CN112409012A - Blocky titanium carbide-silicon carbide composite aerogel material and preparation method thereof - Google Patents
Blocky titanium carbide-silicon carbide composite aerogel material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a massive silicon carbide-titanium carbide composite aerogel material and a preparation method thereof. The shape of the material is a gray black block, and the components of the material are titanium carbide and silicon carbide. Respectively adding acid catalyst to prepare wet gel by a one-step sol-gel process, and performing solvent replacement and supercritical drying on the wet gel to obtain RF/SiO2/TiO2And (3) preparing the blocky TiC/SiC composite porous aerogel material by controlling high-temperature carbothermic reduction and calcination decarburizing in an inert atmosphere by using the composite aerogel precursor. The invention achieves the light requirement by introducing a porous structure, greatly reduces the operation temperature, can be prepared into a block material, and has wider application range. By sol-gel process, reaction particle sizeThe method has the advantages that the method is smaller, the contact area among particles is large, materials can be uniformly mixed in subsequent heat treatment, the reaction is more thorough, carbon generated by pyrolysis and self-generation of organic aerogel (RF aerogel) is used for carrying out carbothermic reduction reaction, a carbon reducing agent is not required to be additionally added, and the operability and controllability of the process are realized on a molecular level.
Description
Technical Field
The invention belongs to the field of preparation processes of bulk carbide porous materials, and particularly relates to a bulk silicon carbide-titanium carbide composite aerogel material and a preparation method thereof.
Background
In recent research, TiC and SiC are compounded to prepare complex phase ceramics, which has been controversial reported. The titanium carbide (TiC) ceramic has high strength, high hardness (25-30 Gpa), high temperature resistance (3260 ℃), corrosion resistance and excellent electric and heat conducting properties, and the silicon carbide (SiC) ceramic has extremely high hardness and wear resistance and excellent high-temperature oxidation resistance. The composite material and the TiC are compounded, so that the advantages of high hardness and high-temperature stability of the composite material can be exerted, the high-temperature oxidation resistance of the composite material is improved by utilizing the strong oxidation resistance of the SiC, and the matrix material is reinforced and toughened through the high fracture toughness of the TiC.
At present, hot-pressing sintering (HP), Spark Plasma Sintering (SPS), self-propagating high-temperature synthesis (SHS), pressureless sintering and the like are adopted in more modes for preparing TiC/SiC composite materials, the reaction conditions of SHS are harsh and difficult to control, the SPS reaction temperature is high, the sintering process is high in speed and short in heat preservation time, most of prepared materials are small sheets with the diameter of 20mm, the yield is low, engineering application is difficult to realize, in addition, most of the preparation methods need to apply high pressure and high temperature of 1800-2300 ℃, uniform mixing of the materials is difficult to ensure in the ball milling process, impurities are easy to introduce, and nano powder with uniform size distribution cannot be prepared.
The aerogel is a nano-porous material formed by mutually aggregating nano-particles, has excellent properties such as high specific surface area, low density, high porosity, low thermal conductivity, low refractive index and the like, and a Sol-Gel (Sol-Gel) process is a key for preparing the aerogel. The sol-gel method can ensure the uniform mixing of the precursors, realize the reaction at the molecular level in a short time, and obtain the nano-particle porous composite material with narrow size distribution under the normal pressure condition and relatively low heat treatment temperature.
With the development of science and technology, people put forward new requirements on thinness, lightness and strength of materials, and the porous structure is characterized by lightness. The application of the catalyst in the electrochemical field as a catalytic electrode is further expanded by introducing the nano-porous aerogel and combining the high conductivity of a TiC material. In addition, the porous structure can improve the wave-absorbing performance of the material, and can further expand the application of the material in wave-absorbing stealth materials by combining with the resistance type loss of TiC materials and the dielectric loss mechanism of SiC materials.
The preparation of TiC/SiC composite materials by a sol-gel method has been reported a lot, but the obtained TiC/SiC composite materials are compact, a carbide skeleton needs to be prepared in advance and subjected to multiple times of vacuum impregnation, and a TiC/SiC composite material with nano-pores needs to be developed due to the advantages of high specific surface area, light weight and the like of the nano-porous materials.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a massive silicon carbide-titanium carbide composite aerogel material, and the invention also aims to provide a preparation method of the material, and firstly proposes to adopt an autogenous carbon source and SiO2，TiO2The method for one-step co-reduction of the composite sol has more convenient and faster operation, realizes uniform mixing of molecular weight by a sol-gel method, supercritical drying and subsequent heat treatment, and prepares the TiC/SiC nano-grain size porous composite aerogel material at a lower heat treatment temperature.
The technical scheme of the invention is as follows: the blocky titanium carbide-silicon carbide composite aerogel material is characterized by being a gray black blocky body, comprising titanium carbide and silicon carbide and having the apparent density of 0.0700-0.100 g/cm3The pore diameter is distributed in the range of 1-180 nm, and the specific surface area is 210-380 m2/g。
Preferably, the mass percent of the titanium carbide in the massive titanium carbide-silicon carbide composite aerogel material is 43-46.5%, and the mass percent of the silicon carbide is 31-37.5%.
The invention also provides a method for preparing the massive titanium carbide-silicon carbide composite aerogel material, which comprises the following specific steps:
(1) tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: the molar ratio of the acid is 1 (0.6-2) to 2.6-8 to 5.7-17 to 0.75-2.2, and the mixture is uniformly mixed by a one-pot method to prepare the benzenediol-formaldehyde-silicon oxide RF/SiO2Sol;
(2) taking the molar weight of tetraethyl orthosilicate in the step (1) as a reference, firstly mixing 9-27 molar parts of ethanol, 2.6-8 molar parts of deionized water and 0.2-0.6 molar part of nitric acid to prepare a solution 1, mixing 0.6-1.8 molar parts of a titanium source and 9-27 molar parts of ethanol to prepare a solution 2;
(3) titanium source according to molar ratio: mixing (0.6-1.8): (0.2-0.6) nitric acid solution 1 and solution 2 obtained in step (2) to obtain TiO2Sol;
(4) tetraethyl orthosilicate according to molar ratio: a titanium source is 1 (0.6-1.8), and RF/SiO in the step (1) is used2Sol and TiO in step (3)2Mixing the sol uniformly to obtain RF/SiO2/TiO2Sol;
(5)RF/SiO2/TiO2reacting the sol at 50-70 ℃ for a period of time to obtain RF/SiO2/TiO2Wet gel;
(6) subjecting the wet gel of step (5) to solvent displacement and CO2Supercritical drying to obtain bulk RF/SiO2/TiO2Compounding aerogel;
(7) the RF/SiO obtained in the step (6) is treated2/TiO2Heating the composite aerogel to 1450-1600 ℃ at a heating rate of 2-5 ℃/min in an inert atmosphere, and preserving heat for 5-10 hours to obtain blocky C/TiC/SiC;
(8) and (4) calcining the C/TiC/SiC composite aerogel obtained in the step (7) to remove carbon to obtain corresponding blocky TiC/SiC.
Preferably, the acid in step (1) is hydrochloric acid or glacial acetic acid.
Preferably, the titanium source in step (2) is tetrabutyl titanate or tetraethyl titanate.
Preferably, the sol-gel reaction time in the step (5) is 4 to 8 hours.
Preferably, the wet gel solvent displacement conditions in step (6) are: the solvent is ethanol, and the replacement is carried out for 3 to 5 days at the temperature of 50 to 70 ℃ and once every 10 to 12 hours.
Preferably, the inert atmosphere in step (7) is argon. Has the advantages that:
the method and the TiC/SiC composite aerogel material prepared by the method have the following characteristics:
(1) a precursor of the TiC/SiC composite aerogel material is prepared by adopting a new method (a sol-gel method). The method adopts an acid-catalyzed one-step sol-gel method, is simple and convenient to operate compared with other aerogel preparation methods, reduces the operation steps in experiments, carries out carbothermic reduction reaction on carbon generated by pyrolysis of organic aerogel (RF aerogel), does not need to additionally add a carbon reducing agent, simplifies the process, ensures uniform mixing of precursors, reduces the production cost, and increases the operability and controllability of the process.
(2) High-temperature resistance is good. Because elements such as oxygen, hydrogen and the like in the aerogel are removed in the heat treatment process, the carbothermic reduction reaction is carried out at high temperature to generate more stable block aerogel material,
(3) high strength and high-temp antioxidizing power. The composite material has the advantages of TiC and SiC, such as high melting point, high hardness, wear resistance, corrosion resistance, oxidation resistance and good chemical stability, and the composite material can exert the advantages of high hardness and high-temperature stability, improve the high-temperature oxidation resistance of the composite material by utilizing the excellent oxidation resistance of SiC and reinforce and toughen the matrix material by utilizing the high fracture toughness of TiC. .
(5) The application range is wide. The blocky TiC/SiC aerogel material prepared by the method has wider application range, and can be used in the fields of rocket nozzle throat linings, high-speed cutting tools, jet engine parts, hypersonic aircrafts, high-temperature catalysis, high-temperature electronic materials, battery catalysis electrodes, battery electrodes, anti-radiation electronic materials, high-frequency high-power devices, wave-absorbing stealth materials and the like.
Drawings
FIG. 1 is a graph showing the nitrogen adsorption/desorption specific surface area of TiC/SiC prepared in example 2;
FIG. 2 is a photograph of a real object of the C/TiC/SiC composite ceramic aerogel obtained in example 3;
FIG. 3 is an XRD characterization of the TiC/SiC composite ceramic aerogel prepared in example 3;
FIG. 4 is the RF/SiO solid prepared in example 52/TiO2SEM photograph of (a).
Detailed Description
Example 1
Tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: preparation of benzenediol-formaldehyde-silicon oxide (RF/SiO) from hydrochloric acid at a molar ratio of 1:0.6:2.6:5.7:0.752) The sol is prepared by mixing 9 parts of ethanol, 2.6 parts of deionized water and 0.2 part of nitric acid to prepare a solution 1, mixing 0.6 part of tetrabutyl titanate and 9 parts of ethanol to prepare a solution 2 according to the molar ratio of tetrabutyl titanate: nitric acid 0.6:0.2, and mixing solution 1 and solution 2 to obtain TiO2Sol, tetraethyl orthosilicate in molar ratio: tetrabutyl titanate 1:0.6, RF/SiO2Sols and TiO2The sol is magnetically stirred and uniformly mixed to obtain RF/SiO2/TiO2Sol, sealing the obtained RF/SiO2/TiO2The sol is put in an oven to react for 6 hours at 50 ℃ to obtain RF/SiO2/TiO2Wet gel, performing ethanol solvent replacement in oven at 60 deg.C for 3 days, and performing CO solvent replacement once every 10 hr2Supercritical drying for 12 hours to obtain bulk RF/SiO2/TiO2And (3) compounding the aerogel. Mixing RF/SiO2/TiO2The composite aerogel is placed in a tube furnace in N2Heating to 1450 ℃ at the heating rate of 2 ℃/min in the atmosphere, preserving the heat for 5 hours, then cooling to room temperature to obtain a blocky C/TiC/SiC aerogel material, and calcining the obtained C/TiC/SiC composite aerogel to remove carbon to obtain the blocky TiC/SiC composite aerogel. The apparent density is 0.0778g/cm3The pore diameter is distributed in the range of 1-180 nm, and the specific surface area is 293m2The result of quantitative analysis according to XRD characterization shows that the content of SiC is 34.7 wt% and the content of TiC is 45.6 wt%.
Example 2
Tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: preparation of benzenediol-formaldehyde-silicon oxide (RF/SiO) by hydrochloric acid according to a molar ratio of 1:1.2:5.2:11.4:1.52) The sol is prepared by mixing 18 parts of ethanol, 5.2 parts of deionized water and 0.4 part of nitric acid to prepare a solution 1, mixing 1.2 parts of tetrabutyl titanate and 18 parts of ethanol to prepare a solution 2 according to the molar ratio of tetrabutyl titanate: nitric acid 1.2:0.4, solution 1 and solution 2 were mixed to give TiO2Sol, tetraethyl orthosilicate in molar ratio: tetrabutyl titanate 1:1.2, RF/SiO2Sols and TiO2The sol is magnetically stirred and uniformly mixed to obtain RF/SiO2/TiO2Sol, sealing to obtain RF/SiO2/TiO2The sol is put in an oven to react for 5 hours at 60 ℃ to obtain RF/SiO2/TiO2Wet gel, performing ethanol solvent replacement in 50 deg.C oven once every 11 hr, performing ethanol solvent replacement for 4 days, and performing CO extraction2Supercritical drying for 12 hours to obtain bulk RF/SiO2/TiO2Composite aerogel of RF/SiO2/TiO2The composite aerogel is placed in a tube furnace in N2Heating to 1500 ℃ at the heating rate of 3 ℃/min in the atmosphere, preserving heat for 6 hours, then cooling to room temperature to obtain a blocky C/TiC/SiC aerogel material, and calcining the obtained C/TiC/SiC composite aerogel to remove carbon to obtain the blocky TiC/SiC composite aerogel. The apparent density is 0.0743g/cm3The pore diameter is distributed in the range of 1-170 nm, and the specific surface area is 317m2The result of quantitative analysis according to XRD characterization shows that the content of SiC is 35.4 wt% and the content of TiC is 46.3 wt%. .
Referring to the attached drawings, fig. 1 shows an isothermal curve and a pore diameter distribution curve of nitrogen adsorption and desorption of a TiC/SiC composite aerogel material prepared in example 2 of the invention, wherein a BET test instrument is a Kangta IQ, and according to a full pore test result, an adsorption and desorption isotherm of the material is an H3 hysteresis loop, and the material has graded micro-meso-macropores, wherein the pore diameter is mainly distributed at 60nm, and is a typical macroporous material.
Example 3
Tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: preparation of benzenediol-formaldehyde-silicon oxide (RF/SiO) by hydrochloric acid according to a molar ratio of 1:1:5:12:1.52) Sol; taking the molar weight of tetraethyl orthosilicate as a reference, firstly mixing 15 parts of ethanol, 5 parts of deionized water and 0.4 part of nitric acid to prepare a solution 1, mixing 1.5 parts of tetrabutyl titanate and 15 parts of ethanol to prepare a solution 2, wherein the molar ratio of tetrabutyl titanate: nitric acid 1.5:0.4, solution 1 and solution 2 were mixed to give TiO2Sol, tetraethyl orthosilicate in molar ratio: tetrabutyl titanate 1:1.5, RF/SiO2Sols and TiO2The sol is magnetically stirred and uniformly mixed to obtain RF/SiO2/TiO2Sol, sealing the obtained RF/SiO2/TiO2The sol is put into an oven to react for 4 hours at 70 ℃ to obtain RF/SiO2/TiO2Wet gel, performing ethanol solvent replacement in 70 deg.C oven once every 12 hr, performing ethanol solvent replacement for 3 days, and performing CO extraction2Supercritical drying for 12 hours to obtain bulk RF/SiO2/TiO2Composite aerogel of RF/SiO2/TiO2The composite aerogel is placed in a tube furnace in N2Heating to 1500 ℃ at the heating rate of 4 ℃/min in the atmosphere, preserving the heat for 7 hours, then cooling to room temperature to obtain a blocky C/TiC/SiC aerogel material, and calcining the obtained C/TiC/SiC composite aerogel to remove carbon to obtain the blocky TiC/SiC composite aerogel. The apparent density is 0.0912g/cm3The pore diameter is distributed in the range of 1-180 nm, and the specific surface area is 316m2The result of quantitative analysis according to XRD characterization shows that the content of SiC is 36.7 wt% and the content of TiC is 44.3 wt%. .
Referring to the attached drawings, fig. 2 and fig. 3 respectively show a physical photograph of the C/TiC/SiC composite aerogel material prepared in example 3 of the present invention and XRD characterization of TiC/SiC after decarburizing, and the prepared C/TiC/SiC composite aerogel has good blocking performance, gray black color and metallic luster on the surface. The XRD test adopts a combined multifunctional X-ray diffractometer Ultima IV and CuKa diffraction, wherein lambda is 0.15406nm, the scanning rate is 10(°)/min, and the range is 10-80 DEGBy searching PDF library card, the obtained XRD characteristic peak shows that: at 1500 ℃, in Ar atmosphere, after 7 hours of heat preservation time, the resorcinol-formaldehyde (RF) aerogel is completely pyrolyzed into carbon which is respectively mixed with TiO2、SiO2The carbothermic reduction reaction is carried out to generate TiC and SiC, the characteristic peak is obvious, and the crystallization is good.
Example 4
Tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: preparation of benzenediol-formaldehyde-silicon oxide (RF/SiO) from glacial acetic acid according to a molar ratio of 1:1.5:6:15:22) Sol; taking the molar weight of tetraethyl orthosilicate as a reference, firstly mixing 20 parts of ethanol, 6 parts of deionized water and 0.6 part of nitric acid to prepare a solution 1, mixing 1.2 parts of tetraethyl titanate and 20 parts of ethanol to prepare a solution 2, wherein the molar ratio of tetraethyl titanate: nitric acid 1.2:0.6, solution 1 and solution 2 were mixed to give TiO2Sol, tetraethyl orthosilicate in molar ratio: tetraethyl titanate 1:1.2, RF/SiO2Sols and TiO2The sol is magnetically stirred and uniformly mixed to obtain RF/SiO2/TiO2Sol, sealing and then mixing RF/SiO2/TiO2The sol is put into an oven to react for 8 hours at 60 ℃ to obtain RF/SiO2/TiO2Wet gel, performing ethanol solvent replacement in oven at 60 deg.C once every 10 hr, performing ethanol solvent replacement for 5 days, and performing CO extraction2Supercritical drying for 12 hours to obtain bulk RF/SiO2/TiO2Composite aerogel of RF/SiO2/TiO2The composite aerogel is placed in a tube furnace in N2Heating to 1600 ℃ at the heating rate of 5 ℃/min in the atmosphere, preserving heat for 8 hours, then cooling to room temperature to obtain a blocky C/TiC/SiC aerogel material, and calcining the obtained C/TiC/SiC composite aerogel to remove carbon to obtain the blocky TiC/SiC composite aerogel. The apparent density is 0.100g/cm3The pore diameter is distributed in the range of 1-130 nm, and the specific surface area is 346m2The result of quantitative analysis according to XRD characterization shows that the content of SiC is 35.8 wt% and the content of TiC is 43.1 wt%. .
Example 5
Tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: preparing benzenediol-formaldehyde-oxygen from glacial acetic acid according to a molar ratio of 1:2:7:16:2Silicon (RF/SiO)2) Sol; taking the molar weight of tetraethyl orthosilicate as a reference, firstly mixing 25 parts of ethanol, 6 parts of deionized water and 0.5 part of nitric acid to prepare a solution 1, mixing 1.8 parts of tetraethyl titanate and 25 parts of ethanol to prepare a solution 2, wherein the molar ratio of tetraethyl titanate: nitric acid 1.8:0.5, solution 1 and solution 2 were mixed to give TiO2Sol, tetraethyl orthosilicate in molar ratio: tetraethyl titanate 1:1.8, RF/SiO2Sols and TiO2The sol is magnetically stirred and uniformly mixed to obtain RF/SiO2/TiO2Sol, sealing and then mixing RF/SiO2/TiO2The sol is put into an oven to react for 8 hours at 50 ℃ to obtain RF/SiO2/TiO2Wet gel; the obtained wet gel is subjected to ethanol solvent replacement in an oven at 50 ℃, the replacement is carried out once every 11 hours, and after the ethanol solvent replacement is carried out for 5 days, CO is used2Supercritical drying for 12 hours to obtain bulk RF/SiO2/TiO2Composite aerogel of RF/SiO2/TiO2The composite aerogel is placed in a tube furnace in N2Heating to 1500 ℃ at the heating rate of 2 ℃/min in the atmosphere, preserving the heat for 8 hours, then cooling to room temperature to obtain a blocky C/TiC/SiC aerogel material, and calcining the obtained C/TiC/SiC composite aerogel to remove carbon to obtain the blocky TiC/SiC composite aerogel. The apparent density was 0.897g/cm3The pore diameter is distributed in 1-120 nm, and the specific surface area is 380m2The result of quantitative analysis according to XRD characterization shows that the content of SiC is 31.3 wt% and the content of TiC is 46.1 wt%. .
Referring to the drawings, FIG. 4 shows RF/SiO solid films prepared in accordance with example 5 of the present invention2/TiO2SEM photograph of composite aerogel material, and prepared RF/SiO2/TiO2The composite aerogel has no cracks on the surface, good blocking performance and gray-brown color. SEM test Using a field emission scanning electron microscope, LEO-1530VP from Cal Zeiss, Germany. As can be seen from SEM pictures, the precursor RF/SiO prepared by the invention2/TiO2The nano-porous structure has a nano-scale particle size and a nano-scale pore size.
Example 6
Tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: glacial acetic acid massagePreparation of benzenediol-formaldehyde-silica (RF/SiO) at a molar ratio of 1:2:8:7:2.22) Taking the molar weight of tetraethyl orthosilicate as a reference, firstly mixing 27 parts of ethanol, 8 parts of deionized water and 0.6 part of nitric acid to prepare a solution 1, mixing 1.8 parts of tetrabutyl titanate and 27 parts of ethanol to prepare a solution 2, and mixing the molar weight of tetrabutyl titanate: nitric acid 1.8:0.6, and mixing solution 1 and solution 2 to obtain TiO2Sol, tetraethyl orthosilicate in molar ratio: tetrabutyl titanate 1:1.8, RF/SiO2Sols and TiO2The sol is magnetically stirred and uniformly mixed to obtain RF/SiO2/TiO2Sealing the sol, and placing the sol in an oven RF/SiO2/TiO2The sol reacts for 8 hours at 60 ℃ to obtain RF/SiO2/TiO2Wet gel, performing ethanol solvent replacement in 70 deg.C oven once every 12 hr, performing ethanol solvent replacement for 3 days, and performing CO extraction2Supercritical drying for 12 hours to obtain bulk RF/SiO2/TiO2Composite aerogel of RF/SiO2/TiO2The composite aerogel is placed in a tube furnace in N2Heating to 1600 ℃ at the heating rate of 5 ℃/min in the atmosphere, preserving the heat for 10 hours, then cooling to room temperature to obtain a blocky C/TiC/SiC aerogel material, and calcining the obtained C/TiC/SiC composite aerogel to remove carbon to obtain the blocky TiC/SiC composite aerogel. The apparent density is 0.0812g/cm3The pore diameter is distributed in the range of 1-100 nm, and the specific surface area is 210m2The result of quantitative analysis according to XRD characterization shows that the content of SiC is 37.5 wt% and the content of TiC is 46.4 wt%.
Claims (8)
1. The blocky titanium carbide-silicon carbide composite aerogel material is characterized by being a gray black blocky body, comprising titanium carbide and silicon carbide and having the apparent density of 0.0700-0.100 g/cm3The pore diameter is distributed in the range of 1-180 nm, and the specific surface area is 210-380 m2/g。
2. The bulk titanium carbide-silicon carbide composite aerogel material according to claim 1, wherein the mass percentage of titanium carbide in the bulk titanium carbide-silicon carbide composite aerogel material is 43-46.5%, and the mass percentage of silicon carbide in the bulk titanium carbide-silicon carbide composite aerogel material is 31-37.5%.
3. A method for preparing the bulk titanium carbide-silicon carbide composite aerogel material according to claim 1, comprising the following specific steps:
(1) tetraethyl orthosilicate: resorcinol: formaldehyde: ethanol: the molar ratio of the acid is 1 (0.6-2) to 2.6-8 to 5.7-17 to 0.75-2.2, and the mixture is uniformly mixed by a one-pot method to prepare the benzenediol-formaldehyde-silicon oxide RF/SiO2Sol;
(2) taking the molar weight of tetraethyl orthosilicate in the step (1) as a reference, firstly mixing 9-27 molar parts of ethanol, 2.6-8 molar parts of deionized water and 0.2-0.6 molar part of nitric acid to prepare a solution 1, mixing 0.6-1.8 molar parts of a titanium source and 9-27 molar parts of ethanol to prepare a solution 2;
(3) titanium source according to molar ratio: mixing (0.6-1.8): (0.2-0.6) nitric acid solution 1 and solution 2 obtained in step (2) to obtain TiO2Sol;
(4) tetraethyl orthosilicate according to molar ratio: a titanium source is 1 (0.6-1.8), and RF/SiO in the step (1) is used2Sol and TiO in step (3)2Mixing the sol uniformly to obtain RF/SiO2/TiO2Sol;
(5)RF/SiO2/TiO2reacting the sol at 50-70 ℃ for a period of time to obtain RF/SiO2/TiO2Wet gel;
(6) subjecting the wet gel of step (5) to solvent displacement and CO2Supercritical drying to obtain bulk RF/SiO2/TiO2Compounding aerogel;
(7) the RF/SiO obtained in the step (6) is treated2/TiO2Heating the composite aerogel to 1450-1600 ℃ at a heating rate of 2-5 ℃/min in an inert atmosphere, and preserving heat for 5-10 hours to obtain blocky C/TiC/SiC;
(8) and (4) calcining the C/TiC/SiC composite aerogel obtained in the step (7) to remove carbon to obtain corresponding blocky TiC/SiC.
4. The method according to claim 3, wherein the acid in the step (1) is hydrochloric acid or glacial acetic acid.
5. The method according to claim 3, wherein the titanium source in the step (2) is tetrabutyl titanate or tetraethyl titanate.
6. The method according to claim 3, wherein the sol-gel reaction time in the step (5) is 4 to 8 hours.
7. The method according to claim 3, wherein the wet gel solvent replacement conditions in the step (6) are: the solvent is ethanol, and the replacement is carried out for 3 to 5 days at the temperature of 50 to 70 ℃ and once every 10 to 12 hours.
8. The method according to claim 3, wherein the inert gas atmosphere in the step (7) is argon gas.
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