite material, and the density of the composite material is not more than 16.0g/cm³. Simultaneously improves the mechanical property of the composite material, the bending strength of the composite material reaches 800MPa to 1300MPa, and the fracture toughness reaches 11 MPa.m^1/2～18MPa·m^1/2The thermal conductivity is not higher than 160W/(mK). In the preparation process, the sand mill is adopted to grind the slurry, so that the particle sizes of the carbide and the tungsten powder are effectively reduced, and the carbide and the tungsten powder are mixed more uniformly; the composite particles with high spheroidization rate and good sphericity can be obtained by adopting a radio frequency plasma spheroidization process, and the original powder with high spheroidization rate improves the strength of a porous skeleton and improves the wettability of the skeleton and copper; the porous preform pore structure and pore size can be regulated and controlled by controlling the pressure and pressure maintaining time of dry pressing and cold isostatic pressing.

Drawings

FIG. 1 is a surface SEM photograph of a porous preform prepared in embodiment 3;

FIG. 2 is a surface SEM photograph of a refractory carbide particle reinforced copper tungsten infiltrated composite made according to embodiment 3.

Detailed Description

The experimental procedures used in the following examples are conventional unless otherwise specified.