CN113416076A - Preparation method of self-reinforced silicon carbide ceramic material - Google Patents

Preparation method of self-reinforced silicon carbide ceramic material Download PDF

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CN113416076A
CN113416076A CN202110934914.5A CN202110934914A CN113416076A CN 113416076 A CN113416076 A CN 113416076A CN 202110934914 A CN202110934914 A CN 202110934914A CN 113416076 A CN113416076 A CN 113416076A
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silicon carbide
ceramic material
carbide ceramic
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茹红强
冯东
秦肇伯
孙是昊
任全兴
夏乾
王伟
张翠萍
岳新艳
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Northeastern University China
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Abstract

The invention relates to a preparation method of a self-reinforced silicon carbide ceramic material, belonging to the technical field of ceramic material preparation, and comprising the following preparation steps: according to the mass percentage, the alpha-SiC powder: beta-SiC powder: b is4C, powder body: charcoal (92% -94%): (1% -3%): (1% -3%): (2% -4%), weighing alpha-SiC powder, beta-SiC powder and B4C, powder and carbon; uniformly mixing, drying and sieving the raw materials, and performing compression molding to obtain a biscuit; placing the biscuit in a vacuum tube furnace for carbonization at the temperature of 600-900 ℃; and sintering the carbonized sample under no pressure, and cooling to obtain the self-reinforced silicon carbide ceramic material. The method prepares the solid-phase pressureless sintering silicon carbide ceramic with high density, high strength, high hardness and uniform tissue by compounding beta-SiC powder with different grain sizes into alpha-SiC powderThe material improves the comprehensive performance of the pressureless sintered silicon carbide ceramic material.

Description

Preparation method of self-reinforced silicon carbide ceramic material
The technical field is as follows:
the invention belongs to the technical field of ceramic material preparation, and particularly relates to a preparation method of a self-reinforced silicon carbide ceramic material.
Background art:
silicon carbide (SiC) materials are often used in the industrial fields of metallurgy, mechatronics, petrochemical industry, aerospace and the like because of their excellent properties of high strength, high hardness, wear resistance, corrosion resistance, strong oxidation resistance, good thermal stability, large thermal conductivity and the like, and thus have received a great deal of attention from researchers. However, because SiC has strong covalent bonds, low grain boundary diffusion and volume diffusion rates, it often needs to be sintered above 2000 ℃ to achieve a fully sintered dense state.
At present, researchers often use metal oxides as sintering aids (Al)2O3、Y2O3、Re2O3、Er2O3、Gd2O3Etc.) are added into SiC, and the SiC ceramic is promoted to complete sintering densification at lower temperature by means of liquid phase sintering action. Unfortunately, liquid phase sintering often results in the formation of low melting point phases at the grain boundary sites of SiC ceramics, and the presence of low melting point phases causes softening of the SiC ceramics during use in high temperature environments, and ultimately leads to poor in-use strength and hardness of SiC materials at high temperatures. In addition, the optimal addition content of the sintering aid is difficult to control, and the addition of too much sintering aid not only causes material waste, but also seriously affects the excellent performance of the SiC ceramic itself. Therefore, how to ensure that the excellent performance of the SiC ceramic is not damaged and the SiC ceramic with high density, high strength, high hardness and uniform tissue can be obtained is important.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provide a preparation method of a self-reinforced silicon carbide ceramic material. According to the method, the beta-SiC powder with different grain sizes is compounded into the alpha-SiC powder, so that the solid-phase pressureless sintering silicon carbide ceramic material with high density, high strength, high hardness and uniform tissue is prepared, and the comprehensive performance of the pressureless sintering silicon carbide ceramic material is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a self-reinforced silicon carbide ceramic material comprises the following steps:
step 1, batching:
according to the mass percentage, the alpha-SiC powder: beta-SiC powder: b is4C, powder body: charcoal (92% -94%): (1% -3%): (1% -3%): (2% -4%), weighing alpha-SiC powder, beta-SiC powder and B4C, powder and carbon;
step 2, wet mixing and forming
Uniformly mixing, drying and sieving the raw materials, and performing compression molding to obtain a biscuit;
step 3, vacuum carbonization:
placing the biscuit in a vacuum tube furnace for carbonization at the temperature of 600-900 ℃;
step 4, pressureless sintering:
and sintering the carbonized sample under no pressure, and cooling to obtain the self-reinforced silicon carbide ceramic material.
In the step 1, the particle size range of the alpha-SiC powder is 0.3 to 1.5 mu m, the particle size range of the beta-SiC powder is 10 to 100nm, B4The C powder is used as a sintering aid, and the particle size range of the C powder is 0.3-1.5 mu m.
In the step 1, the carbon is added in the form of phenolic resin, the carbon residue rate in the phenolic resin is 50-55%, and the carbon is used as a binder and a carbon source.
In the step 1, preferably, the alpha-SiC powder is prepared by the following steps by mass percent: beta-SiC powder: B4C powder: charcoal (92% -94%): (1% -3%): 1.5%: 3.5 percent.
In the step 2, the wet mixing and molding process comprises the following specific steps:
(1) respectively putting the weighed powder into a ball milling tank, and uniformly mixing the powder by high-speed ball milling for later use, wherein the alumina balls are used as milling balls, the ethanol is used as a milling medium, the rotating speed is 50-200rpm, and the mixing time is 12-24 h;
(2) drying the uniformly mixed powder in an oven at 60-110 ℃, and then sieving the powder by a 40-60-mesh sieve for later use;
(3) placing the dried powder in a 37 x 6.5 x 50mm mould, compacting the powder in the mould under the pressure of 100-200MPa to obtain a biscuit, wherein the dried powder is firstly pre-pressed and formed under the unidirectional pressure of 100MPa, and then is subjected to isostatic pressing and forming under 200 MPa;
in the step 3, the carbonization heating rate is 1-4 ℃/min.
In the step 3, the carbonization heat preservation time is 2-4 h.
In the step 4, the pressureless sintering process comprises the following specific steps: and (3) placing the carbonized sample in a pressureless sintering furnace, vacuumizing to less than 20Pa, manually heating to 500-plus-one temperature of 700 ℃, then adjusting automatic heating, wherein the heating rate is 1-5 ℃/min, keeping the temperature for 40-80min when the temperature reaches 1400-plus-one temperature of 1500 ℃, introducing high-purity Ar gas, continuing heating, keeping the temperature at the heating rate of 1-5 ℃/min, keeping the temperature for 30-60min after reaching the sintering temperature of 1800-plus-one temperature of 2000 ℃, and cooling along with the furnace to obtain the self-reinforced silicon carbide ceramic material.
In the step 4, the grain size distribution range of the silicon carbide ceramic material is 2.05-9.28 microns, the average grain size is 4.18-4.36 microns, and the volume density is 3.14-3.16g/cm3The relative density is 98.13-98.51%, the open porosity is 0.07-0.09%, the bending strength is 403-420MPa, and the fracture toughness is 5.07-5.35 MPa.m1/2The Vickers hardness is 27.6-27.9 GPa.
The invention has the beneficial effects that:
the invention utilizes the high-temperature phase change and evaporation-condensation of beta-SiC powder as B4C and C are used as sintering aids, and SiC ceramics are prepared by adding beta-SiC powder with specific grain size into the alpha-SiC powder and sintering. The beta-SiC powder prepared by the combustion synthesis method is a thermodynamically unstable phase and has sintering activity far higher than that of alpha-SiC powder. In addition, the main crystal form of the beta-SiC is a 3C structure, which belongs to a crystal with low-temperature stabilityThe crystal grains are easy to slip and rearrange under the action of external pressure, and the crystal always shows a long shaft shape and plays a pinning role. Because the beta-SiC powder has high-temperature phase change action to promote the existence of compressive stress between beta-SiC grains and alpha-SiC grains in the sintering process, the abnormal growth of SiC grains can be effectively inhibited, so that the silicon carbide ceramic material with uniform and higher tissue, finer grains and excellent performance is obtained, the bending strength of the prepared silicon carbide ceramic material can be improved by more than 40 percent on the basis of the silicon carbide ceramic material prepared from single alpha-SiC powder, and the application field of the silicon carbide ceramic material is wider.
Description of the drawings:
FIG. 1 is a photograph taken by means of a scanning electron microscope showing a polished surface of a silicon carbide ceramic material prepared in examples 2 to 5 of the present invention at 2000 times magnification; wherein: in the figure, (a) is a silicon carbide ceramic material prepared in example 2; (b) the silicon carbide ceramic material prepared for example 3; (c) the silicon carbide ceramic material prepared for example 4; (d) the silicon carbide ceramic material prepared in example 5 was used.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
The weight purity of the SiC powder adopted in the embodiment of the invention is more than 98.5%, and the particle size range is 0.3-1.5 μm; b is4The weight purity of the C powder is more than 99 percent, and the particle size range is 0.3-1.5 mu m.
The phenolic resin and the ethanol adopted in the embodiment of the invention are industrial products.
The ball milling and mixing equipment in the embodiment of the invention is a GMS1-4 horizontal ball mill.
The equipment adopted by the compression molding in the embodiment of the invention is a W-486 type hydraulic universal tester.
The sintering process in the embodiment of the invention adopts ZGRY-50-24 plasma sintering furnace as equipment.
In the embodiment of the invention, an Archimedes drainage method is adopted as the method for testing the volume density and the open porosity.
The bending strength test method in the embodiment of the invention is a three-point bending strength method, and an AG-Xplus100kN electronic universal tester is adopted.
The method for testing the fracture toughness in the embodiment of the invention is the SENB method, and an AG-Xplus100kN electronic universal tester is adopted.
The Vickers hardness test method in the embodiment of the invention is a Vickers indentation hardness method, and an HV120 Vickers hardness tester is adopted.
The scanning electron microscope picture provided by the embodiment of the invention adopts JSM-7001 type field emission electron scanning electron microscope.
Example 1
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 95%, B4C, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5% with a particle size range of 0.3-1.5. mu.m, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder and B according to mass percent respectively4C powder and phenolic resin;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.14g/cm through detection397.82% in relative density, 0.11% in apparent porosity, 295.1MPa in bending strength and 4.61MPa · m in fracture toughness1/2The Vickers hardness was 25.5 GPa.
Example 2
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 94%, beta-SiC powder: 1%, B4C, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5 percent of beta-SiC powder with the granularity range of 0.3-1.5 mu m>99% of particle size range of 10-100nm, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder, beta-SiC powder and B according to mass percent respectively4C powder and phenolic resin;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.15g/cm through detection398.13% in relative density, 0.09% in apparent porosity, 403.6MPa in bending strength, and 5.07MPa · m in fracture toughness1/2The Vickers hardness is 27.9Gpa, the grain size distribution is 2.24-9.28 μm, and the average grain size is 4.31 μm. The photograph of the polished surface of the material taken by a scanning electron microscope at 2000 times magnification is shown in FIG. 1 (a).
Example 3
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 93%, beta-SiC powder: 2%, B4C, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5 percent of beta-SiC powder with the granularity range of 0.3-1.5 mu m>98% with a particle size range of 10-100nm, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder, beta-SiC powder and B according to mass percent respectively4C powder and phenolic resinA lipid;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.16g/cm through detection3A relative density of 98.51%, an apparent porosity of 0.07%, a bending strength of 419.1MPa, and a fracture toughness of 5.35MPa m1/2The Vickers hardness is 27.9GPa, the grain size distribution range is 2.05-8.15 μm, and the average grain size is 4.18 μm. The photograph of the polished surface of the material taken by scanning electron microscope at 2000 times magnification is shown in FIG. 1 (b).
Example 4
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 92%, beta-SiC powder:3％，B4c, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5 percent of beta-SiC powder with the granularity range of 0.3-1.5 mu m>98% with a particle size range of 10-100nm, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder, beta-SiC powder and B according to mass percent respectively4C powder and phenolic resin;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.16g/cm through detection3The relative density is 98.51 percent, and the apparent porosity is 0.08 percentThe flexural strength was 406.6MPa, and the fracture toughness was 5.29MPa · m1/2The Vickers hardness is 27.6GPa, the grain size distribution range is 2.17-9.16 μm, and the average grain size is 4.36 μm. The photograph of the polished surface of the material taken by a scanning electron microscope at 2000 times magnification is shown in FIG. 1 (c).
Example 5
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 90%, beta-SiC powder: 5%, B4C, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5 percent of beta-SiC powder with the granularity range of 0.3-1.5 mu m>99% of particle size range of 10-100nm, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder, beta-SiC powder and B according to mass percent respectively4C powder and phenolic resin;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.15g/cm through detection3A relative density of 98.13%, an apparent porosity of 0.08%, a bending strength of 352.1MPa, and a fracture toughness of 4.81MPa m1/2The Vickers hardness is 26.0GPa, the grain size distribution range is 2.56-13.68 mu m, and the average grain size is 5.92 mu m. The picture of a scanning electron microscope photo of the polished surface of the material magnified by 2000 times is shown in (d) in fig. 1, and it can be seen that excessive beta-SiC powder causes SiC crystal grains to grow and cannot be effectively regulated, so that abnormal growth of the crystal grains is caused, and the product performance is obviously influenced.
Example 6
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 90%, beta-SiC powder: 5%, B4C, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5 percent of beta-SiC powder with the granularity range of 0.3-1.5 mu m>98% of particle size range of 0.3-1.5 mu m, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder, beta-SiC powder and B according to mass percent respectively4C powder and phenolic resin;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.15g/cm through detection3A relative density of 98.13%, an apparent porosity of 0.08%, a bending strength of 333.2MPa, and a fracture toughness of 4.65MPa m1/2The Vickers hardness was 25.6 GPa.
Example 7
The preparation method based on the self-reinforced silicon carbide ceramic material comprises the following steps:
the powder comprises the following components in percentage by mass: alpha-SiC powder: 85%, beta-SiC powder: 10%, B4C, powder body: 1.5%, carbon: 3.5 percent.
Wherein, the alpha-SiC powder>98.5 percent of beta-SiC powder with the granularity range of 0.3-1.5 mu m>98% of particle size range of 0.3-1.5 mu m, B4C powder>99%, particle size range 0.3-1.5 μm, phenolic resin as carbon source and binder: the carbon residue rate is 52.5%.
The method comprises the following specific steps:
step 1, batching: weighing alpha-SiC powder and beta-SiC powder according to mass percent respectively、B4C powder and phenolic resin;
step 2, mixing materials: respectively putting the weighed powder and phenolic resin dissolved in ethanol into a ball milling tank, and uniformly mixing the weighed powder and the phenolic resin by high-speed ball milling for later use;
selecting an alumina ball as a grinding ball, adding ethanol for mixing, wherein the mass ratio of the ball to the material to the ethanol is 2:1:1.5, the rotating speed is 100rpm, and the mixing time is 12 hours;
and 3, drying: respectively drying the uniformly mixed powder in an oven at 85 ℃, grinding the powder by an agate mortar and sieving the powder by a 40-60 sieve for later use;
step 4, prepressing and forming: placing the dried and sieved powder into a 37 multiplied by 6.5 multiplied by 50mm die, pre-pressing and molding under 100MPa of unidirectional pressure, and then performing isostatic pressing and molding under 200 MPa;
step 5, vacuum carbonization: placing the pressed biscuit in a vacuum tube furnace, wherein the carbonization temperature is 700 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 3 h;
step 6, pressureless sintering: and (2) placing the sample after carbonization in a graphite crucible, manually heating to 600 ℃ after the vacuum degree in the furnace is less than or equal to 20Pa, then adjusting automatic heating, wherein the heating rate is 3 ℃/min, keeping the temperature for 60min when the temperature reaches 1450 ℃, introducing high-purity Ar gas, continuing heating, the heating rate is 3 ℃/min, reaching the sintering temperature of 2000 ℃, keeping the temperature for 60min, and naturally cooling along with the furnace after the heat preservation process is finished to obtain the silicon carbide ceramic material.
The silicon carbide ceramic material prepared in the embodiment has a volume density of 3.14g/cm through detection397.82% in relative density, 0.13% in apparent porosity, 302.8MPa in bending strength and 4.58MPa · m in fracture toughness1/2The Vickers hardness was 24.9 GPa.
Example 8
The difference from example 3 is that the pressureless sintering mode was adjusted as follows:
placing the carbonized sample in a pressureless sintering furnace, vacuumizing to less than 20Pa, manually heating to 600 ℃, adjusting automatic heating with the heating rate of 3 ℃/min, introducing high-purity Ar gas, directly heating to the sintering temperature of 2000 ℃, and preserving heat for 12 DEG CCooling with the furnace for 0min to obtain self-reinforced silicon carbide ceramic material with volume density of 3.11g/cm3A relative density of 96.88%, an apparent porosity of 0.8%, a bending strength of 240.1MPa, and a fracture toughness of 4.23MPa m1/2The Vickers hardness was 22.6 GPa. Therefore, the improper sintering process causes the carbonized ceramic material to be incapable of reaching a fully sintered compact state, and the prepared ceramic material has obvious abnormal growth of crystal grains, and finally causes the material performance to be seriously deteriorated.

Claims (8)

1. The preparation method of the self-reinforced silicon carbide ceramic material is characterized by comprising the following steps:
step 1, batching:
according to the mass percentage, the alpha-SiC powder: beta-SiC powder: b is4C, powder body: charcoal (92% -94%): (1% -3%): (1% -3%): (2% -4%), weighing alpha-SiC powder, beta-SiC powder and B4C, powder and carbon;
step 2, wet mixing and forming
Uniformly mixing, drying and sieving the raw materials, and performing compression molding to obtain a biscuit;
step 3, vacuum carbonization:
placing the biscuit in a vacuum tube furnace for carbonization at the temperature of 600-900 ℃;
step 4, pressureless sintering:
and sintering the carbonized sample under no pressure, and cooling to obtain the self-reinforced silicon carbide ceramic material.
2. The method for preparing the self-reinforced silicon carbide ceramic material according to claim 1, wherein in the step 1, the grain size range of the alpha-SiC powder is 0.3-1.5 μm, the grain size range of the beta-SiC powder is 10-100nm, and B4The C powder is used as a sintering aid, and the particle size range of the C powder is 0.3-1.5 mu m.
3. The method for preparing self-reinforced silicon carbide ceramic material according to claim 1, wherein in the step 1, the carbon is added in the form of phenolic resin, the carbon residue rate in the phenolic resin is 50-55%, and the carbon is used as a binder and a carbon source.
4. The method for preparing the self-reinforced silicon carbide ceramic material according to claim 1, wherein in the step 2, the wet mixing and molding process comprises the following specific steps:
(1) respectively putting the weighed powder into a ball milling tank, and uniformly mixing the powder by high-speed ball milling for later use, wherein the alumina balls are used as milling balls, the ethanol is used as a milling medium, the rotating speed is 50-200rpm, and the mixing time is 12-24 h;
(2) drying the uniformly mixed powder in an oven at 60-110 ℃, and then sieving the powder by a 40-60-mesh sieve for later use;
(3) placing the dried powder into a die with the diameter of 37 multiplied by 6.5 multiplied by 50mm, compacting the powder in the die under the pressure of 100-200MPa to obtain a biscuit, wherein the dried powder is pre-pressed and molded under the unidirectional pressure of 100MPa firstly, and then is subjected to isostatic pressing and molding under the pressure of 200 MPa.
5. The method for preparing a self-reinforced silicon carbide ceramic material as claimed in claim 1, wherein in the step 3, the temperature rising rate of carbonization is 1-4 ℃/min.
6. The method for preparing the self-reinforced silicon carbide ceramic material according to claim 1, wherein in the step 3, the carbonization holding time is 2-4 h.
7. The method for preparing the self-reinforced silicon carbide ceramic material according to the claim 1, wherein in the step 4, the pressureless sintering comprises the following specific processes: and (3) placing the carbonized sample in a pressureless sintering furnace, vacuumizing to less than 20Pa, manually heating to 500-plus-one temperature of 700 ℃, then adjusting automatic heating, wherein the heating rate is 1-5 ℃/min, keeping the temperature for 40-80min when the temperature reaches 1400-plus-one temperature of 1500 ℃, introducing high-purity Ar gas, continuing heating, keeping the temperature at the heating rate of 1-5 ℃/min, keeping the temperature for 30-60min after reaching the sintering temperature of 1800-plus-one temperature of 2000 ℃, and cooling along with the furnace to obtain the self-reinforced silicon carbide ceramic material.
8. The method for preparing a self-reinforced silicon carbide ceramic material as claimed in claim 1, wherein in the step 4, the silicon carbide ceramic material has a grain size distribution range of 2.05-9.28 μm, an average grain size of 4.18-4.36 μm, and a bulk density of 3.14-3.16g/cm3The relative density is 98.13-98.51%, the open porosity is 0.07-0.09%, the bending strength is 403-420MPa, and the fracture toughness is 5.07-5.35 MPa.m1/2The Vickers hardness is 27.6-27.9 GPa.
CN202110934914.5A 2021-08-16 2021-08-16 Preparation method of self-reinforced silicon carbide ceramic material Pending CN113416076A (en)

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