CN111875406A - Wet spinning coextrusion for preparing SiCwFibrous monolithic zirconium boride ceramic as interface - Google Patents

Wet spinning coextrusion for preparing SiCwFibrous monolithic zirconium boride ceramic as interface Download PDF

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CN111875406A
CN111875406A CN202010557814.0A CN202010557814A CN111875406A CN 111875406 A CN111875406 A CN 111875406A CN 202010557814 A CN202010557814 A CN 202010557814A CN 111875406 A CN111875406 A CN 111875406A
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monolithic
fibrous
precursor
ceramic
interface layer
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魏春城
温广武
李双
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Shandong University of Technology
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Abstract

The invention provides a method for preparing SiC by wet spinning coextrusionwThe fibrous monolithic zirconium boride ceramic as an interface is characterized by adopting the following steps: 1) firstly adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a monolithic precursor cell body and ceramic powder of a monolithic precursor cell body interface layer, uniformly stirring to form two spinning slurry with different components, and co-extruding and spinning under mechanical pressureSpraying the head into a gel tank to obtain a fibrous monolith precursor with an interface layer; 2) cutting, arranging in parallel, and compacting by warm pressing; 3) vacuum degreasing; 4) hot pressing and sintering to obtain the high interface fibrous monolithic zirconium boride ultrahigh temperature ceramic with fracture toughness up to 11 MPa.m1/2The above. The wet spinning co-extrusion method for forming the fibrous monolithic precursor simplifies the process, is beneficial to mechanical arrangement, and the obtained fibrous monolithic zirconium boride ceramic has the advantages of accurate control of microstructure and synergistic improvement of fracture toughness and oxidation and ablation resistance.

Description

Wet spinning coextrusion for preparing SiCwFibrous monolithic zirconium boride ceramic as interface
Technical Field
The present invention provides aPreparation of SiC by wet spinning coextrusionwA fibrous monolithic zirconium boride ceramic used as an interface belongs to the technical field of preparation of ultra-high temperature ceramics.
Background
Zirconium boride ceramics have superior high temperature and corrosion resistance and relatively low theoretical density and have thus been considered as one of the most promising materials in the family of ultra-high temperature ceramics (UHTCs). Currently, zirconium boride ceramics have been widely used as various high temperature structural and functional materials, such as: turbine blades in the aerospace industry, magnetohydrodynamic power generation electrodes, and the like. However, the zirconium boride ceramic has lower fracture toughness and the toughness value is only 4-5 MPa1/2And the application of the composite material in harsh operating environments is limited, such as a nose cone and a leading edge of a supersonic aircraft, a hot end part of a scramjet engine and the like. Therefore, in order to ensure reliability and safety during use, it is necessary to improve the brittleness of the zirconium boride ceramic, thereby improving the thermal shock resistance thereof. Inspired by the microstructure of shells and bamboos in nature, high-temperature-resistant soft materials are added into brittle ceramic materials, and bionic layered and fibrous monolithic composites are designed and prepared to improve the toughness of the ceramics.
The research on the bionic fiber monolithic composite material. Si prepared by mud extrusion method of Qinghua university3N4A fibrous monolith precursor having a diameter of 1mm was dip-coated with the BN suspension to prepare Si3N4BN fiber monolithic ceramic having a flexural strength of 700MPa and a fracture toughness of 23.9MPa m1/2. The fibrous monolithic ZrB is prepared by co-extruding pug at 120 ℃ by using ethylene-ethyl acrylate as a bonding agent and high-temperature mineral oil as a plasticizer at American Soxhlet university, then directionally arranging, cracking at 800 ℃, and performing hot-pressing sintering at 1900 ℃ and 32MPa2The composite material has a cell body composition of ZrB230vol.% SiC, the interfacial layer forming graphite-15 vol.% ZrB2Fibrous monolith ZrB2The bending strength of the composite material is 375MPa, and the critical thermal shock temperature difference delta TcIt was 1400 ℃.
The traditional preparation process of the fiber monolithic ceramics has the following problems:
the first is that: the traditional forming process of the fiber monolithic precursor is pug extrusion forming, namely dry spinning forming, a green body is aged and pugged in vacuum to enable the green body to have certain plasticity, then the green body is extruded and formed through a spinning nozzle of an extruder, the diameter of the spinning nozzle determines the diameter of the fiber monolithic precursor, the smaller the diameter of the spinning nozzle is, the larger the resistance is, namely, the smaller the diameter of the spinning nozzle needs larger extrusion pressure, and the extrusion forming for preparing the fiber monolithic precursor smaller than 1mm is very difficult, therefore, researchers improve the original extrusion forming process, improve the fluidity of the pug by preheating the pug to 120 ℃, enable the extrusion forming for the finer fiber monolithic precursor, but the essential attribute of poor fluidity of the pug is not changed, the smaller the diameter of the spinning nozzle is, the larger the extrusion pressure is, the extrusion forming is more difficult, and after the fiber monolithic precursor is extruded, because the solvent is volatilized and cured quickly, the fibrous monolithic precursor has poor toughness, is in a thin rod shape and has poor continuity, so that a novel forming process of the fibrous monolithic precursor is required to be developed for preparing the high-toughness fibrous monolithic ceramic.
Secondly, the following steps: the traditional fibrous monolithic precursor cell body interface layer is formed by dip coating, and the thickness of the dip coated interface layer is uneven, so that the microstructure of the fibrous monolithic ceramic cannot be accurately controlled; and repeated impregnation also makes the fiber monolithic precursor easy to break, and the impregnated fiber monolithic precursor cell body becomes hard and brittle, and the material performance is greatly reduced.
Thirdly, the method comprises the following steps: the traditional fibromonolithic ceramic cell body interface layer is made of weak materials such as graphite and boron nitride, the oxidation temperatures of the graphite and the boron nitride are respectively 400 ℃ and 800 ℃, and the oxidation resistance of the cell body interface layer is poor; meanwhile, the difference between the cell body and the cell body interface layer is large, so that the cell body is easy to peel off in the thermal coupling environment of the fiber monolithic composite material.
Disclosure of Invention
The invention aims to solve the problems of low toughness, difficult preparation of a fibrous monolithic precursor and poor oxidation resistance of a cell interface layer of the existing zirconium boride ultrahigh-temperature ceramic, and provides a method for preparing SiC by wet spinning coextrusionwFibrous monolith as an interfaceZirconium boride ceramics. The technical scheme is as follows:
wet spinning coextrusion preparation of SiCwThe fibrous monolithic zirconium boride ceramic as an interface is characterized by adopting the following steps:
1) preparing a fibrous monolith precursor with an interface layer by wet spinning coextrusion: firstly adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a monolithic precursor cell body and ceramic powder of a monolithic precursor cell body interface layer, uniformly stirring to form two kinds of spinning slurry with different components, then respectively pouring the spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning nozzle under mechanical pressure, wherein the water temperature of the gel tank is 0-10 ℃, soaking for 8-24 hours after solidification and forming to obtain the monolithic precursor with the interface layer, wherein the monolithic precursor with the interface layer consists of the monolithic precursor cell body and the monolithic precursor cell body interface layer, the diameter of the monolithic precursor cell body is 500-1000 mu m, the thickness of the monolithic precursor cell body interface layer is 50-100 mu m, and the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol;
2) warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor at the temperature of 60-100 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
3) vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.25-1 ℃/min, the temperature is increased to 600-700 ℃, and the temperature is kept for 0.5-1 h;
4) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere at the sintering temperature of 1900-2000 ℃, keeping the temperature for 0.5-2 h and the pressure of 20-60 MPa to obtain SiCwA fibrous monolithic zirconium boride ceramic as an interface.
The wet spinning coextrusion method is used for preparing SiCwThe fibrous monolithic zirconium boride ceramic used as the interface is prepared by the step 1) that the ceramic powder for preparing the fibrous monolithic precursor cell body consists of zirconium boride powder and silicon carbide powder80-90% by mass: 10-20% by weight.
The wet spinning coextrusion method is used for preparing SiCwThe method comprises the following steps of 1) preparing ceramic powder for a cell interface layer of a fibrous monolithic precursor from silicon carbide whisker powder and zirconium boride powder in a mass percent of 70-90% in step 1): 10-30% of the above-mentioned raw materials.
The wet spinning coextrusion method is used for preparing SiCwIn the step 1), based on the weight of the ceramic powder for preparing the cell body of the fibrous monolithic precursor, 10-20% of a curing agent, 10-20% of a plasticizer and 100-200% of an organic solvent are weighed according to weight percentage.
The wet spinning coextrusion method is used for preparing SiCwIn the step 1), 30-40% of a curing agent, 30-40% of a plasticizer and 300-500% of an organic solvent are weighed according to the weight percentage based on the weight of the ceramic powder for preparing the cell interface layer of the fibrous monolithic precursor.
The working principle of the invention is as follows: a process for preparing the fibrous monolithic precursor with boundary layer by wet spinning and co-extruding method includes such steps as dissolving solidifying agent and plasticizer in organic solvent while stirring, adding the ceramic powder at boundary layer between cell body and cell body of fibrous monolithic precursor, stirring to obtain two different spinning slurries, extruding out, solidifying and shaping in a gel tank full of water to obtain the fibrous monolithic precursor with boundary layer, which has uniform thickness and structure as shown in FIG. 1. The fibrous monolithic precursor with the interface layer is in the shape of an ellipsoid, a rhombohedron, a spindle, a flat body and a cylinder. By regulating and controlling parameters such as curing agent, plasticizer, solid-liquid ratio, viscosity of spinning slurry, extrusion speed, temperature of solidified liquid and the like, the shape of the fibrous monolithic precursor is controllable, the compactness of the fibrous monolithic precursor is improved, the deformation of the cell shape of the fibrous monolithic material during hot-pressing sintering is reduced, and the continuous, superfine, high-toughness and compact cylindrical fibrous monolithic precursor is prepared. Wherein the solid-liquid ratio is controlled by the mass ratio of the organic solvent to the ceramic powder; the viscosity of the spinning slurry is controlled by a curing agent, a plasticizer, an organic solvent, ceramic powder and stirring time; the extrusion speed is controlled by mechanical pressure; the coagulation speed is controlled by the water temperature of the gel tank.
SiC prepared from a fibrous monolith precursor having an interfacial layerwThe structural schematic diagram of the fibrous monolithic zirconium boride ceramic used as the interface is shown in FIG. 2, and the fibrous monolithic zirconium boride ceramic is composed of cells and cell interface layers. When the sample is broken, the crack deflects and bifurcates, and the expansion path of the crack is increased, so that the fracture toughness of the material is improved and can reach 11MPa1/2The above.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the steps of forming a fibrous monolithic precursor with an interface layer by a wet spinning co-extrusion method, preparing the continuous, superfine, high-toughness and compact fibrous monolithic precursor with the interface layer, wherein the diameter of a cell body can reach 500 mu m, the thickness of the cell body interface layer can reach 50 mu m, the length of the cell body interface layer can reach more than 10 meters, and the fibrous monolithic precursor can not be broken when bent by 180 degrees. Thoroughly overcomes the defects of extrusion molding of pug, poor flowability of the pug, and thick diameter, poor toughness and discontinuity of the fiber monolithic precursor;
2. the wet spinning co-extrusion method for forming the fibrous monolithic precursor overcomes the defects of uneven coating thickness of a dipping method and reduced toughness of the fibrous monolithic precursor, simplifies the process and achieves the accurate control of the microstructure of the fibrous monolithic zirconium boride ultrahigh-temperature ceramic;
3. the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, after the ceramic green body is degreased in vacuum, the polyvinyl butyral and the polyethylene glycol are cracked at high temperature into micromolecular carbon particles to be removed, no carbon residue exists, and the residual carbon can reduce the bending strength and the fracture toughness of the fibrous monolithic zirconium boride ultrahigh-temperature ceramic;
4. the water temperature of the gel tank is 0-10 ℃, the gel tank is rapidly solidified at low temperature, and the fiber monolithic precursor is not adhered;
5. SiC produced in the inventionwIn the fibrous monolithic zirconium boride ceramic used as the interface, the cell body composition is zirconium boride-silicon carbide, and the cell body interface layer composition isThe SiC crystal whisker has longer length-diameter ratio, is beneficial to the deflection and the bifurcation of an interface layer to cracks, increases crack propagation paths, improves the fracture toughness of the material, and can reach 11MPa1/2The above;
6. the SiC crystal whisker is used as a cell interface material, has the oxidation temperature of 1100 ℃, and has excellent oxidation resistance, so that the SiC crystal whiskerwThe monolithic zirconium boride ceramic used as the interface fiber has excellent oxidation ablation resistance.
7. The block ceramic is brittle fracture, while the fiber monolithic zirconium boride ceramic is non-brittle fracture, and has a certain tolerance capacity for crack damage.
Drawings
FIG. 1 is a schematic structural view of a fibrous monolith precursor having an interfacial layer according to the present invention;
FIG. 2 shows SiC of the present inventionwSchematic structural diagram of fibrous monolithic zirconium boride ceramic as interface.
In the figure: 1. a cell of a fibrous monolith precursor having an interfacial layer; 2. a cell interface layer of the fibrous monolith precursor having an interface layer; 3. SiCwA cell body of the fibrous monolithic zirconium boride ceramic as an interface; 4. SiCwA cell interface layer of the fibrous monolithic zirconium boride ceramic as an interface.
Detailed Description
Example 1
1. Preparing fiber monolith precursor cell spinning slurry: firstly, stirring and dissolving 10 g of polyvinyl butyral and 10 g of polyethylene glycol in 100 g of absolute ethanol, and then adding ceramic powder of a fibrous monolith precursor cell body, wherein the ceramic powder of the fibrous monolith precursor cell body is prepared from 80 g of zirconium boride powder and 20 g of silicon carbide powder according to the mass percentage of 80%: 20 percent of the mixture is mixed and evenly stirred to prepare fiber monolith precursor cell spinning slurry;
2. preparing fiber monolith precursor cell interface layer spinning slurry: firstly, stirring and dissolving 30 g of polyvinyl butyral and 30 g of polyethylene glycol in 300 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is prepared from 70 g of silicon carbide whisker powder and 30 g of zirconium boride powder according to the mass percentage of 70%: 30 percent of the mixture is mixed and stirred evenly to prepare spinning slurry of a cell interface layer of the fibrous monolith precursor;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring fiber monolith precursor cell spinning slurry and fiber monolith precursor cell interface layer spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning nozzle under the mechanical pressure, wherein the water temperature of the gel tank is 0 ℃, and soaking for 8 hours after solidification forming to obtain the fiber monolith precursor with an interface layer, wherein the fiber monolith precursor with the interface layer consists of a fiber monolith precursor cell and a cell interface layer, the diameter of the fiber monolith precursor cell is 1000 mu m, and the thickness of the cell interface layer is 100 mu m;
4. warm-pressing and forming: cutting the fiber monolithic precursor of the interface layer after dipping and coating according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor by warm pressing at 60 ℃ and 20MPa to obtain a ceramic green body;
5. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 600 ℃ at the heating speed of 0.25 ℃/min, and keeping the temperature for 0.5 h;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at the sintering temperature of 1900 ℃, the temperature is kept for 0.5h and the pressure is 20MPa, and SiC is obtainedwA fibrous monolithic zirconium boride ceramic as an interface.
Example 2
1. Preparing fiber monolith precursor cell spinning slurry: firstly stirring and dissolving 20 g of polyvinyl butyral and 20 g of polyethylene glycol in 200 g of absolute ethanol, and then adding ceramic powder of a fibrous monolith precursor cell body, wherein the ceramic powder of the fibrous monolith precursor cell body is prepared from 90 g of zirconium boride powder and 10 g of silicon carbide powder according to the mass percentage of 90%: 10 percent of the mixture is mixed and evenly stirred to prepare fiber monolith precursor cell spinning slurry;
2. preparing fiber monolith precursor cell interface layer spinning slurry: firstly, stirring and dissolving 40 g of polyvinyl butyral and 40 g of polyethylene glycol in 500 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is prepared from 90 g of silicon carbide whisker powder and 10 g of zirconium boride powder according to the mass percentage of 90%: 10 percent of the mixture is mixed and stirred evenly to prepare spinning slurry of a cell interface layer of the fibrous monolith precursor;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fiber monolith precursor cell spinning slurry and the fiber monolith precursor cell interface layer spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning nozzle under mechanical pressure, wherein the water temperature of the gel tank is 10 ℃, and soaking for 24 hours after solidification forming to obtain the fiber monolith precursor with an interface layer, wherein the fiber monolith precursor with the interface layer consists of a fiber monolith precursor cell and a cell interface layer, the diameter of the fiber monolith precursor cell is 500 mu m, and the thickness of the cell interface layer is 50 mu m;
4. warm-pressing and forming: cutting the fiber monolithic precursor of the interface layer after dipping and coating according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor by warm pressing at 100 ℃ and 50MPa to obtain a ceramic green body;
5. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 700 ℃ at the heating speed of 1 ℃/min, and keeping the temperature for 1 h;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at the sintering temperature of 2000 ℃, keeping the temperature for 2h and the pressure of 60MPa to obtain SiCwA fibrous monolithic zirconium boride ceramic as an interface.
Example 3
1. Preparing fiber monolith precursor cell spinning slurry: firstly, stirring and dissolving 15 g of polyvinyl butyral and 15 g of polyethylene glycol in 150 g of absolute ethanol, and then adding ceramic powder of a monolithic precursor cell body, wherein the ceramic powder of the monolithic precursor cell body consists of 85 g of zirconium boride powder and 15 g of silicon carbide powder according to the mass percentage of 85%: 15 percent of the mixture is mixed and evenly stirred to prepare fiber monolith precursor cell spinning slurry;
2. preparing fiber monolith precursor cell interface layer spinning slurry: firstly, stirring and dissolving 35 g of polyvinyl butyral and 35 g of polyethylene glycol in 400 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is prepared from 80 g of silicon carbide whisker powder and 20 g of zirconium boride powder according to the mass percentage of 80%: 20 percent of the mixture is mixed and stirred evenly to prepare spinning slurry of a cell interface layer of the fibrous monolith precursor;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fiber monolith precursor cell spinning slurry and the fiber monolith precursor cell interface layer spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning head under the mechanical pressure, wherein the water temperature of the gel tank is 5 ℃, and soaking for 12 hours after solidification forming to obtain the fiber monolith precursor with an interface layer, wherein the fiber monolith precursor with the interface layer consists of a fiber monolith precursor cell and a cell interface layer, the diameter of the fiber monolith precursor cell is 800 mu m, and the thickness of the cell interface layer is 60 mu m;
4. warm-pressing and forming: cutting the fiber monolithic precursor of the interface layer after dipping and coating according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor by warm pressing at 80 ℃ and 30MPa to obtain a ceramic green body;
5. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.5 ℃/min, the temperature is increased to 650 ℃, and the temperature is kept for 0.75 h;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1950 ℃ for 1h under the pressure of 40MPa to obtain SiCwA fibrous monolithic zirconium boride ceramic as an interface.
Example 4
1. Preparing fiber monolith precursor cell spinning slurry: firstly, stirring and dissolving 18 g of polyvinyl butyral and 18 g of polyethylene glycol in 120 g of absolute ethyl alcohol, and then adding ceramic powder of a fibrous monolith precursor cell body, wherein the ceramic powder of the fibrous monolith precursor cell body is prepared from 88 g of zirconium boride powder and 12 g of silicon carbide powder according to the mass percentage of 88%: 12 percent of the mixture is mixed and evenly stirred to prepare fiber monolith precursor cell spinning slurry;
2. preparing fiber monolith precursor cell interface layer spinning slurry: firstly, stirring and dissolving 38 g of polyvinyl butyral and 38 g of polyethylene glycol in 450 g of absolute ethyl alcohol, and then adding ceramic powder of a cell interface layer of a fiber monolithic precursor, wherein the ceramic powder of the cell interface layer of the fiber monolithic precursor is prepared from 75 g of silicon carbide whisker powder and 25 g of zirconium boride powder according to the mass percentage of 75%: 25 percent of the mixture is mixed and stirred evenly to prepare spinning slurry of the cell interface layer of the fibrous monolith precursor;
3. wet spinning coextrusion to prepare a fibrous monolith precursor with an interfacial layer: respectively pouring the fiber monolith precursor cell spinning slurry and the fiber monolith precursor cell interface layer spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning nozzle under mechanical pressure, wherein the water temperature of the gel tank is 2 ℃, and soaking for 10 hours after solidification forming to obtain the fiber monolith precursor with an interface layer, wherein the fiber monolith precursor with the interface layer consists of a fiber monolith precursor cell and a cell interface layer, the diameter of the fiber monolith precursor cell is 700 mu m, and the thickness of the cell interface layer is 80 mu m;
4. warm-pressing and forming: cutting the fiber monolithic precursor of the interface layer after dipping and coating according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor by warm pressing at 70 ℃ and 40MPa to obtain a ceramic green body;
5. vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, degreasing in vacuum, heating to 650 ℃ at the heating speed of 1 ℃/min, and keeping the temperature for 0.5 h;
6. hot-pressing and sintering: after degreasing, hot-pressing and sintering in argon atmosphere at 1950 ℃ for 1h under the pressure of 30MPa to obtain SiCwA fibrous monolithic zirconium boride ceramic as an interface.

Claims (5)

1. Wet spinning coextrusion preparation of SiCwAsThe fibrous monolithic zirconium boride ceramic of the interface is characterized by adopting the following steps:
1) preparing a fibrous monolith precursor with an interface layer by wet spinning coextrusion: firstly adding a curing agent and a plasticizer into an organic solvent, stirring and dissolving, then respectively adding ceramic powder of a monolithic precursor cell body and ceramic powder of a monolithic precursor cell body interface layer, uniformly stirring to form two kinds of spinning slurry with different components, then respectively pouring the spinning slurry into different injectors, spraying the spinning slurry into a gel tank filled with water through a co-extrusion spinning nozzle under mechanical pressure, wherein the water temperature of the gel tank is 0-10 ℃, soaking for 8-24 hours after solidification and forming to obtain the monolithic precursor with the interface layer, wherein the monolithic precursor with the interface layer consists of the monolithic precursor cell body and the monolithic precursor cell body interface layer, the diameter of the monolithic precursor cell body is 500-1000 mu m, the thickness of the monolithic precursor cell body interface layer is 50-100 mu m, and the curing agent is polyvinyl butyral, the plasticizer is polyethylene glycol, and the organic solvent is absolute ethyl alcohol;
2) warm-pressing and forming: cutting a fiber monolithic precursor with an interface layer according to the size of a graphite die for hot-pressing sintering, arranging the fiber monolithic precursor in the graphite die in parallel, and compacting the fiber monolithic precursor at the temperature of 60-100 ℃ and under the pressure of 20-50 MPa to obtain a ceramic green body;
3) vacuum degreasing: putting the ceramic green body and the graphite mold into a vacuum degreasing furnace, performing vacuum degreasing, wherein the heating rate is 0.25-1 ℃/min, the temperature is increased to 600-700 ℃, and the temperature is kept for 0.5-1 h;
4) hot-pressing and sintering: after degreasing, hot-pressing and sintering in an argon atmosphere at the sintering temperature of 1900-2000 ℃, keeping the temperature for 0.5-2 h and the pressure of 20-60 MPa to obtain SiCwA fibrous monolithic zirconium boride ceramic as an interface.
2. Wet-spinning co-extrusion SiC as claimed in claim 1wThe fibrous monolithic zirconium boride ceramic as the interface is characterized in that: in the step 1), the ceramic powder for preparing the cell body of the fibrous monolith precursor is prepared from zirconium boride powder and silicon carbide powder according to the mass percentage of 80-90%: 10 to 20% by weight of a mixtureAnd (4) obtaining.
3. Wet-spinning co-extrusion SiC as claimed in claim 1wThe fibrous monolithic zirconium boride ceramic as the interface is characterized in that: in the step 1), the ceramic powder for preparing the cell interface layer of the fibrous monolithic precursor is prepared from silicon carbide whisker powder and zirconium boride powder according to the mass percentage of 70-90%: 10-30% of the above-mentioned raw materials.
4. Wet-spinning co-extrusion SiC as claimed in claim 1wThe fibrous monolithic zirconium boride ceramic as the interface is characterized in that: in the step 1), based on the weight of the ceramic powder for preparing the monolithic precursor cell body, 10-20% of a curing agent, 10-20% of a plasticizer and 100-200% of an organic solvent are weighed according to weight percentage.
5. Wet-spinning co-extrusion SiC as claimed in claim 1wThe fibrous monolithic zirconium boride ceramic as the interface is characterized in that: in the step 1), 30-40% of a curing agent, 30-40% of a plasticizer and 300-500% of an organic solvent are weighed according to the weight percentage based on the weight of the ceramic powder for preparing the cell interface layer of the fibrous monolithic precursor.
CN202010557814.0A 2020-06-18 2020-06-18 Wet spinning coextrusion for preparing SiCwFibrous monolithic zirconium boride ceramic as interface Withdrawn CN111875406A (en)

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JP2016519639A (en) * 2013-03-15 2016-07-07 ロールス−ロイス・コーポレーション Reactive melt-penetrating ceramic matrix composites
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JP2016519639A (en) * 2013-03-15 2016-07-07 ロールス−ロイス・コーポレーション Reactive melt-penetrating ceramic matrix composites
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