CN116023150B - High-temperature-resistant transition metal carbide (nitride)/silicon-boron-carbon-nitrogen composite ceramic aerogel and preparation method thereof - Google Patents
High-temperature-resistant transition metal carbide (nitride)/silicon-boron-carbon-nitrogen composite ceramic aerogel and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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Abstract
The invention relates to a high-temperature-resistant transition metal carbide (nitride)/silicon-boron-carbon-nitrogen composite ceramic aerogel and a preparation method thereof. Adding polyborosilazane, divinylbenzene and transition metal complex into an organic solvent, uniformly mixing, and transferring into a hydrothermal kettle for solvothermal reaction, crosslinking and gelation; drying the step wet gel to obtain a transition metal modified PBSZ aerogel; and (3) putting the aerogel into a high-temperature furnace, and pyrolyzing in a protective atmosphere to obtain the transition metal carbide (nitride)/silicon-boron-carbon-nitrogen composite ceramic aerogel. The aerogel has low density of 0.16-0.32g/cm 3 The low thermal conductivity is 0.062-0.082W/m.K, the high compression strength reaches 2.0-6.0MPa, the excellent high temperature tissue structure stability is that the weight loss is not higher than 12wt% after high temperature treatment at 1800 ℃ for 2 hours, and the linear shrinkage is not higher than 7%; meets the requirements of a heat protection system on high-performance heat insulation materials.
Description
Technical Field
The invention relates to the field of aerospace high-temperature heat insulation, in particular to a high-temperature-resistant transition metal carbide (nitride)/silicon-boron-carbon-nitrogen composite ceramic aerogel and a preparation method thereof.
Background
With the continuous improvement of the running speed and the running time of the aircraft, the surface of the aircraft is subjected to severe pneumatic heating, the temperature of parts such as a nose cone and the like can reach more than 1800 ℃, and higher requirements are put on a thermal protection system of the aircraft. Because of the unique nanoscale pore structure, the ceramic aerogel material has low density, high specific surface area and low thermal conductivity, and is an ideal heat insulation material. Currently, research on aerogels has focused mainly on oxide systems (such as silica, alumina, zirconia and composite oxides), however, they are prone to sintering, devitrification or phase transformation when applied at higher ambient temperatures, which results in collapse of their pore structure and rapid degradation of thermal insulation properties. In addition, the weak inter-particle connection of the oxide aerogel results in poor mechanical properties, and these disadvantages all result in difficulty in functioning in the field of high temperature insulation. Compared to oxide aerogels, non-oxide aerogel materials are more excellent in high temperature stability and strength, which is associated with strong covalent or ionic bonding itself, but their preparation process is complex, which often results in materials with structure and properties that are difficult to control accurately, and with higher densities and thermal conductivities (J.Eur.Ceram.Soc.2021, 4,4710;Chem.Mater.2019,31,3700). In general, non-oxide based aerogels have less research, have poor overall properties, and are a long distance from practical applications. Therefore, the development of a novel high-temperature-resistant aerogel material easy to prepare has great significance for heat insulation application in high-temperature environment.
The precursor converted ceramics (PDCs) is an amorphous ceramic material obtained by utilizing pyrolysis of a polymer precursor at high temperature to generate ceramic conversion, has the advantages of convenient component regulation and control, good formability, low density, good high-temperature stability, good oxidation resistance and corrosion resistance and the like, and is widely applied to the preparation of ceramic fibers, films, coatings and ceramic matrix composite materials (J.Am.Ceram.Soc.2010, 93,1805). Aerogel materials such as SiOC, siC, siCN (curr. Opin. Solid State Mater. Sci.2021,25,100936) can be prepared by the PDC route in combination with freeze drying or supercritical drying. Compared with the traditional ceramic aerogel, the method has the advantages of simple preparation flow, controllable components, structure and performance, good mechanical performance and heat insulation performance, excellent high temperature resistance and great application potential in the field of high temperature heat insulation. However, most of the research on PDC aerogel is focused on developing its versatility, such as electromagnetic wave absorption, water treatment, secondary battery energy storage electrode, etc., and the application in the field of high temperature heat insulation is still blank, because the problems of unclear tissue structure evolution mechanism, immature preparation process, deficient research on heat insulation performance and high temperature performance, etc. exist at present.
Among many precursor ceramics, silicon boron carbon nitrogen (SiBCN) ceramics have the most excellent high temperature stability and high temperature oxidation resistance, the crystallization temperature in an inert atmosphere can reach 1800 ℃, the weight loss is hardly caused by heating to 2000 ℃, and the ceramics can be stabilized to 1600 ℃ or above in air, so that the ceramics are in the spotlight of academia and industry (adv. Eng. Mater.2018,20,1800360). The transition metal modification is an effective method for improving the high-temperature stability of SiBCN ceramicsZrO preparation by zirconium butoxide-modified polyborosilazanes, e.g. Liu et al (Ceram. Int.2018,44,22991) 2 SiBCN aerogel still having 100m after pyrolysis at 1550 DEG C 2 High specific surface area per gram. However, the oxide phase formed still undergoes carbothermal reactions at high temperatures, affecting its performance at higher temperatures. Therefore, the transition metal modified SiBCN ceramic precursor is utilized to prepare the transition metal carbonitride/SiBCN composite ceramic aerogel, so that the high-temperature heat insulation requirement below 1800 ℃ can be met, and the method can be applied to the fields of aircraft heat protection systems and the like.
Disclosure of Invention
Aiming at the problems of tissue instability, structural damage and performance deterioration of the prior aerogel material at high temperature, the invention provides a transition metal carbon (nitrogen) compound/silicon boron carbon nitrogen (MC (N)/SiBCN) composite ceramic aerogel and a preparation method thereof. As shown in fig. 1, the aerogel is characterized by microscopically distributing transition metal carbon (nitride) nanocrystals in a silicon-boron-carbon-nitrogen matrix, and is characterized by X-ray diffraction peaks of metal carbon (nitride) crystal phases, for example, as shown in fig. 2, the titanium-carbon-nitrogen/silicon-boron-carbon-nitrogen composite ceramic has diffraction peaks 2θ=36.2 °, 42.0 °, 60.9 °, 73.0 ° of titanium-carbon-nitrogen crystal phases. The structure has excellent high temperature resistance, and is particularly characterized by stable microstructure, structure and heat insulation performance at high temperature. Meanwhile, the aerogel has low density, low thermal conductivity and high compression strength, and meets the requirements of a thermal protection system on high-temperature-resistant, light-weight and high-strength heat insulation materials.
According to the invention, polyborosilazane (PBSZ) is used as a ceramic precursor, a transition metal organic complex is used as a transition metal source, divinylbenzene (DVB) is used as a cross-linking agent, the polyborosilazane and the DVB are dissolved in an organic solvent to form a dilute solution, then solvothermal cross-linking gelation is carried out to form a transition metal modified PBSZ precursor wet gel, and finally MC (N)/SiBCN composite ceramic aerogel is obtained through freeze drying and pyrolysis. All the steps are carried out in an anhydrous and anaerobic environment, and the specific implementation steps are as follows:
1) Preparation of transition metal modified PBSZ precursor wet gel: adding polyborosilazane, divinylbenzene and transition metal complex into an organic solvent, uniformly mixing, and transferring into a hydrothermal kettle for solvothermal reaction, crosslinking and gelation;
2) Drying of transition metal modified PBSZ wet gel: drying the wet gel obtained in the step 1) to obtain a transition metal modified PBSZ aerogel;
3) Pyrolysis of transition metal modified PBSZ aerogel: and (3) putting the aerogel obtained in the step (2) into a high-temperature furnace, and pyrolyzing in a protective atmosphere to obtain the transition metal carbon (nitrogen) compound/silicon boron carbon nitrogen compound ceramic aerogel (MC (N)/SiBCN).
Preferably, the transition metal in step 1) comprises titanium, zirconium, hafnium.
Preferably, the transition metal complex in step 1) is an alkoxide or acetylacetonate of one or more transition metals.
Preferably, the organic solvent in step 1) is cyclohexane, tetrahydrofuran, N-dimethylformamide or acetylacetone.
Preferably, the mass ratio of PBSZ to metal complex in step 1) is 1 (0.5-2).
Preferably, the mass ratio of PBSZ to DVB in step 1) is 1 (0.5-2).
Preferably, the solvothermal temperature in step 1) is 120 to 180 ℃.
Preferably, the drying mode in step 2) is freeze drying or supercritical drying.
Preferably, the pyrolysis temperature in the step 3) is 1000-1500 ℃, and the pyrolysis atmosphere is argon and nitrogen.
The invention provides a preparation method of novel MC (N)/SiBCN composite aerogel, which has simple process flow and easy regulation and control of the composition, structure and performance of the obtained aerogel.
The MC (N)/SiBCN composite aerogel provided by the invention has low density which reaches 0.16-0.32g/cm 3 The low thermal conductivity is 0.062-0.082W/m.K, the high compression strength reaches 2.0-6.0MPa, the excellent high temperature tissue structure stability is that the weight loss is not higher than 12wt% after high temperature treatment at 1800 ℃ for 2 hours, and the linear shrinkage is not higher than 7%; meets the requirements of a heat protection system on high-performance heat insulation materials. Therefore, in the high-speed aircraft heat protection system, nuclear radiation protection and metallurgyThe heat-insulating material has important application prospect in the fields of electric power, high-temperature furnace heat-insulating protection and the like.
According to the invention, the transition metal is utilized to modify the PBSZ precursor, and the transition metal element forms ultrahigh temperature phases such as carbide, nitride, carbonitride and the like in situ after pyrolysis, so that the aerogel shows excellent decomposition resistance, crystallization resistance and sintering resistance at the temperature of up to 1800 ℃, the nano-pore structure of the aerogel can be highly maintained, the stable heat insulation performance is maintained, the defects of structural damage and performance reduction of a common aerogel material at high temperature are fully overcome, and the aerogel has important theoretical significance and application value for developing a high-temperature-resistant heat insulation material.
Drawings
FIG. 1 is a schematic of the microstructure of an MC (N)/SiBCN composite aerogel.
FIG. 2 is an XRD spectrum of TiCN/SiBCN composite ceramic aerogel prepared in example 1.
FIG. 3 is a TEM image of TiCN/SiBCN composite ceramic aerogel prepared in example 1.
FIG. 4 is an SEM image of TiCN/SiBCN composite ceramic aerogel prepared in example 1.
FIG. 5 is an SEM image of the TiCN/SiBCN composite ceramic aerogel prepared in example 1 after heat treatment at 1800℃for 2 hours.
FIG. 6 is an XRD spectrum of the TiN/SiBCN composite ceramic aerogel prepared in example 2.
FIG. 7 is an XRD spectrum of TiCN/SiBCN composite ceramic aerogel prepared in example 3.
FIG. 8 is an XRD spectrum of ZrC/SiBCN composite ceramic aerogel prepared in example 9.
FIG. 9 is an XRD spectrum of the HfC/SiBCN composite ceramic aerogel prepared in example 10.
FIG. 10 is an XRD spectrum of ZrC/HfC/SiBCN composite ceramic aerogel prepared in example 11.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
Example 1
1) Preparation of titanium modified PBSZ precursor wet gel: adding 1.5g of PBSZ, 0.75g of DVB and 0.75g of titanium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 120 ℃ in an oven for 20 hours to obtain a titanium modified PBSZ precursor wet gel;
2) Drying of titanium modified PBSZ wet gel: putting the wet gel obtained in the step 1) into a refrigerator to be frozen for 30min, and then transferring the wet gel into a freeze dryer to be dried for 24h at the temperature of 0 ℃ to obtain the titanium modified PBSZ aerogel;
3) Pyrolysis of titanium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain TiCN/SiBCN composite ceramic aerogel.
Microscopic morphology and phase composition of the aerogel were analyzed using a scanning electron microscope (SEM, s4800, japan), a transmission electron microscope (TEM, JEOL-200CX, japan) and an X-ray diffractometer (XRD, D8 advanced, germany). The density of the aerogel was calculated by volumetric method. The aerogels were tested for compressive strength and thermal conductivity using a universal tester (LD 24.204, china) and a thermal constant analyzer (Hot Disk TPS2500S, sweden). The obtained aerogel was subjected to heat treatment in a high temperature furnace at 1800 ℃ under an argon atmosphere for 2 hours, and its high temperature stability was evaluated by weight loss, linear shrinkage, density and microstructure change after the heat treatment.
As shown in FIG. 2, tiCN/SiBCN composite ceramic aerogel is formed by detecting that TiCN crystals are formed in situ in the SiBCN matrix through XRD. TiCN crystals were observed by TEM to be 10-20 nanometers in size and uniformly distributed in the SiBCN matrix, as shown in FIG. 3. The TiCN/SiBCN composite ceramic aerogel has a beaded three-dimensional nano-pore structure observed by SEM, as shown in figure 4. The aerogel was tested to have a low density of 0.16g/cm 3 The low thermal conductivity is 0.062W/m.K, the high compression strength is 2.0MPa, and the practical application requirements are met. After further heat treatment for 2 hours at 1800 ℃, the TiCN/SiBCN composite ceramic aerogel has the weight loss of only 8.4wt percent, the linear shrinkage rate of only 6.9 percent, and the micro-level structure of the beaded nano-pore is still highly maintained without damage, as shown in figure 5, and has excellent high temperature resistance.
Example 2
1) Preparation of titanium modified PBSZ precursor wet gel: adding 1g of PBSZ, 1g of DVB and 1g of titanium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment in an oven at 120 ℃ for 20 hours to obtain a titanium modified PBSZ precursor wet gel;
2) Drying of titanium modified PBSZ wet gel: putting the wet gel obtained in the step 1) into a refrigerator to be frozen for 30min, and then transferring the wet gel into a freeze dryer to be dried for 24h at the temperature of 0 ℃ to obtain the titanium modified PBSZ aerogel;
3) Pyrolysis of titanium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1200 ℃ in a nitrogen atmosphere to obtain the TiN/SiBCN composite ceramic aerogel.
The formation of TiN crystals in situ in the SiBCN matrix was detected by XRD, as shown in FIG. 6, to form a TiN/SiBCN composite ceramic aerogel. The density of the aerogel was measured by the volumetric method to be 0.30g/cm 3 Meets the actual application requirements.
Example 3
1) Preparation of titanium modified PBSZ precursor wet gel: adding 0.6g of PBSZ, 1.2g of DVB and 1.2g of titanium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 150 ℃ in an oven for 20 hours to obtain a titanium modified PBSZ precursor wet gel;
2) Drying of titanium modified PBSZ wet gel: putting the wet gel obtained in the step 1) into a refrigerator to be frozen for 30min, and then transferring the wet gel into a freeze dryer to be dried for 24h at the temperature of 0 ℃ to obtain the titanium modified PBSZ aerogel;
3) Pyrolysis of titanium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1000 ℃ in an argon atmosphere to obtain TiCN/SiBCN composite ceramic aerogel.
As shown in FIG. 7, tiCN/SiBCN composite ceramic aerogel is formed by detecting that TiCN crystals are formed in situ in the SiBCN matrix through XRD. The aerogel was tested to have a low density of 0.32g/cm 3 Low thermal conductivity 0.082W/m.K, high compression strength of 6.0MPa, and meeting the practical application requirements. After further heat treatment for 2 hours at 1800 ℃, the TiCN/SiBCN composite ceramic aerogel has the weight loss of only 2.2wt% and the linear shrinkage rate of only 2.5 percent, and has excellent high temperature resistance.
Example 4
1) Preparation of zirconium-modified PBSZ precursor wet gel: adding 0.86g of PBSZ, 1.7g of DVB and 0.43g of zirconium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 150 ℃ in an oven for 20 hours to obtain zirconium-modified PBSZ precursor wet gel;
2) Drying of zirconium modified PBSZ wet gel: putting the wet gel obtained in the step 1) into a refrigerator to be frozen for 30min, and then transferring the wet gel into a freeze dryer to be dried for 24h at the temperature of 0 ℃ to obtain zirconium modified PBSZ aerogel;
3) Pyrolysis of zirconium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1500 ℃ in an argon atmosphere to obtain the ZrCN/SiBCN composite ceramic aerogel.
Example 5
1) Preparation of hafnium modified PBSZ precursor wet gel: adding 0.86g of PBSZ, 0.43g of DVB and 1.7g of hafnium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 150 ℃ in an oven for 20 hours to obtain a hafnium modified PBSZ precursor wet gel;
2) Drying of hafnium modified PBSZ wet gel: putting the wet gel obtained in the step 1) into a refrigerator to be frozen for 30min, and then transferring the wet gel into a freeze dryer to be dried for 24h at the temperature of 0 ℃ to obtain hafnium modified PBSZ aerogel;
3) Pyrolysis of hafnium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1500 ℃ in an argon atmosphere to obtain the HfCN/SiBCN composite ceramic aerogel.
Example 6
1) Preparation of titanium-zirconium co-modified PBSZ precursor wet gel: adding 1g of PBSZ, 1g of DVB, 0.5g of titanium butoxide and 0.5g of zirconium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 150 ℃ in an oven for 20 hours to obtain a titanium-zirconium co-modified PBSZ precursor wet gel;
2) Drying of the titanium zirconium co-modified PBSZ wet gel: freezing the wet gel obtained in the step 1) in a refrigerator for 30min, and then transferring the wet gel into a freeze dryer to dry for 24h at 0 ℃ to obtain the titanium-zirconium co-modified PBSZ aerogel;
3) Pyrolysis of titanium zirconium co-modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain the TiN/ZrN/SiBCN composite ceramic aerogel.
Example 7
1) Preparation of titanium zirconium hafnium co-modified PBSZ precursor wet gel: adding 1g of PBSZ, 1g of DVB, 0.33g of titanium butoxide, 0.33g of zirconium butoxide and 0.33g of hafnium butoxide into 17g of cyclohexane under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 150 ℃ in an oven for 20 hours to obtain a titanium-zirconium-hafnium co-modified PBSZ precursor wet gel;
2) Drying of titanium zirconium hafnium co-modified PBSZ wet gel: freezing the wet gel obtained in the step 1) in a refrigerator for 30min, and then transferring the wet gel into a freeze dryer to dry for 24h at 0 ℃ to obtain the titanium-zirconium-hafnium co-modified PBSZ aerogel;
3) Pyrolysis of titanium zirconium hafnium co-modified PBSZ aerogel: and (3) putting the aerogel obtained in the step (2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1500 ℃ in an argon atmosphere to obtain TiCN/ZrCN/HfCN/SiBCN composite ceramic aerogel.
Example 8
1) Preparation of titanium modified PBSZ precursor wet gel: adding 1.5g of PBSZ, 0.75g of DVB and 0.75g of titanium acetylacetonate into 17g of tetrahydrofuran under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 180 ℃ in an oven for 20 hours to obtain a titanium modified PBSZ precursor wet gel;
2) Drying of titanium modified PBSZ wet gel: CO processing the wet gel obtained in the step 1) 2 Supercritical drying to obtain titanium modified PBSZ aerogel;
3) Pyrolysis of titanium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain the TiC/SiBCN composite ceramic aerogel.
Example 9
1) Preparation of zirconium-modified PBSZ precursor wet gel: adding 0.75g of PBSZ, 1.5g of DVB and 0.75g of zirconium acetylacetonate into 17g of acetylacetone under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 180 ℃ in an oven for 20 hours to obtain zirconium-modified PBSZ precursor wet gel;
2) Drying of zirconium modified PBSZ wet gel: CO processing the wet gel obtained in the step 1) 2 Supercritical drying to obtain zirconium modified PBSZ aerogel;
3) Pyrolysis of zirconium modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain the ZrC/SiBCN composite ceramic aerogel.
The ZrC crystals were formed in situ in the SiBCN matrix as detected by XRD, as shown in FIG. 8, to form a ZrC/SiBCN composite ceramic aerogel. The aerogel was tested to have a low density of 0.32g/cm 3 The high compression strength is 4.0MPa, and the practical application requirement is met. After further heat treatment for 2 hours at 1800 ℃, the weight loss of the ZrC/SiBCN composite ceramic aerogel is only 10.3 weight percent, and the high-temperature resistance is excellent.
Example 10
1) Preparation of hafnium modified PBSZ precursor wet gel: adding 1g of PBSZ, 1g of DVB and 1g of hafnium acetylacetonate into 17g of N, N-dimethylformamide under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 180 ℃ in an oven for 20 hours to obtain hafnium modified PBSZ precursor wet gel;
2) Drying of hafnium modified PBSZ wet gel: freezing the wet gel obtained in the step 1) in a refrigerator for 2 hours, and then transferring the wet gel into a freeze dryer to dry the wet gel at the temperature of 50 ℃ below zero for 48 hours to obtain hafnium modified PBSZ aerogel;
3) Pyrolysis of hafnium modified PBSZ aerogel: and 2) placing the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain the HfC/SiBCN composite ceramic aerogel.
The formation of HfC crystals in situ in the SiBCN matrix was detected by XRD, as shown in fig. 9, forming an HfC/SiBCN composite ceramic aerogel. The aerogel was tested to have a low density of 0.23g/cm 3 Meets the actual application requirements. After further heat treatment for 2 hours at 1800 ℃, the weight loss of the HfC/SiBCN composite ceramic aerogel is only 12.0wt%, and the high-temperature resistance is excellent.
Example 11
1) Preparation of zirconium hafnium co-modified PBSZ precursor wet gel: adding 1g of PBSZ, 1g of DVB, 0.5g of zirconium acetylacetonate and 0.5g of hafnium acetylacetonate into 17g of N, N-dimethylformamide under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 180 ℃ in an oven for 20 hours to obtain zirconium-hafnium co-modified PBSZ precursor wet gel;
2) Drying of zirconium hafnium co-modified PBSZ wet gel: freezing the wet gel obtained in the step 1) in a refrigerator for 2 hours, and then transferring the wet gel into a freeze dryer to dry the wet gel at the temperature of 50 ℃ below zero for 48 hours to obtain the zirconium-hafnium co-modified PBSZ aerogel;
3) Pyrolysis of zirconium hafnium co-modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain the ZrC/HfC/SiBCN composite ceramic aerogel.
ZrC, hfC crystals were formed in situ in the SiBCN matrix as detected by XRD, as shown in FIG. 10, to form ZrC/HfC/SiBCN composite ceramic aerogel.
Example 12
1) Preparation of titanium zirconium hafnium co-modified PBSZ precursor wet gel: adding 1g of PBSZ, 1g of DVB, 0.33g of titanium acetylacetonate, 0.33g of zirconium acetylacetonate and 0.33g of hafnium acetylacetonate into 17g of N, N-dimethylformamide under the protection of flowing inert gas, magnetically stirring to obtain a uniform solution, transferring the uniform solution into a hydrothermal kettle, and carrying out solvothermal treatment at 180 ℃ in an oven for 20 hours to obtain a titanium-zirconium-hafnium co-modified PBSZ precursor wet gel;
2) Drying of titanium zirconium hafnium co-modified PBSZ wet gel: freezing the wet gel obtained in the step 1) in a refrigerator for 2 hours, and then transferring the wet gel into a freeze dryer to dry the wet gel at the temperature of 50 ℃ below zero for 48 hours to obtain the titanium zirconium hafnium co-modified PBSZ aerogel;
3) Pyrolysis of titanium zirconium hafnium co-modified PBSZ aerogel: and 2) putting the aerogel obtained in the step 2) into a tube furnace, and pyrolyzing the aerogel for 2 hours at 1400 ℃ in an argon atmosphere to obtain the TiC/ZrC/HfC/SiBCN composite ceramic aerogel.
The invention relates to a high-temperature-resistant MC (N)/SiBCN composite ceramic aerogel and a preparation method thereof. PBSZ is used as a precursor, DVB is used as a cross-linking agent, a transition metal complex is used as a transition metal source, the MC (N)/SiBCN composite ceramic aerogel is obtained through solvothermal cross-linking gelation and drying pyrolysis, and the aerogel has low density, low thermal conductivity and high compression strength. The formation of MC (N) phase significantly improves the high temperature stability of the aerogel, and can maintain the stability of the tissue structure in an environment of up to 1800 ℃ so as to maintain good heat insulation performance. The invention provides a simple preparation method of a novel high-temperature-resistant aerogel material, which improves the upper temperature limit of the aerogel material, and the aerogel can play a role in heat insulation at a higher temperature so as to ensure the normal operation of an aircraft at a higher speed and longer operation time.
The preparation of MC (N)/SiBCN composite ceramic aerogel can be realized by adjusting the technological parameters recorded in the invention, and the performances basically consistent with the examples are shown. The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (6)
1. The preparation method of the high-temperature-resistant transition metal carbo/nitride and silicon-boron-carbon-nitrogen composite ceramic aerogel is characterized by comprising the following steps of:
1) Adding polyborosilazane, divinylbenzene and transition metal complex into an organic solvent, uniformly mixing, and transferring into a hydrothermal kettle for solvothermal reaction, crosslinking and gelation;
2) Drying the wet gel obtained in the step 1) to obtain the transition metal modified polyborosilazane aerogel;
3) Putting the aerogel obtained in the step 2) into a high-temperature furnace, and pyrolyzing in a protective atmosphere to obtain the transition metal carbon/nitride and silicon-boron-carbon-nitrogen composite ceramic aerogel;
the transition metal carbon/nitride nanocrystals are microscopically distributed in the silicon-boron-carbon-nitrogen matrix, and the aerogel is characterized by having an X-ray diffraction peak of a metal carbon/nitride crystal phase, and the titanium-carbon-nitrogen/silicon-boron-carbon-nitrogen composite ceramic has diffraction peaks 2 theta = 36.2 °, 42.0 °, 60.9 °, 73.0 ° of a titanium-carbon-nitrogen crystal phase;
the transition metal in step 1) comprises titanium, zirconium or hafnium; the mass ratio of the polyborosilazane to the metal complex is 1 (0.5-2); the mass ratio of the polyborosilazane to the divinylbenzene is 1 (0.5-2).
2. The method of claim 1, wherein the transition metal complex of step 1) is one or more transition metal alkoxides or acetylacetonates.
3. The method according to claim 1, wherein the organic solvent in step 1) is cyclohexane, tetrahydrofuran, N-dimethylformamide or acetylacetone.
4. The method of claim 1, wherein the solvothermal temperature in step 1) is 120-180 ℃.
5. The method according to claim 1, wherein the drying in step 2) is freeze-drying or supercritical drying.
6. The method of claim 1, wherein the pyrolysis temperature in step 3) is 1000-1500 ℃, and the pyrolysis atmosphere is argon or nitrogen.
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| CN102557637A (en) * | 2011-12-14 | 2012-07-11 | 天津大学 | Silicon boron carbon nitrogen-based composite material and preparation method thereof |
| CN103755348A (en) * | 2013-11-22 | 2014-04-30 | 天津大学 | Silicon boron carbon nitrogen ceramic and preparation method thereof |
| CN110818431A (en) * | 2018-08-14 | 2020-02-21 | 天津城建大学 | Zirconium-containing polyborosilazane precursor aerogel, silicon boron carbon nitrogen/zirconium dioxide ceramic aerogel, and preparation method and application thereof |
| CN114105646A (en) * | 2021-12-20 | 2022-03-01 | 哈尔滨工业大学 | Preparation method of in-situ SiC-BN (C) -Ti (C, N) nanocrystalline complex phase ceramic |
| WO2022174624A1 (en) * | 2021-11-02 | 2022-08-25 | 航天材料及工艺研究所 | High-temperature-resistant and oxidation-resistant light-weight heat-insulation foam material and preparation method therefor |
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| CN102557637A (en) * | 2011-12-14 | 2012-07-11 | 天津大学 | Silicon boron carbon nitrogen-based composite material and preparation method thereof |
| CN103755348A (en) * | 2013-11-22 | 2014-04-30 | 天津大学 | Silicon boron carbon nitrogen ceramic and preparation method thereof |
| CN110818431A (en) * | 2018-08-14 | 2020-02-21 | 天津城建大学 | Zirconium-containing polyborosilazane precursor aerogel, silicon boron carbon nitrogen/zirconium dioxide ceramic aerogel, and preparation method and application thereof |
| WO2022174624A1 (en) * | 2021-11-02 | 2022-08-25 | 航天材料及工艺研究所 | High-temperature-resistant and oxidation-resistant light-weight heat-insulation foam material and preparation method therefor |
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