CN113563083A - Ultrahigh-temperature ceramic prepreg, ultrahigh-temperature ceramic and preparation method thereof - Google Patents
Ultrahigh-temperature ceramic prepreg, ultrahigh-temperature ceramic and preparation method thereof Download PDFInfo
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- CN113563083A CN113563083A CN202110900083.XA CN202110900083A CN113563083A CN 113563083 A CN113563083 A CN 113563083A CN 202110900083 A CN202110900083 A CN 202110900083A CN 113563083 A CN113563083 A CN 113563083A
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
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- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5622—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on zirconium or hafnium carbides
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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- C04B41/5059—Silicon carbide
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention relates to an ultrahigh-temperature ceramic prepreg, ultrahigh-temperature ceramic and a preparation method thereof, wherein the preparation method of the ultrahigh-temperature ceramic prepreg comprises the following steps: ball-milling and mixing the raw materials of the ultrahigh-temperature ceramic prepreg with a solvent, adjusting the pH value to 7.5-9.0, controlling the viscosity value to be 200-CPS, and performing spray drying and sieving to obtain the ultrahigh-temperature ceramic prepreg, wherein the raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 90.60-97.55 parts of ultrahigh-temperature ceramic powder, 1.45-6.25 parts of organic resin and 0.75-3.25 parts of carbon black. The method for preparing the ultrahigh-temperature ceramic by using the carbon-containing prepreg comprises the steps of forming the ultrahigh-temperature ceramic prepreg, carbonizing and impregnating liquid-phase silicon, wherein the bending strength of the carbon-containing preform is more than 50MPa, and the porosity is less than 0.5%. The ultrahigh-temperature ceramic prepreg has the characteristics of long-term storage, easiness in molding, high strength of a biscuit after biscuit firing, good processing performance, large-scale production and the like, and realizes near net-size molding and rapid densification of ultrahigh-temperature ceramic.
Description
Technical Field
The invention relates to the technical field of ultrahigh-temperature ceramics, in particular to an ultrahigh-temperature ceramic prepreg, an ultrahigh-temperature ceramic and a preparation method thereof.
Background
The ultrahigh-temperature ceramic is boride, carbide and nitride of transition metal with high melting point of more than 3000 ℃ and excellent high-temperature oxidation resistance, ablation resistance and thermal shock resistance, and is a candidate material for ultrahigh-temperature protection of a novel aerospace vehicle. But because of the ubiquitous characteristic of strong covalent bonds, the material is difficult to densify and sinter in the preparation process, the fracture toughness and the impact resistance are poor, and the oxidation resistance at a low temperature stage is also poor.
The forming process and the densification process of the ultrahigh-temperature ceramic have certain inherent relation. The reactive infiltration is a low-temperature rapid densification process for preparing the ultrahigh-temperature ceramic, the existing ultrahigh-temperature ceramic can be prepared by combining a forming process with a densification process of embedding reactive infiltration, but the existing forming process has the defects of complex process steps, difficulty in forming, easiness in generating defects and the like, particularly the defects of cracking, deformation and the like in the drying process of a blank body, and the blank body after biscuit firing has low strength, poor processability and low yield and is not suitable for large-scale production.
Disclosure of Invention
The invention mainly aims to provide an ultrahigh-temperature ceramic prepreg, an ultrahigh-temperature ceramic and a preparation method thereof, and aims to solve the technical problems of preparing the ultrahigh-temperature ceramic prepreg which is easy to densify and sinter ultrahigh-temperature ceramic, so that the ultrahigh-temperature ceramic prepreg is easy to form, high in strength of a blank after biscuit firing, good in processing performance and high in density after sintering, and large-scale production of the ultrahigh-temperature ceramic is realized.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a preparation method of an ultrahigh-temperature ceramic prepreg, which comprises the following steps: ball-milling and mixing the raw materials of the ultrahigh-temperature ceramic prepreg with a solvent, adjusting the pH value to 7.5-9.0, controlling the viscosity value to be 200-CPS, and performing spray drying and sieving to obtain the ultrahigh-temperature ceramic prepreg, wherein the raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 90.60-97.55 parts of ultrahigh-temperature ceramic powder, 1.45-6.25 parts of organic resin and 0.75-3.25 parts of carbon black.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method of the ultrahigh-temperature ceramic prepreg, the mass ratio of the organic resin to the carbon black is 8-12: 5.
Preferably, in the preparation method of the ultrahigh-temperature ceramic prepreg, the ultrahigh-temperature ceramic powder is at least one of boron carbide, hafnium carbide, titanium carbide, zirconium boride and hafnium boride; the particle size of the ultrahigh-temperature ceramic powder is 1-10 mu m;
the organic resin is at least one of phenolic resin, epoxy resin and benzoxazine resin.
Preferably, the preparation method of the ultrahigh-temperature ceramic prepreg further includes: the ceramic powder comprises a pore-forming agent, a dispersant I and a dispersant II, wherein the dosage of the pore-forming agent is 10-20% of the mass of the organic resin, the dosage of the dispersant I is 0.5-2% of the mass of the ultrahigh-temperature ceramic powder, and the dosage of the dispersant II is 6-12% of the mass of the carbon black.
Preferably, in the preparation method of the ultrahigh-temperature ceramic prepreg, the pore-forming agent is at least one of methyl cellulose, melamine, potassium chloride and potassium acetate;
the dispersant I is at least one of triethyl phosphate, polyvinyl alcohol, polyethyleneimine, tetramethylammonium hydroxide, ammonium polymethacrylate and gum arabic;
the dispersant II is at least one of polyvinylpyrrolidone, hydroxymethyl cellulose and polyvinyl alcohol.
Preferably, in the preparation method of the ultrahigh-temperature ceramic prepreg, the volume ratio of the raw material to the solvent of the ultrahigh-temperature ceramic prepreg is 1: 1.5-2.5;
the solvent is ethanol or acetone;
the ball milling mixing comprises the following steps: adopting zirconia grinding balls, and mixing for 24-48h in a resin tank at the rotating speed of 400-800 r/min;
the drying is pressure spray drying or centrifugal spray drying, and the air inlet temperature is 110-130 ℃;
the mesh number of the sieve is 10-300 meshes.
Preferably, in the preparation method of the ultrahigh-temperature ceramic prepreg, the raw materials of the ultrahigh-temperature ceramic prepreg include, by mass: ZrB290.60-93.95 parts of powder, 3.75-6.65 parts of organic resin and 1.85-3.45 parts of carbon black; or
The raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 92.25-96.50 parts of ZrC powder, 2.05-5.25 parts of organic resin and 1.25-2.55 parts of carbon black; or
The raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 95.75-97.55 parts of HfC powder, 1.55-3.0 parts of organic resin and 0.75-1.50 parts of carbon black.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the ultrahigh-temperature ceramic prepreg provided by the invention, the ultrahigh-temperature ceramic prepreg is prepared by any one of the preparation methods.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the ultrahigh-temperature ceramic provided by the invention comprises the following steps:
molding the ultrahigh-temperature ceramic prepreg to obtain an ultrahigh-temperature ceramic biscuit;
carbonizing the ultrahigh-temperature ceramic biscuit to obtain an ultrahigh-temperature ceramic carbon-containing preform;
and carrying out liquid-phase silicon infiltration on the ultrahigh-temperature ceramic carbon-containing preform by adopting a silicon powder or silicon alloy powder embedding method to obtain the ultrahigh-temperature ceramic.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method of the ultrahigh-temperature ceramic, the molding is compression molding, isostatic pressing or injection molding; wherein the content of the first and second substances,
the pressure for compression molding is 100-300MPa, and the temperature is 80-150 ℃;
the pressure of the isostatic compaction is 100-300MPa, and the temperature is 80-150 ℃;
the pressure of the injection molding is 40-100MPa, and the temperature is 100-150 ℃;
the carbonization conditions are as follows: under the pressure of 20-80MPa, firstly heating to 180 ℃ with the heating rate of 2-10 ℃/min, preserving heat for 1-3h, then heating to 380 ℃ with the heating rate of 320 ℃/min, preserving heat for 2-4h, then heating to 550 ℃ with the heating rate of 0.5-1 ℃/min, preserving heat for 2-4h, and carrying out low-temperature cracking; then heating to 800-;
the liquid phase silicon infiltration comprises: silicon powder or silicon alloy powder is used for embedding the ultrahigh-temperature ceramic carbon-containing preform, and the temperature is kept for 15-60min at 1300-1800 ℃.
Preferably, in the method for preparing the ultra-high temperature ceramic, the bending strength of the carbon-containing preform of the ultra-high temperature ceramic is 50 to 70 MPa.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the ultrahigh-temperature ceramic provided by the invention, the porosity of the ultrahigh-temperature ceramic is less than 0.5%; the silicon carbide content of the ultrahigh-temperature ceramic is 10-25 vol.%; the bending strength of the ultrahigh-temperature ceramic is 350-410 MPa.
By means of the technical scheme, the ultrahigh-temperature ceramic prepreg, the ultrahigh-temperature ceramic and the preparation method thereof at least have the following advantages:
1. the ultrahigh-temperature ceramic prepreg provided by the invention mainly takes ultrahigh-temperature ceramic powder, organic resin and carbon black as raw materials, and the organic resin can be used as a carbon source and a bonding curing agent, so that the ultrahigh-temperature ceramic prepreg has the characteristics of long-term storage, easiness in molding, convenience in use and the like, and is suitable for various high-efficiency and low-cost molding processes.
2. After the ultrahigh-temperature ceramic prepreg is molded and biscuited, the strength of a carbon-containing prefabricated body can reach 50-70MPa, which is 3-5 times of the strength of a blank body after biscuiting of the conventional gel casting, so that the ultrahigh-temperature ceramic prepreg has excellent machining performance, reduces the machining of high-hardness materials with high difficulty after sintering, improves the working efficiency, improves the quality and yield of products, and reduces the production cost.
3. The carbon-containing preform obtained by biscuiting the ultrahigh-temperature ceramic prepreg disclosed by the invention can realize near net size rapid densification of ultrahigh-temperature ceramic with a complex shape by adopting a liquid-phase silicon infiltration process, and has the advantages of simple equipment, low process temperature, low porosity, high efficiency, low cost, easiness in popularization and the like, and the large-scale production of the ultrahigh-temperature ceramic can be realized.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects of the ultra-high temperature ceramic prepreg, the ultra-high temperature ceramic and the method for preparing the same according to the present invention will be made with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The preparation method of the ultrahigh-temperature ceramic prepreg provided by the embodiment of the invention comprises the following steps:
(1) preparing ultrahigh-temperature ceramic slurry;
ball-milling and mixing the raw materials of the ultrahigh-temperature ceramic prepreg and a solvent, adjusting the pH value to 7.5-9.0, and controlling the viscosity value to be 200-800CPS to obtain ultrahigh-temperature ceramic slurry; the ultrahigh-temperature ceramic prepreg comprises the following raw materials in parts by mass: 90.60-97.55 parts of ultrahigh-temperature ceramic powder, 1.45-6.25 parts of organic resin and 0.75-3.25 parts of carbon black.
Further, the ultrahigh-temperature ceramic powder is at least one of boron carbide, hafnium carbide, titanium carbide, zirconium boride and hafnium boride; the particle size of the ultrahigh-temperature ceramic powder is 1-10 mu m.
In the embodiment, the particle size of the ultrahigh-temperature ceramic powder in the raw material is limited to 1-10 μm, and although the particle size can be reduced by ball milling in the preparation process, the influence on the particle size is very small when the ball milling is carried out at the rotating speed of 400-. The smaller the grain size of the ultra-high temperature ceramic powder is, the higher the strength of the sintered material is, and the ultra-high temperature ceramic should have high mechanical properties as much as possible; the grain size of the ultrahigh-temperature ceramic powder is small, and the strength and hardness of the ultrahigh-temperature ceramic powder corresponding to carbide and boride are higher. Therefore, it is necessary to define the particle size of the ultrahigh-temperature ceramic powder in the raw material. The organic resin of the embodiment is preferably resin with good temperature resistance and high carbon content, the curing temperature is higher than 150 ℃, and the carbon content is higher than 50 percent, such as thermosetting phenolic resin.
In some embodiments, the organic resin is at least one of a phenolic resin, an epoxy resin, and a benzoxazine resin.
Further, the phenolic resin is at least one of ammonia phenolic resin and boron phenolic resin. The boron phenolic resin has good temperature resistance and a large temperature operation window; the curing performance of the ammonia phenolic resin is good.
Different ultrahigh-temperature ceramic powder needs different amounts of organic resin and carbon black to achieve better collocation, so that the forming performance and the finished product performance are better.
In some embodiments, the raw material of the ultrahigh-temperature ceramic prepreg comprises, in parts by mass: ZrB290.60-93.95 parts of powder, 3.75-6.65 parts of organic resin and 1.85-3.45 parts of carbon black.
In other embodiments, the raw material of the ultrahigh-temperature ceramic prepreg comprises, by mass: 92.25-96.50 parts of ZrC powder, 2.05-5.25 parts of organic resin and 1.25-2.55 parts of carbon black.
In still other embodiments, the raw material of the ultrahigh-temperature ceramic prepreg comprises, in parts by mass: the composite material comprises the following raw materials in parts by mass: 95.75-97.55 parts of HfC powder, 1.55-3.0 parts of organic resin and 0.75-1.50 parts of carbon black.
According to the embodiment of the invention, the carbonized organic resin is introduced into the ultrahigh-temperature ceramic powder, the liquid phase is mixed and dried to obtain the ultrahigh-temperature ceramic prepreg, the obtained ultrahigh-temperature ceramic prepreg is powder for preparing ultrahigh-temperature ceramic, the organic resin can be used as a carbon source and a bonding curing agent, and simultaneously carbon black is added to be used as a carbon source supplement, so that the ultrahigh-temperature ceramic prepreg has the characteristics of long-term storage, easiness in molding, convenience in use and the like, and is suitable for various high-efficiency and low-cost molding processes. The prepreg powder also has the characteristics of high green body strength and low-temperature densification, realizes the near-net forming of composite material products, and realizes the large-scale production of ultrahigh-temperature ceramics.
The prior prepreg is an intermediate material for manufacturing a polymer matrix composite material, and a resin matrix is adopted to impregnate continuous fibers or fabrics. The development of the prepreg technology enables the high-molecular-weight composite material to have the advantages of low defect, designability, controllable quality, standardized production and the like.
In some embodiments, the mass ratio of organic resin to carbon black is from 8 to 12:5, preferably 2: 1.
In the embodiment, the organic resin and the carbon black are both carbon sources for reaction sintering, the residual carbon rate of the organic resin is about 60 wt%, the total volume of the organic resin is shrunk in the carbonization and reaction process to generate the silicon carbide, the carbon black is expanded in the reaction process to generate the silicon carbide, the two carbon sources are complementary, the volume of the silicon carbide generated in the reaction process after carbonization is 68% of the volume of the resin, the volume of the silicon carbide generated in the reaction process after the carbon black is reacted to generate the silicon carbide is about 2 times, the volume of the silicon carbide formed in the reaction process is basically unchanged by adopting the mass ratio of 8-12:5, and the volume fraction of free silicon can be reduced as much as possible. And there is a preferred ratio of 2: 1.
Because part of the organic resin is liquid or stored in a solution mode, the wet mixing is convenient, in addition, even dry powder organic resin has the problems of wall sticking, agglomeration and the like during mixing and grinding, the mixing uniformity is poor, and the silicon carbide has relatively high density and also has the problem of sedimentation, so that the auxiliary agent can be added into the raw materials to improve the mixing uniformity. In general, no auxiliary agent is added in the existing preparation, and a pore-forming agent and a dispersing agent are required to be added in the long-term storage.
In some embodiments, in step (1), the raw material of the ultra-high temperature ceramic prepreg further includes: the ceramic powder comprises a pore-forming agent, a dispersant I and a dispersant II, wherein the dosage of the pore-forming agent is 10-20% of the mass of the organic resin, the dosage of the dispersant I is 0.5-2% of the mass of the ultrahigh-temperature ceramic powder, and the dosage of the dispersant II is 6-12% of the mass of the carbon black.
In the present embodiment, the pore-forming agent functions to control the pore structure, making it easy to infiltrate; the dispersant I is used for dispersing the silicon carbide powder; the dispersant II is used for dispersing carbon black powder.
The pore-forming agent is at least one of methyl cellulose, melamine, potassium chloride and potassium acetate;
the dispersant I is at least one of triethyl phosphate, polyvinyl alcohol, polyethyleneimine, tetramethylammonium hydroxide, ammonium polymethacrylate and gum arabic;
the dispersant II is at least one of polyvinylpyrrolidone, hydroxymethyl cellulose and polyvinyl alcohol.
In some embodiments, the solvent makes the viscosity of the ultrahigh-temperature ceramic prepreg 200-800CPS, and the volume ratio of the raw materials of the ultrahigh-temperature ceramic prepreg to the solvent is 1: 1.5-2.5; the solvent is ethanol or acetone;
the ball milling mixing comprises the following steps: zirconium oxide grinding balls are adopted to be mixed in a resin tank for 24-48h at the rotating speed of 400-800 r/min.
(2) Preparing ultrahigh-temperature ceramic prepreg powder:
and (3) carrying out spray drying and screening on the ultrahigh-temperature ceramic slurry obtained in the step (1) to obtain the ultrahigh-temperature ceramic prepreg.
The drying is pressure spray drying or centrifugal spray drying, and the air inlet temperature is 110-130 ℃;
the mesh number of the sieve is 10-300 meshes so as to keep better flowability of the powder and facilitate the molding of the powder.
In the step (2), the powder is prepared by spray drying by a slurry method, so that the resin completely coats the silicon carbide powder particles to form a prepreg, the dry ball milling mixing is not uniform, the coating cannot be formed, and the thermosetting resin is stored in a solution state under many conditions to delay the crosslinking aging. Therefore, the present application does not require direct powder milling mixing, but rather requires a solvent, followed by drying.
The embodiment of the invention designs the powder composition to form the preparation method of the ultrahigh-temperature ceramic composite powder which is easy to form and compact at low temperature.
The invention further provides the ultrahigh-temperature ceramic prepreg which is prepared by the preparation method of the ultrahigh-temperature ceramic prepreg.
The ultrahigh-temperature ceramic prepreg provided by the embodiment of the invention mainly takes ultrahigh-temperature ceramic powder, organic resin and carbon black as raw materials, so that the ultrahigh-temperature ceramic prepreg has the characteristics of long-term storage, easiness in molding, convenience in use, large-scale production and the like, and is suitable for various high-efficiency and low-cost molding processes.
Another embodiment of the present invention provides a method for preparing an ultrahigh-temperature ceramic by using the prepared ultrahigh-temperature ceramic prepreg, and on the basis of the above embodiment, the method of the present embodiment further comprises the following steps:
(3) forming a ceramic prepreg:
molding the ultrahigh-temperature ceramic prepreg obtained in the step (2) to obtain an ultrahigh-temperature ceramic biscuit;
specifically, in the step (3), the molding is compression molding, isostatic pressing or injection molding; wherein the content of the first and second substances,
the pressure for compression molding is 100-300MPa, and the temperature is 80-100 ℃;
the pressure of the isostatic compaction is 100-300MPa, and the temperature is 80-100 ℃;
the temperature of the injection molding is 100-120 ℃, and the pressure is 40-100 MPa.
(4) Preparing an ultrahigh-temperature ceramic carbon-containing preform:
carbonizing the ultrahigh-temperature ceramic biscuit obtained in the step (3) to obtain an ultrahigh-temperature ceramic carbon-containing preform;
in the embodiment, the formed biscuit is carbonized under certain pressure and temperature rise under the condition of using or not using a vacuum mould to obtain the ultrahigh-temperature ceramic carbon-containing preform.
Specifically, in the step (4), the carbonization conditions are as follows: under the pressure of 20-80MPa, firstly heating to 100-180 ℃ at the heating rate of 2-10 ℃/min, preserving heat for 1-3h, then heating to 350 ℃ at the heating rate of 0.5-1 ℃/min, preserving heat for 2-4h, then heating to 500 ℃ at the heating rate of 0.5-1 ℃/min, preserving heat for 2-4h, and carrying out low-temperature cracking; then heating to 1000 ℃ at the heating rate of 1-3 ℃/min, preserving heat for 1-2h, heating to 1500 ℃ at the heating rate of 5-10 ℃/min, and preserving heat for 1-2 h.
The above carbonization conditions vary depending on the kind of the resin.
In some embodiments, the bending strength of the ultrahigh-temperature ceramic carbonaceous preform is 50 to 70 MPa.
The prepared carbon-containing ultrahigh-temperature ceramic preform can be preprocessed by adopting a surface grinding machine, a numerical control engraving machine tool and other equipment, and has better machining performance. Due to the high bending strength, ceramic products with large sizes, such as ceramic products with the size larger than 1 meter, can be processed, and ceramic products with special structures, such as thin-wall weight-reducing structural parts with the size of more than 900mm, can also be processed. The method of the invention enables the carbon-containing prefabricated body to be processed more easily and has higher yield.
The embodiment realizes the carbon-containing prefabricated body suitable for the embedding liquid-phase silicon infiltration densification process through the ultrahigh-temperature ceramic prepreg and the heat treatment process which are reasonably designed.
(5) Reaction, dissolution, infiltration and densification of the ultrahigh-temperature ceramic:
and (4) carrying out liquid-phase silicon infiltration on the carbon-containing prefabricated body of the ultrahigh-temperature ceramic obtained in the step (4) by adopting an embedding method to obtain the ultrahigh-temperature ceramic.
In the step (5), the liquid-phase silicon infiltration includes: silicon powder or silicon alloy powder is used for embedding the ultrahigh-temperature ceramic carbon-containing preform, and the temperature is kept for 15-60min at 1300-1800 ℃.
The liquid-phase silicon impregnation (also referred to as melt siliconizing, LSI) of the present embodiment employs a silicon powder or silicon alloy powder embedding method, and specifically includes: placing the carbon-containing ultrahigh-temperature ceramic preform in a graphite tool after silicification, embedding the carbon-containing ultrahigh-temperature ceramic preform by using silicon powder or silicon alloy powder with the granularity of 0.2-0.5mm, placing the graphite tool in a vacuum high-temperature furnace for reaction at the reaction temperature of 1300-1800 ℃ and keeping the temperature for 15-60 min.
In some embodiments, the silicon alloy includes, but is not limited to, at least one of the following: silicon-zirconium alloy, silicon-titanium alloy, silicon-hafnium alloy, silicon-tantalum alloy, etc.
Another embodiment of the present invention also provides an ultra-high temperature ceramic, which is prepared by the preparation method of the ultra-high temperature ceramic.
The porosity of the ultrahigh-temperature ceramic is less than 0.5%; the silicon carbide content of the ultrahigh-temperature ceramic is 10-25 vol.%; the bending strength of the ultrahigh-temperature ceramic is 350-410 MPa.
According to the embodiment of the invention, the carbonized organic resin is introduced into the ultrahigh-temperature ceramic powder, so that the automatic preparation and storage of the ultrahigh-temperature ceramic raw material are realized, and the prepared ultrahigh-temperature ceramic prepreg can be molded by adopting efficient molding processes such as compression molding, cold isostatic pressing, injection molding, tape casting and the like, so that the near-net-size molding of the ultrahigh-temperature ceramic part is realized. According to the embodiment of the invention, silicon carbide is introduced in a reaction sintering manner, so that the sintering temperature is effectively reduced, and the density of the material is improved.
The invention develops a high-efficiency near-net-size forming and carbon-containing preform heat treatment process based on prepreg, improves the production efficiency of ultrahigh-temperature ceramics and reduces the cost by embedding liquid-phase silicon infiltration.
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with certain insubstantial modifications and adaptations of the invention based on the teachings of the invention set forth herein.
In the following examples of the present invention, all reagents used are commercially available unless otherwise specified, and the methods involved are conventional unless otherwise specified. In the following examples of the present invention, the components referred to are all commercially available products well known to those skilled in the art unless otherwise specified.
Example 1
ZrB2-20 vol.% preparation method of SiC ultra high temperature ceramic, which comprises the following steps:
(1) ZrB at 930g2(the grain diameter D50 is 5.5 mu m), 60.5g of boron phenolic resin and 25.5g of carbon black are used as raw materials, absolute ethyl alcohol is used as a medium, zirconia grinding balls are selected, the mixture is ball-milled in a resin tank at the rotating speed of 600r/min for 24 hours, the pH value is adjusted to 7.5, the viscosity value is 350CPS, the mixture is spray-dried at the temperature of 145 ℃, and the mixture is sieved by a 20-mesh sieve, so that the ultrahigh-temperature ceramic prepreg is obtained;
(2) carrying out vacuum compression molding on the ultrahigh-temperature ceramic prepreg obtained in the step (1) at 100MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 185 ℃ for 2h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain ZrB2-C ultra high temperature ceramic carbonaceous preform;
(4) ZrB obtained in the step (3)2Putting the-C ultrahigh-temperature ceramic carbon-containing preform into a high-temperature vacuum furnace, and carrying out liquid-phase siliconizing at 1600 ℃ by adopting a silicon powder embedding method to obtain ZrB2-20 vol.% SiC ultra high temperature ceramic.
Detected ZrB2The bending strength of the carbon-containing prefabricated body of the ultrahigh-temperature ceramic is 71.3 +/-3 MPa; ZrB2-20 vol.% SiC ultra high temperature ceramic having a density of 4.58 + -0.05 g/cm3The porosity is 0.4 plus or minus 0.05 percent and the bending strength is 361 plus or minus 10 MPa.
In each example, flexural strength and flexural strength were tested using the flexural strength test method of the ceramic material GB T4741-1999, and density and porosity were tested using the test method GB/T25995-2010 fine ceramic density and apparent porosity.
Example 2
A preparation method of ZrC-25 vol.% SiC superhigh temperature ceramic specifically comprises the following steps:
(1) 925g of ZrC (the grain diameter D50 is 5.5 mu m), 50g of boron phenolic resin and 25g of carbon black are taken as raw materials, 10g of methyl cellulose is added as a pore-forming agent, absolute ethyl alcohol is taken as a medium, zirconium oxide grinding balls are selected, the mixture is ball-milled in a resin tank at the rotating speed of 600r/min for 24 hours, the pH value is adjusted to 8.0, the viscosity value is 350CPS, spray drying is carried out at 145 ℃, and the mixture is sieved by a 20-mesh sieve, so that the ultrahigh-temperature ceramic prepreg is obtained;
(2) carrying out cold isostatic pressing on the ultrahigh-temperature ceramic prepreg obtained in the step (1) at 150MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 185 ℃ for 2h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain a ZrC-C ultrahigh temperature ceramic carbon-containing prefabricated body;
(4) and (4) placing the ZrC-C ultrahigh-temperature ceramic carbon-containing preform obtained in the step (3) in a high-temperature vacuum furnace, and performing liquid-phase siliconizing at 1600 ℃ by adopting a silicon powder embedding method to obtain ZrC-25 vol.% SiC ultrahigh-temperature ceramic.
Through detection, the bending strength of the ZrC-C ultrahigh-temperature ceramic carbon-containing preform is 65.3 +/-3 MPa, and the density of the ZrC-25 vol.% SiC ultrahigh-temperature ceramic is 5.61 +/-0.05 g/cm3The porosity is 0.3 plus or minus 0.02 percent, and the bending strength is 373 plus or minus 10 MPa.
Example 3
ZrB2-20 vol.% preparation method of SiC ultra high temperature ceramic, which comprises the following steps:
(1) ZrB at 930g2(particle size D50 ═ 5.5 μm), 51g of boron phenol resin, and 32g of carbon black as raw materials, and 9.30g of (ZrB) was added21.0% of polyethyleneimine by mass and 1.89g (10% of carbon black by mass) of polyvinylpyrrolidone by mass as a dispersing agent, and selecting anhydrous ethanol as a medium, ball-milling and mixing materials in a resin tank at a rotating speed of 600r/min for 24 hours, adjusting the pH value to 8.0, adjusting the viscosity value to 350CPS, spray-drying at 145 ℃, and sieving with a 20-mesh sieve to obtain the ultrahigh-temperature ceramic prepreg;
(2) carrying out cold isostatic pressing on the ultrahigh-temperature ceramic prepreg obtained in the step (1) at 150MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 185 ℃ for 2h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain ZrB2-C ultra high temperature ceramic carbonaceous preform;
(4) ZrB obtained in the step (3)2Putting the-C ultrahigh-temperature ceramic carbon-containing preform into a high-temperature vacuum furnace, and carrying out liquid-phase siliconizing at 1600 ℃ by adopting a silicon powder embedding method to obtain ZrB2-20 vol.% SiC ultra high temperature ceramic.
Detected ZrB2-C superhigh temperature potteryThe bending strength of the ceramic carbon-containing preform is 65.3 +/-3 MPa, ZrB2-20 vol.% SiC ultra high temperature ceramic having a density of 4.66. + -. 0.05g/cm3The porosity is 0.3 plus or minus 0.03 percent, and the bending strength is 368 plus or minus 10 MPa.
Example 4
ZrB2-15 vol.% SiC ultra high temperature ceramic preparation method, which specifically comprises the following steps:
(1) 955g of ZrB2(particle size D50 ═ 5.5 μm), 34.5g of an aminophenol resin, and 21.5g of carbon black as raw materials, and 16g of (ZrB) was added21.7% of polyethyleneimine by mass and 1.2g (6% of carbon black by mass) of polyvinylpyrrolidone by mass as dispersing agents, and selecting zirconium oxide grinding balls as media, ball-milling the mixed materials in a resin tank at a rotating speed of 400r/min for 24 hours, adjusting the pH value to 9.0, adjusting the viscosity value to 275CPS, spray-drying at 125 ℃, and sieving to obtain an ultrahigh-temperature ceramic prepreg;
(2) carrying out vacuum compression molding on the ultrahigh-temperature ceramic prepreg obtained in the step (1) at 90MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 175 ℃ for 3h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain ZrB2-C ultra high temperature ceramic carbonaceous preform.
(4) ZrB obtained in the step (3)2Placing the-C ultrahigh-temperature ceramic carbon-containing preform in a high-temperature vacuum furnace, and siliconizing in a liquid phase at 1550 ℃ by adopting a SiZr10 alloy embedding method to obtain ZrB2-15 vol.% SiC ultra high temperature ceramic.
Detected ZrB2The bending strength of the-C ultrahigh-temperature ceramic carbon-containing preform is 60.4 +/-2 MPa, and ZrB2-15 vol.% SiC ultra high temperature ceramic having a density of 4.75 + -0.08 g/cm3The porosity is 0.4 +/-0.05%, and the bending strength is 365 +/-15 MPa.
Example 5
ZrB2-15 vol.% SiC ultra high temperature ceramic preparation method, which specifically comprises the following steps:
(1) ZrB at 980g2(the grain diameter D50 is 5.0 mu m), 40.5g of FBA phenolic resin and 17g of carbon black are taken as raw materials, 18g of triethyl phosphate and 4g of polyvinylpyrrolidone are added as dispersing agents, 25g of melamine is added as a pore-forming agent, absolute ethyl alcohol is taken as a medium, zirconium oxide grinding balls are selected, the mixed materials are ball-milled in a resin tank at the rotating speed of 800r/min for 24 hours, the pH value is adjusted to 8.0, the viscosity value is 280CPS, spray drying is carried out at the temperature of 145 ℃, and sieving is carried out to obtain the ultrahigh-temperature ceramic prepreg;
(2) carrying out vacuum compression molding on the ultrahigh-temperature ceramic prepreg obtained in the step (1) at 90MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 180 ℃ for 3h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain ZrB2-C ultra high temperature ceramic carbonaceous preform.
(4) ZrB obtained in the step (3)2Placing the-C ultrahigh-temperature ceramic carbon-containing preform in a high-temperature vacuum furnace, and siliconizing in a liquid phase at 1800 ℃ by adopting a SiZr30 alloy embedding method to obtain ZrB2-15 vol.% SiC ultra high temperature ceramic.
Detected ZrB2The bending strength of the-C ultrahigh-temperature ceramic carbon-containing preform is 61.5 +/-2 MPa, ZrB2-15 vol.% SiC ultra high temperature ceramic having a density of 4.76. + -. 0.10g/cm3The porosity is 0.5 plus or minus 0.05 percent and the bending strength is 373 plus or minus 15 MPa.
Example 6
ZrB2-20 vol.% preparation method of SiC ultra high temperature ceramic, which comprises the following steps:
(1) ZrB at 930g2(the grain diameter D50 is 5.5 mu m), 60.5g of boron phenolic resin and 25.5g of carbon black are taken as raw materials, 18g of polyvinyl alcohol and 6g of polyvinylpyrrolidone are added as dispersing agents, absolute ethyl alcohol is taken as a medium, zirconium oxide grinding balls are selected, ball milling and mixing are carried out in a resin tank at the rotating speed of 600r/min for 24h, the pH value is adjusted to 7.5, the viscosity value is 350CPS, spray drying is carried out at 145 ℃, and the mixture is sieved by a 20-mesh sieve, so as to obtain the ultrahigh-temperature ceramic prepreg;
(2) carrying out vacuum compression molding on the ultrahigh-temperature ceramic prepreg obtained in the step (1) at 100MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 185 ℃ for 2h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain ZrB2-C ultra high temperature ceramic carbonaceous preform;
(4) ZrB obtained in the step (3)2Putting the-C ultrahigh-temperature ceramic carbon-containing preform into a high-temperature vacuum furnace, and carrying out liquid-phase siliconizing at 1600 ℃ by adopting a silicon powder embedding method to obtain ZrB2-20 vol.% SiC ultra high temperature ceramic.
Detected ZrB2The bending strength of the-C ultrahigh-temperature ceramic carbon-containing preform is 71.3 +/-3 MPa, ZrB2-20 vol.% SiC ultra high temperature ceramic having a density of 4.68. + -. 0.05g/cm3The porosity is 0.4 plus or minus 0.05 percent and the bending strength is 357 plus or minus 15 MPa.
Comparative example 1
ZrB2-20 vol.% preparation method of SiC ultra high temperature ceramic, which comprises the following steps:
(1) ZrB at 930g2(the grain diameter D50 is 5.5 mu m), 61g of carbon black is taken as a raw material, 18g of acrylamide and 2g of methylene bisacrylamide are added, 18g of polyvinyl alcohol and 6g of polyvinylpyrrolidone are added as dispersing agents, 80g of water is added as a medium, zirconium oxide grinding balls are selected and mixed by ball milling in a resin tank at the rotating speed of 600r/min for 24h, and vacuum degassing is carried out to obtain ultrahigh-temperature ceramic slurry;
(2) adding an initiator into the ultrahigh-temperature ceramic slurry obtained in the step (1), slowly stirring for 2-5 minutes, injecting the ultrahigh-temperature ceramic slurry into a mold, sealing with a preservative film, and standing for 4-8 hours for curing and molding; carrying out isothermal and equal-humidity drying at 80 ℃ for 24 hours, and then drying in an oven for 6-8 hours to obtain an ultrahigh-temperature ceramic blank;
(3) placing the ultrahigh-temperature ceramic blank obtained in the step (2) in a vacuum high-temperature furnace, preserving heat for 0.5h at 5 ℃/min → 300 ℃, preserving heat for 0.5h at 1 ℃/min → 500 ℃, preserving heat for 0.5h at 2 ℃/min → 800 ℃, and then preserving heat for 5 DEG CKeeping the temperature of 1500 ℃ for 1h at the temperature of/min → ZrB is obtained after high-temperature degumming2-C ultra high temperature ceramic carbonaceous preform;
(4) ZrB obtained in the step (3)2Putting the-C ultrahigh-temperature ceramic carbon-containing preform into a high-temperature vacuum furnace, and carrying out liquid-phase siliconizing at 1600 ℃ by adopting a silicon powder embedding method to obtain ZrB2-20 vol.% SiC ultra high temperature ceramic.
Detected ZrB2The bending strength of the-C ultrahigh-temperature ceramic carbon-containing preform is 13.5 +/-1.5 MPa, ZrB2-20 vol.% SiC ultra high temperature ceramic having a density of 4.63. + -. 0.05g/cm3The porosity is 0.6 plus or minus 0.05 percent and the bending strength is 352 plus or minus 15 MPa.
Example 7
A preparation method of HfC-15 vol.% SiC superhigh temperature ceramic specifically comprises the following steps:
(1) using 980g of HfC (particle size D50 is 5.0 μm), 16g of FBA phenolic resin and 10g of carbon black as raw materials, adding 18g of polyvinyl alcohol and 4g of polyvinylpyrrolidone as dispersing agents, using absolute ethyl alcohol as a medium, selecting zirconium oxide grinding balls, ball-milling and mixing the materials in a resin tank at the rotating speed of 800r/min for 24 hours, adjusting the pH value to 8.5, adjusting the viscosity value to 280CPS, spray-drying at 145 ℃, and sieving to obtain the ultrahigh-temperature ceramic prepreg;
(2) carrying out vacuum compression molding on the ultrahigh-temperature prepreg obtained in the step (1) at 90MPa to obtain an ultrahigh-temperature ceramic biscuit;
(3) placing the ultrahigh-temperature ceramic biscuit obtained in the step (2) in a vacuum high-temperature furnace and a hot-pressing furnace, and carrying out low-temperature cracking at the temperature of 5 ℃/min → 180 ℃ for 3h, 0.5 ℃/min → 350 ℃ for 2h and 0.5 ℃/min → 500 ℃ for 2 h; then preserving heat for 2h at the temperature of 2 ℃/min → 1000 ℃, preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ to obtain an HfC-C ultrahigh-temperature ceramic carbon-containing prefabricated body;
(4) and (4) placing the HfC-C ultrahigh-temperature ceramic carbon-containing preform obtained in the step (3) in a high-temperature vacuum furnace, and performing liquid-phase siliconizing at 1800 ℃ by adopting a SiZr30 alloy embedding method to obtain HfC-15 vol.% SiC ultrahigh-temperature ceramic.
Through detection, the bending strength of the HfC-C ultrahigh-temperature ceramic carbon-containing preform is 58.5 +/-2 MPa, and the density of the HfC-15 vol.% SiC ultrahigh-temperature ceramic is 5.76 +/-0.10 g/cm3The porosity is 0.4 plus or minus 0.05 percent and the bending strength is 373 plus or minus 15 MPa.
Comparative example 2
A preparation method of HfC-15 vol.% SiC superhigh temperature ceramic specifically comprises the following steps:
(1) using 980g of HfC (particle size D50 is 5.5 mu m) and 19g of carbon black as raw materials, adding 9g of acrylamide and 1g of methylene bisacrylamide, adding 18g of polyvinyl alcohol and 4g of polyvinylpyrrolidone as dispersing agents, using water as a medium, selecting zirconium oxide grinding balls, ball-milling and mixing materials in a resin tank at the rotating speed of 600r/min for 24h, and performing vacuum degassing to obtain ultrahigh-temperature ceramic slurry;
(2) adding an initiator into the ultrahigh-temperature ceramic slurry obtained in the step (1), slowly stirring for 2-5 minutes, injecting the ultrahigh-temperature ceramic slurry into a mold, sealing with a preservative film, and standing for 4-8 hours for curing and molding; carrying out isothermal and equal-humidity drying at 80 ℃ for 24 hours, and then drying in an oven for 6-8 hours to obtain an ultrahigh-temperature porcelain blank;
(3) and (3) placing the ultrahigh-temperature ceramic blank obtained in the step (2) into a vacuum high-temperature furnace, preserving heat for 0.5h at the temperature of 5 ℃/min → 300 ℃, preserving heat for 0.5h at the temperature of 1 ℃/min → 500 ℃, preserving heat for 1h at the temperature of 2 ℃/min → 800 ℃, and then preserving heat for 1h at the temperature of 5 ℃/min → 1500 ℃ for high-temperature glue removal to obtain the HfC-C ultrahigh-temperature ceramic carbon-containing preform.
(4) And (4) placing the HfC-C ultrahigh-temperature ceramic carbon-containing preform obtained in the step (3) in a high-temperature vacuum furnace, and performing liquid-phase siliconizing at 1600 ℃ by adopting a SiZr30 alloy embedding method to obtain HfC-15 vol.% SiC ultrahigh-temperature ceramic.
Through detection, the bending strength of the HfC-C ultrahigh-temperature ceramic carbon-containing preform is 11.3 +/-1.5 MPa, and the density of the HfC-15 vol.% SiC ultrahigh-temperature ceramic is 5.73 +/-0.05 g/cm3The porosity is 0.7 plus or minus 0.05 percent and the bending strength is 351 plus or minus 20 MPa.
As can be seen from the above, the ultrahigh temperature ceramics prepared by the method of the present embodiment have simple processes, examples 1 to 7 adopt compression molding, isostatic pressing or injection molding, and comparative examples 1 to 2 adopt gel injection molding.
As can be seen from the results of the tests of examples 1 to 7 and comparative examples 1 to 2, the ultra-high temperature ceramic carbonaceous preforms of examples 1 to 7 had flexural strengths of about 50 to 70MPa and poresThe porosity is less than 0.5%. Example 6 and comparative example 1 were all to obtain ZrB220 vol.% SiC, but the raw materials and processes used for both differ, both in the bending strength of the carbon-containing preform and in the density, porosity and bending strength of the ultra-high temperature ceramic; example 7 and comparative example 2 both obtained HfC-15 vol.% SiC, which had different raw materials and methods, and had different flexural strength of the carbon-containing preform and different densities, porosities, and flexural strengths of the ultra-high temperature ceramics; as can be seen from the comparative data, the bending strength of the carbon-containing preform of the example is much higher than that of the carbon-containing preform of the comparative example, the porosity of the ultra-high temperature ceramic of the example is lower than that of the ultra-high temperature ceramic of the comparative example, and the density of the ultra-high temperature ceramic of the example is slightly higher than that of the ultra-high temperature ceramic of the comparative example. Therefore, the method provided by the embodiment of the invention has the characteristics of high green body strength, high density, low porosity and the like, and can realize various forming processes and provide initial high strength mainly because the organic resin has certain fluidity under pressure and temperature and has the bonding characteristic. Especially compared with the traditional gel injection molding process, the strength of the blank is improved by more than 4 times, mainly because the continuous carbon formed after the high molecular resin is carbonized bonds the ceramic powder, the partial sintering of the powder is realized, and the ceramic powder has certain sintering strength.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. The preparation method of the ultrahigh-temperature ceramic prepreg is characterized by comprising the following steps of: ball-milling and mixing the raw materials of the ultrahigh-temperature ceramic prepreg with a solvent, adjusting the pH value to 7.5-9.0, controlling the viscosity value to be 200-CPS, and performing spray drying and sieving to obtain the ultrahigh-temperature ceramic prepreg, wherein the raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 90.60-97.55 parts of ultrahigh-temperature ceramic powder, 1.45-6.25 parts of organic resin and 0.75-3.25 parts of carbon black.
2. The method for preparing ultrahigh-temperature ceramic prepreg according to claim 1,
the mass ratio of the organic resin to the carbon black is 8-12: 5.
3. The method for preparing the ultrahigh-temperature ceramic prepreg according to claim 1 or 2, wherein the ultrahigh-temperature ceramic powder is at least one of boron carbide, hafnium carbide, titanium carbide, zirconium boride and hafnium boride; the particle size of the ultrahigh-temperature ceramic powder is 1-10 mu m;
the organic resin is at least one of phenolic resin, epoxy resin and benzoxazine resin.
4. The method for preparing the ultrahigh-temperature ceramic prepreg according to claim 1 or 2, wherein the raw material of the ultrahigh-temperature ceramic prepreg further comprises: the carbon black composite material comprises a pore-forming agent, a dispersant I and a dispersant II, wherein the dosage of the pore-forming agent is 0-20% of the mass of the organic resin, the dosage of the dispersant I is 0-2% of the mass of the ultrahigh-temperature ceramic powder, and the dosage of the dispersant II is 6-12% of the mass of the carbon black.
5. The method for preparing ultra-high temperature ceramic prepreg according to claim 4,
the pore-forming agent is at least one of methyl cellulose, melamine, potassium chloride and potassium acetate;
the dispersant I is at least one of triethyl phosphate, polyvinyl alcohol, polyethyleneimine, tetramethylammonium hydroxide, ammonium polymethacrylate and gum arabic;
the dispersant II is at least one of polyvinylpyrrolidone, hydroxymethyl cellulose and polyvinyl alcohol.
6. The method for preparing ultrahigh-temperature ceramic prepreg according to claim 1,
the volume ratio of the raw materials of the ultrahigh-temperature ceramic prepreg to the solvent is 1: 1.5-2.5;
the solvent is ethanol or acetone;
the ball milling mixing comprises the following steps: adopting zirconia grinding balls, and mixing for 24-48h in a resin tank at the rotating speed of 400-800 r/min;
the drying is pressure spray drying or centrifugal spray drying, and the air inlet temperature is 110-130 ℃;
the mesh number of the sieve is 10-300 meshes.
7. The method for preparing ultrahigh-temperature ceramic prepreg according to claim 1,
the raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: ZrB290.60-93.95 parts of powder, 3.75-6.65 parts of organic resin and 1.85-3.45 parts of carbon black; or
The raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 92.25-96.50 parts of ZrC powder, 2.05-5.25 parts of organic resin and 1.25-2.55 parts of carbon black; or
The raw materials of the ultrahigh-temperature ceramic prepreg comprise the following components in parts by mass: 95.75-97.55 parts of HfC powder, 1.55-3.0 parts of organic resin and 0.75-1.50 parts of carbon black.
8. An ultrahigh-temperature ceramic prepreg, characterized in that the ultrahigh-temperature ceramic prepreg is prepared by the preparation method according to any one of claims 1 to 7.
9. A preparation method of the ultrahigh-temperature ceramic is characterized by comprising the following steps:
molding the ultrahigh-temperature ceramic prepreg to obtain an ultrahigh-temperature ceramic biscuit;
carbonizing the ultrahigh-temperature ceramic biscuit to obtain an ultrahigh-temperature ceramic carbon-containing preform;
and carrying out liquid-phase silicon infiltration on the ultrahigh-temperature ceramic carbon-containing preform by adopting a silicon powder or silicon alloy powder embedding method to obtain the ultrahigh-temperature ceramic.
10. The method for preparing ultra-high temperature ceramic according to claim 9,
the molding is compression molding, isostatic pressing or injection molding; wherein the content of the first and second substances,
the pressure for compression molding is 100-300MPa, and the temperature is 80-150 ℃;
the pressure of the isostatic compaction is 100-300MPa, and the temperature is 80-150 ℃;
the pressure of the injection molding is 40-100MPa, and the temperature is 100-150 ℃;
the carbonization conditions are as follows: under the pressure of 20-80MPa, firstly heating to 180 ℃ with the heating rate of 2-10 ℃/min, preserving heat for 1-3h, then heating to 400 ℃ with the heating rate of 300-1 ℃/min, preserving heat for 2-4h, then heating to 550 ℃ with the heating rate of 0.5-1 ℃/min, preserving heat for 2-4h, and carrying out low-temperature cracking; then heating to 800-;
the liquid phase silicon infiltration comprises: silicon powder or silicon alloy powder is used for embedding the ultrahigh-temperature ceramic carbon-containing preform, and the temperature is kept for 15-60min at 1300-1800 ℃.
11. The method for preparing ultra-high temperature ceramic according to claim 9,
the bending strength of the ultrahigh-temperature ceramic carbon-containing preform is 50-70 MPa.
12. An ultra-high temperature ceramic is characterized in that the porosity of the ultra-high temperature ceramic is less than 0.5%; the silicon carbide content of the ultrahigh-temperature ceramic is 10-25 vol.%; the bending strength of the ultrahigh-temperature ceramic is 350-410 MPa.
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