CN116768652A - Preparation method of high-temperature-resistant ceramic and high-temperature-resistant ceramic - Google Patents
Preparation method of high-temperature-resistant ceramic and high-temperature-resistant ceramic Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 238000005245 sintering Methods 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 111
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 95
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- 239000011214 refractory ceramic Substances 0.000 claims description 8
- 229920003257 polycarbosilane Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005524 ceramic coating Methods 0.000 abstract description 8
- 238000010304 firing Methods 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 32
- 239000011159 matrix material Substances 0.000 description 23
- 238000005336 cracking Methods 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 16
- 239000010439 graphite Substances 0.000 description 16
- 238000004132 cross linking Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001709 polysilazane Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
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- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
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Abstract
The invention provides a preparation method of high-temperature-resistant ceramic and the high-temperature-resistant ceramic. The preparation method comprises the following steps: s1: PIP process treatment is carried out on the substrate by using the SiC ceramic precursor; s2: coating SiC slurry on the surface of the substrate treated in the step S1, and performing primary sintering in a protective atmosphere; s3: embedding the substrate processed in the step S2 into SiC powder, and performing secondary sintering in protective atmosphere to obtain the high-temperature-resistant ceramic. The method has the advantages of simple operation, low cost, good temperature resistance of the ceramic coating in the firing process, no pulverization and the like. The invention also provides the high-temperature resistant ceramic prepared by the preparation method.
Description
Technical Field
The invention belongs to the field of inorganic functional coating materials, and particularly relates to a preparation method of high-temperature-resistant ceramic and the high-temperature-resistant ceramic.
Background
Silicon carbide is a covalent bond compound, has strong bond energy of atomic combination, has excellent physical and chemical properties, such as corrosion resistance, oxidation resistance, high hardness, small thermal expansion coefficient and the like, and has wide application prospect in the fields of aviation, aerospace, electronic elements, semiconductors and the like. However, silicon carbide itself cannot be used as a structural material, so a method of preparing a coating layer is generally employed to utilize its wear resistance, ablation resistance, and the like.
Slurry brushing is a common method of preparing silicon carbide coatings, and is typically performed by combining ceramic precursors such as Polycarbosilane (PCS), polymethylsilane (PMS), polysiloxane (PSO), polysilazane (PSN), etc. with various ceramic powders to prepare the desired ceramic coating slurry. Since the ceramic precursor undergoes transformation from amorphous to crystalline and from crystalline to crystalline during firing into ceramic, and crystal grains grow during crystallization, the above factors cause changes in the structure and quality of the fired ceramic when the coating is used at too high a temperature, resulting in pulverization of the coating. Therefore, ceramic coatings fired from such coating slurries have poor temperature resistance, and typically the highest use temperature of such ceramic coating applications is less than 1450 ℃. Therefore, a new preparation method is still needed to be developed to solve the problem that the existing high-temperature-resistant ceramic surface coating is poor in temperature resistance.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a preparation method of high-temperature resistant ceramic, which has simple operation, low cost and good temperature resistance of ceramic coating in the firing process, and does not generate the phenomena of pulverization and the like.
The invention also provides a high-temperature resistant ceramic.
The first aspect of the invention provides a preparation method of high temperature resistant ceramic, comprising the following steps:
s1: PIP process treatment is carried out on the substrate by using the SiC ceramic precursor;
s2: coating SiC slurry on the surface of the substrate treated in the step S1, and performing primary sintering in a protective atmosphere;
s3: embedding the substrate processed in the step S2 into SiC powder, and performing secondary sintering in protective atmosphere to obtain the high-temperature-resistant ceramic.
The invention relates to a technical scheme in a preparation method of high-temperature resistant ceramics, which at least has the following beneficial effects:
in the preparation method of the high-temperature resistant ceramic, in the step S1, the SiC ceramic precursor is used for carrying out PIP process treatment on the substrate, so that a large amount of SiC ceramic substrates are contained in the substrate, and in the subsequent sintering process, the SiC ceramic substrates can be evaporated and diffused to the coating positions on the surface of the substrate, on one hand, siC sintering necks are formed, the SiC coating layers on the surface of the substrate are favorable for sintering together, and on the other hand, holes and cracks formed in the cracking process of the ceramic precursor in the SiC coating layers on the surface of the substrate can be filled, so that the SiC coating layers on the surface of the substrate are densified.
In the preparation method of the high-temperature-resistant ceramic, in the step S2, siC slurry is coated on the surface of the substrate treated in the step S1, and the substrate is sintered for the first time in protective atmosphere, so that a high-temperature-resistant SiC coating is formed on the surface of the substrate preliminarily.
According to the preparation method of the high-temperature-resistant ceramic, in the step S3, the substrate treated in the step S2 is embedded in the SiC powder, and the second sintering is carried out in the protective atmosphere, so that part of the SiC powder can be filled in holes and cracks formed in the cracking process of the ceramic precursor in the SiC coating on the surface of the substrate, a certain SiC atmosphere can be formed on the surface of the substrate, the quality loss of the SiC coating on the surface of the substrate in the high-temperature phase transition process is reduced, and the surface coating is compact.
SiC has a boiling point of about 2700 ℃, but SiC starts to evaporate and agglomerate at 1800 ℃, and the gas volatilized by SiC can deposit on large-particle SiC to form sintering necks, and finally, the large-particle SiC is combined, which is the sintering principle of recrystallized silicon carbide. In the step S3, the matrix is embedded in silicon carbide powder for sintering, and in the second sintering process, siC is evaporated, so that the matrix is placed in a steam atmosphere of SiC, the concentration of SiC steam outside the matrix is higher than that in the matrix, the SiC steam diffuses towards the inside of the matrix, and the diffused SiC steam can be deposited on the silicon carbide in the matrix, so that the purpose of filling holes is achieved.
The preparation method of the high-temperature-resistant ceramic is simple to operate and low in cost.
The high-temperature resistant ceramic disclosed by the invention has the coating temperature resistance of more than or equal to 1700 ℃.
According to some embodiments of the invention, in step S1:
according to some embodiments of the invention, the SiC ceramic precursor includes at least one of polymethylsilane and polycarbosilane.
According to some embodiments of the invention, the matrix comprises a graphite matrix, a carbon-carbon matrix, and a ceramic matrix.
According to some embodiments of the invention, the substrate has a through hole therein.
According to some embodiments of the invention, the PIP process is performed between 2 and 3 cycles.
According to some embodiments of the invention, the PIP process treatment temperature is 850-950 ℃.
According to some embodiments of the invention, the temperature of the PIP process treatment is 900-950 ℃.
According to some embodiments of the invention, the PIP process treatment temperature is around 900 ℃.
According to some embodiments of the invention, the PIP process is performed for a period of 18-24 hours.
In the PIP process treatment, the sintering procedure is as follows: heating to 240-280 ℃ at 1-3 ℃/min, preserving heat for 2-5 h for crosslinking treatment, continuously heating to 450-550 ℃ at 1-3 ℃/min, preserving heat for 1-3 h for cracking treatment, heating to 850-950 ℃ at 3-5 ℃/min, preserving heat for 1-3 h for inorganization treatment, cooling to 300-200 ℃ at the rate of 2-3 ℃/min, and cooling to room temperature along with a furnace.
The temperature is raised to 250 ℃ at 2 ℃/min, and the heat is preserved for 4 hours for crosslinking treatment, so as to improve the crosslinking degree of the ceramic precursor and the ceramic yield. The cracked silicon carbide is not pulverized and integrated.
Heating to 500 ℃ at 1 ℃/min, and preserving heat for 2 hours to carry out cracking treatment, so as to lead the crosslinked ceramic precursor to be cracked slowly, reduce the overflow of cracking atmosphere and improve the integrity of the cracking product of the ceramic precursor.
Heating to 900 ℃ at 3 ℃/min, and preserving heat for 1h to carry out inorganic treatment, so as to ensure that the ceramic precursor is converted from organic to inorganic, and reduce the overflow of other components in the later sintering.
The temperature is reduced to 300 ℃ at a rate of 2 ℃/min, so as to release the stress generated in the phase transition process of the ceramic precursor.
In step S2:
according to some embodiments of the invention, the SiC slurry comprises, in mass percent:
polymethylsilane: 30 to 40 weight percent,
toluene: 10 to 20 weight percent,
silicon carbide powder: 30 to 50 weight percent.
According to some embodiments of the invention, the silicon carbide powder in the SiC slurry has a particle size in the range of 400nm to 600nm.
The grain diameter range of the silicon carbide powder is 400 nm-600 nm, which is favorable for the generation of a densification coating.
According to some embodiments of the invention, the silicon carbide powder in the SiC slurry has a particle size in the range of about 500nm.
According to some embodiments of the invention, the temperature of the first sintering is 850 ℃ to 950 ℃.
According to some embodiments of the invention, the temperature of the first sintering is 900 ℃ to 950 ℃.
According to some embodiments of the invention, the temperature of the first sintering is around 900 ℃.
According to some embodiments of the invention, the time for the first sintering is 19-26 hours.
The first sintering is carried out, and the sintering procedure is as follows: heating to 240-280 ℃ at 1-3 ℃/min, preserving heat for 3-5 h for crosslinking treatment, continuously heating to 450-550 ℃ at 1-3 ℃/min, preserving heat for 1-3 h for cracking treatment, heating to 850-950 ℃ at 3-5 ℃/min, preserving heat for 1-3 h for inorganization treatment, cooling to 300-200 ℃ at the rate of 2-3 ℃/min, and cooling to room temperature along with a furnace.
The crosslinking treatment is carried out to remove the solvent in the slurry and improve the crosslinking degree of the ceramic precursor.
The cracking treatment is carried out, so that the ceramic precursor after crosslinking is slowly cracked, the overflow of cracking atmosphere is reduced, the compactness of the coating is improved, and the coating is not pulverized.
The inorganic treatment is carried out to ensure that the ceramic precursor is converted from organic to inorganic, thereby reducing the overflow of other components in the later sintering.
After the inorganic treatment, the temperature is reduced to 300-200 ℃ at the speed of 2-3 ℃/min, so as to control the temperature reduction speed, release the stress generated in the coating forming process and avoid the generation of cracks.
In step S3:
according to some embodiments of the invention, the SiC powder has a particle size of 10 μm to 100 μm.
According to some embodiments of the invention, the second sintering is performed at a temperature of 1900 ℃ to 2100 ℃.
According to some embodiments of the invention, the second sintering is performed for a time period of 40-52 hours.
And sintering for the second time, wherein the sintering procedure is as follows: heating to 1000-1200 deg.C at 3-5 deg.C/min, heating to 1550-1650 deg.C at 1-3 deg.C/min, heating to 1900-2100 deg.C at 1-2 deg.C/min, maintaining for 2-4 h, cooling to 500-300 deg.C at 2-3 deg.C/min, and cooling to room temperature with furnace.
Firstly, heating to 1000-1200 ℃, and the aim is to uniformly heat the material and reduce the temperature difference.
And then heating to 1550-1650 ℃ to crystallize amorphous silicon carbide generated by cracking the ceramic precursor in the material.
And then heating to 1900-2100 ℃ to evaporate silicon carbide particles as much as possible, so that high-concentration silicon carbide vapor around the material diffuses into the low-concentration material, the condensation phenomenon of the silicon carbide vapor in the material and on the surface is improved, sintering necks are formed on the silicon carbide in the material and on the surface, and the integrity of the silicon carbide in the material and the compactness of the coating are improved.
The temperature is reduced to 500-300 ℃ at the speed of 2-3 ℃/min, so as to control the temperature reduction speed and avoid cracking of the coating caused by too fast temperature reduction.
The second aspect of the invention provides a high temperature resistant ceramic prepared by the preparation method of the invention.
The invention relates to a technical scheme of high temperature resistant ceramics, which has at least the following beneficial effects:
the SiC coating on the surface of the substrate of the high-temperature-resistant ceramic has the characteristics of low cost, high density and good temperature resistance, and is suitable for industrial production.
According to some embodiments of the invention, a high temperature resistant SiC coating is included on a substrate and a surface.
According to some embodiments of the invention, the thickness of the high temperature resistant SiC coating on the substrate surface is 0.5-1.2mm.
Drawings
FIG. 1 is a microstructure of the refractory ceramic surface coating prepared in example 1.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the present invention, the present invention provides a method for preparing a high temperature resistant ceramic, comprising the steps of:
s1: PIP process treatment is carried out on the substrate by using the SiC ceramic precursor;
s2: coating SiC slurry on the surface of the substrate treated in the step S1, and performing primary sintering in a protective atmosphere;
s3: embedding the substrate treated in the step S2 into SiC powder, and performing secondary sintering in protective atmosphere to obtain the high-temperature resistant ceramic.
It can be understood that in the preparation method of the high temperature resistant ceramic, in step S1, the SiC ceramic precursor is used to perform PIP process treatment on the substrate, so that a large amount of SiC ceramic substrates are contained in the substrate, and in the subsequent sintering process, the SiC ceramic substrates can be evaporated and diffused to the coating layer on the surface of the substrate, on one hand, the SiC sintering neck is formed, which is favorable for sintering together the SiC coating layer on the surface of the substrate, and on the other hand, holes and cracks formed in the cracking process of the ceramic precursor in the SiC coating layer on the surface of the substrate can be filled, so that the SiC coating layer on the surface of the substrate is densified.
It can be further understood that in the preparation method of the high temperature resistant ceramic, in the step S2, the SiC slurry is coated on the surface of the substrate treated in the step S1, and the first sintering is performed in a protective atmosphere, so that the high temperature resistant SiC coating is primarily formed on the surface of the substrate.
In the preparation method of the high-temperature resistant ceramic, in the step S3, the substrate treated in the step S2 is embedded in the SiC powder, and the second sintering is carried out in the protective atmosphere, so that part of the SiC powder can be filled in holes and cracks formed in the cracking process of the ceramic precursor in the SiC coating on the surface of the substrate, a certain SiC atmosphere can be formed on the surface of the substrate, the quality loss of the SiC coating on the surface of the substrate in the high-temperature phase transition process is reduced, and the surface coating is compact.
It should be noted that SiC has a boiling point of about 2700 ℃, but SiC starts to evaporate and agglomerate at 1800 ℃, and the gas volatilized by SiC can deposit on the large-particle SiC to form sintering necks, and finally, the large-particle SiC is combined, which is the sintering principle of recrystallized silicon carbide. In the step S3, the matrix is embedded in silicon carbide powder for sintering, and in the second sintering process, siC is evaporated, so that the matrix is placed in a steam atmosphere of SiC, the concentration of SiC steam outside the matrix is higher than that in the matrix, the SiC steam diffuses towards the inside of the matrix, and the diffused SiC steam can be deposited on the silicon carbide in the matrix, so that the purpose of filling holes is achieved.
Therefore, the preparation method of the high-temperature-resistant ceramic is simple to operate and low in cost.
The high-temperature resistant ceramic disclosed by the invention has the coating temperature resistance of more than or equal to 1700 ℃. In some embodiments of the invention, in step S1:
the SiC ceramic precursor includes at least one of polymethylsilane and polycarbosilane. The matrix includes graphite matrix, carbon-carbon matrix and ceramic matrix.
The base body has a through hole therein.
The PIP process is carried out for 2-3 cycles.
The PIP process treatment temperature is 850-950 ℃.
The PIP process treatment temperature is 900-950 ℃.
The PIP process treatment temperature is about 900 ℃.
The PIP process treatment time is 20 hours.
In step S2:
the SiC slurry comprises the following components in percentage by mass:
polymethylsilane: 30 to 40 weight percent,
toluene: 10 to 20 weight percent,
silicon carbide powder: 30 to 50 weight percent.
In the SiC slurry, the grain diameter range of the silicon carbide powder is 400 nm-600 nm.
The grain diameter of the silicon carbide powder ranges from 400nm to 600nm, which is favorable for forming a compact coating. In the SiC slurry, the grain size range of the silicon carbide powder is about 500nm.
The temperature of the first sintering is 850-950 ℃.
The temperature of the first sintering is 900-950 ℃.
The temperature of the first sintering is about 900 ℃.
The time for the first sintering was 22h.
In step S3:
the particle size of the SiC powder is 10-100 mu m.
The temperature of the second sintering is 1900-2100 ℃.
The second sintering time was 45h.
In other embodiments of the invention, the invention provides a refractory ceramic prepared by the preparation method of the invention.
It can be understood that the SiC coating on the surface of the substrate of the high-temperature-resistant ceramic has the characteristics of low cost, high density and good temperature resistance, and is suitable for industrial production.
In some embodiments of the invention, the refractory ceramic includes a substrate and a refractory SiC coating on a surface.
In some embodiments of the invention, the thickness of the refractory SiC coating on the surface of the refractory ceramic substrate is 0.5-1.2mm.
The technical solution of the present invention will be better understood by combining the following specific embodiments.
Examples
The embodiment prepares the high temperature resistant ceramic, which comprises the following steps:
the step S1 specifically comprises the following steps:
the density was set at 1.82g/cm 3 The graphite substrate is placed in an impregnating tank and vacuumized to about-0.09 MPa.
Polymethylsilane (PMS) was sucked into the impregnation tank, submerging the graphite substrate, and vacuum impregnating for 2h.
The tank was pressurized to 5MPa with nitrogen and immersed under pressure for 3 hours.
The mixture was discharged to normal pressure, and Polymethylsilane (PMS) was discharged from the bottom of the tank.
Opening the dipping tank, taking out the graphite substrate, putting the graphite substrate into a stainless steel tool, putting the graphite substrate and the stainless steel tool into a sintering furnace, and sintering the graphite substrate at 900 ℃ in a nitrogen atmosphere.
The sintering procedure is as follows: heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours for crosslinking treatment, continuously heating to 500 ℃ at 1 ℃/min, preserving heat for 2 hours for cracking treatment, heating to 900 ℃ at 3 ℃/min, preserving heat for 1 hour for inorganization treatment, cooling to 300 ℃ at the speed of 2 ℃/min, and cooling to a room temperature state with a furnace.
Repeating the PIP process for 2 cycles to obtain a density of 1.91g/cm 3 Is a substrate of a (c).
The step S2 specifically comprises the following steps:
and (2) uniformly coating the prepared SiC slurry on the surface of the substrate treated in the step (S1), and then placing the substrate in a sintering furnace to perform sintering treatment at 900 ℃ in a nitrogen atmosphere.
The sintering procedure is as follows: heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours for crosslinking treatment, continuously heating to 500 ℃ at 1 ℃/min, preserving heat for 2 hours for cracking treatment, heating to 900 ℃ at 3 ℃/min, preserving heat for 1 hour for inorganization treatment, cooling to 300 ℃ at the speed of 2 ℃/min, and cooling to a room temperature state with a furnace.
Opening the furnace, cleaning the workpiece to obtain a substrate with a layer of compact ceramic coating on the surface, wherein the density of the substrate is 1.95g/cm 3 。
The preparation method of the SiC slurry comprises the following steps:
weighing polymethylsilane (40 wt%), toluene (20 wt%) and 500nm silicon carbide powder (40 wt%) and placing them into ball-milling tank, vacuum-pumping to about-0.09 MPa, vacuum ball-milling for 20 hr, then charging nitrogen gas to normal pressure.
The step S3 specifically comprises the following steps:
embedding the substrate treated in the step S2 into silicon carbide powder, and sintering at 1900-2100 ℃ in inert atmosphere.
The sintering procedure is as follows: heating to 1000 ℃ at 3 ℃/min, then heating to 1600 ℃ at 2 ℃/min, heating to 2000 ℃ at 1 ℃/min, preserving heat for 3 hours, cooling to 300 ℃ at the rate of 3 ℃/min, and cooling to a room temperature state along with a furnace.
Wherein the particle size of the silicon carbide powder is 30 mu m.
And (5) after sintering, discharging from the furnace and cleaning. The density was 1.98g/cm 3 The surface of the ceramic is provided with a layer of SiC coating with high density and good temperature resistance.
The prepared high-temperature resistant ceramic can be placed in an argon atmosphere at 1700 ℃ for heat treatment for 3h according to the requirement. After the coating is discharged from the furnace, the surface coating is not chalked, which indicates that the temperature resistance of the coating is more than or equal to 1700 ℃.
The prepared high-temperature resistant ceramic is placed in an argon atmosphere at 1700 ℃ for heat treatment for 3 hours, so that the high-temperature resistant ceramic has two functions, firstly, the stress generated in the silicon carbide sintering process can be eliminated, and the thermal shock resistance of a workpiece is further improved; second, the temperature resistance of the ceramic surface coating can be checked.
The microscopic state of the refractory ceramic surface coating was observed (magnification 400 times), see fig. 1 for a graph. It can be seen that the surface coating has higher density and basically has no holes.
The high-temperature resistant ceramic of the embodiment has good temperature resistance of the ceramic coating in the firing process, and no phenomena such as pulverization and the like occur.
Comparative example 1
The comparison provides a high temperature resistant ceramic, which comprises the following steps:
the step S1 specifically comprises the following steps:
the density was set at 1.82g/cm 3 Placing the graphite matrix in an impregnation tank, and vacuumizing to about-0.09 MPa.
Polymethylsilane (PMS) was sucked into the impregnation tank to impregnate the graphite sample, and vacuum impregnation was performed for 2h.
The tank was pressurized to 5MPa with nitrogen and immersed under pressure for 3 hours.
The mixture was discharged to normal pressure, and Polymethylsilane (PMS) was discharged from the bottom of the tank.
And opening the dipping tank, taking out the graphite sample, putting the graphite sample into a stainless steel tool, putting the stainless steel tool and the graphite sample into a sintering furnace, and performing sintering treatment at 900 ℃ in a nitrogen atmosphere.
The sintering procedure is as follows: heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours for crosslinking treatment, continuously heating to 500 ℃ at 1 ℃/min, preserving heat for 2 hours for cracking treatment, heating to 900 ℃ at 3 ℃/min, preserving heat for 1 hour for inorganization treatment, cooling to 300 ℃ at the speed of 2 ℃/min, and cooling to a room temperature state with a furnace.
Repeating the PIP process for 2 cycles to obtain a density of 1.90g/cm 3 Is a graphite matrix of the above-mentioned graphite material.
The step S2 specifically comprises the following steps:
and uniformly coating the prepared SiC slurry on the surface of the graphite substrate, and then placing the graphite substrate in a sintering furnace to perform sintering treatment at 900 ℃ in a nitrogen atmosphere.
The sintering procedure is as follows: heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours for crosslinking treatment, continuously heating to 500 ℃ at 1 ℃/min, preserving heat for 2 hours for cracking treatment, heating to 900 ℃ at 3 ℃/min, preserving heat for 1 hour for inorganization treatment, cooling to 300 ℃ at the speed of 2 ℃/min, and cooling to a room temperature state with a furnace.
Opening the furnace, cleaning the workpiece to obtain a substrate with a layer of compact ceramic coating on the surface, wherein the density of the substrate is 1.95g/cm 3 。
The preparation method of the SiC slurry comprises the following steps: weighing polymethylsilane (40 wt%), toluene (20 wt%) and 500nm silicon carbide powder (40 wt%) and placing them into ball-milling tank, vacuum-pumping to about-0.1, vacuum ball-milling for 20 hr, then charging nitrogen gas to normal pressure.
The step S3 specifically comprises the following steps:
and (3) placing the substrate treated in the step (S2) in an argon atmosphere at 1700 ℃ for heat treatment for 3 hours. After the furnace is discharged, the surface coating has the chalking phenomenon, and the coating is easily scraped by hard substances, which indicates that the temperature resistance of the coating can not reach 1700 ℃.
In some embodiments of the invention, the invention provides a refractory ceramic prepared by the preparation method of the invention.
It can be understood that the SiC coating on the surface of the substrate of the high-temperature-resistant ceramic has the characteristics of low cost, high density and good temperature resistance, and is suitable for industrial production.
It will be appreciated that the refractory ceramic includes a substrate and a refractory SiC coating on the surface.
In a specific embodiment, the thickness of the high temperature resistant SiC coating on the surface of the high temperature resistant ceramic matrix is 0.8mm.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the high-temperature-resistant ceramic is characterized by comprising the following steps of:
s1: PIP process treatment is carried out on the substrate by using the SiC ceramic precursor;
s2: coating SiC slurry on the surface of the substrate treated in the step S1, and performing primary sintering in a protective atmosphere;
s3: embedding the substrate processed in the step S2 into SiC powder, and performing secondary sintering in protective atmosphere to obtain the high-temperature-resistant ceramic.
2. The method of preparing according to claim 1, wherein the SiC ceramic precursor comprises at least one of polymethylsilane and polycarbosilane.
3. The method of claim 1, wherein the PIP process is performed for a number of 2 to 3 cycles.
4. The method of claim 1, wherein the PIP process is performed at a temperature of 850 ℃ to 950 ℃.
5. The production method according to claim 1, wherein the SiC slurry comprises, in mass percent: polymethylsilane: 30 to 40 weight percent,
toluene: 10 to 20 weight percent,
silicon carbide powder: 30 to 50 weight percent.
6. The method according to claim 1, wherein the particle size of the SiC powder is 10 μm to 100 μm.
7. The method of claim 1, wherein the first sintering is performed at a temperature of 850 ℃ to 950 ℃.
8. The method of claim 1, wherein the second sintering is performed at a temperature of 1900 ℃ to 2100 ℃.
9. A high temperature resistant ceramic prepared by the method of any one of claims 1 to 8.
10. The refractory ceramic of claim 9, comprising a substrate and a surface refractory SiC coating.
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