CN114853470B - Enhanced thermal insulation zirconium dioxide composite ceramic aerogel and preparation method thereof - Google Patents
Enhanced thermal insulation zirconium dioxide composite ceramic aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of ceramic materials, and discloses enhanced thermal insulation dioxideFirstly, zirconium oxychloride octahydrate is used as a raw material, hexadecyl trimethyl ammonium bromide is used as a dispersing agent, propylene oxide is used as a cross-linking agent, and ZrO is prepared by a sol-gel method and supercritical drying 2 A particulate aerogel; then ZrO is reacted 2 Putting the particle aerogel into a mould, introducing a polyborosilazane ceramic precursor or a polycarbosilane ceramic precursor through vacuum impregnation, and obtaining ZrO with a three-dimensional network structure through hydrothermal reaction and supercritical drying 2 A composite aerogel precursor; finally ZrO is reacted 2 Performing pyrolysis on the composite aerogel precursor to form the enhanced heat-insulation ZrO 2 Composite ceramic aerogel. The high-strength heat-insulation zirconium dioxide composite ceramic aerogel obtained by the invention has excellent mechanical properties and good high-temperature heat-insulation properties, and can be used as a high-quality structural material to have important application prospects in the fields of civil use, military use, aerospace and the like.
Description
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to an aerogel material based on composite ceramic and a preparation method thereof.
Technical Field
Aerogel materials have pore sizes smaller than the mean free path of air, limiting gas convection during heat conduction, and thus exhibit extremely low thermal conductivity. ZrO (ZrO) 2 The particulate aerogel has a multi-stage structure, primary particles are connected with each other as small units to form secondary particles, the secondary particles are crosslinked with each other to form dendritic clusters, and pores having a diameter of about 20nm exist among the clusters. At high temperatures, the high specific surface area of the aerogel increases the surface energy, and in order to reach a steady state, necking of primary particles in contact with each other occurs, reducing the surface free energy. This will destroy the nanoporous structure inside the aerogel, clusteringThe phenomenon is more and more obvious, after the heat treatment temperature is higher than 800 ℃, the framework structure collapses, the density is obviously increased, the heat conductivity is also sharply increased, the characteristic that the aerogel has light and porous properties is not possessed at the moment, the heat insulation performance can be considered to be invalid, and the granular aerogel can not be directly applied to the fields of chemical engineering and the like as a structural material.
Disclosure of Invention
Aiming at the technical defects of the existing particle aerogel material in the aspects of high temperature resistance, mechanical property and the like, the invention provides a ZrO enhanced thermal insulation material 2 Composite ceramic aerogel and preparation method thereof, and ZrO prepared from composite ceramic aerogel 2 Taking particle aerogel as a matrix material, taking a ceramic precursor of polyborosilazane or polycarbosilane as an adhesive, and obtaining ZrO through hydrothermal reaction and supercritical drying 2 A composite aerogel precursor; then the ZrO is cracked at high temperature to form enhanced heat insulation ZrO 2 Composite ceramic aerogel; the aerogel material imparts ZrO 2 Good structural mechanics of the particle aerogel and can effectively promote ZrO 2 High temperature stability of the aerogel; the high-temperature heat insulation material has high-temperature stability and excellent mechanical property, and can be directly applied to industrial production as a structural material to realize high-strength heat insulation.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the invention, a preparation method of a zirconium dioxide composite ceramic aerogel with enhanced thermal insulation is provided, which comprises the following steps:
(1) Taking zirconium oxychloride octahydrate as a raw material, hexadecyl trimethyl ammonium bromide as a dispersing agent and propylene oxide as a cross-linking agent, and preparing ZrO by a sol-gel method and supercritical drying 2 A particulate aerogel;
(2) Subjecting the ZrO to 2 Putting the particle aerogel into a mould, introducing a polyborosilazane ceramic precursor or a polycarbosilane ceramic precursor through vacuum impregnation, and obtaining ZrO with a three-dimensional network structure through hydrothermal reaction and supercritical drying 2 A composite aerogel precursor; the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor is used as a bonding phase to bond the ZrO 2 Particulate aerogelsBonding into a block structure;
(3) Subjecting the ZrO to 2 Performing pyrolysis on the composite aerogel precursor to form the enhanced heat-insulation ZrO 2 Composite ceramic aerogel.
Further, the step (1) comprises the following steps: adding zirconyl chloride octahydrate into an ethanol water solution, and stirring at room temperature until the zirconyl chloride octahydrate and the ethanol water solution are uniformly mixed; adding cetyl trimethyl ammonium bromide in the stirring process until the solution becomes clear and transparent, adding epoxypropane, stirring uniformly, pouring into a mould, and standing to obtain wet gel; aging the wet gel in absolute ethyl alcohol, and performing supercritical drying to obtain the ZrO 2 A particulate aerogel.
Further, the zirconium oxychloride octahydrate comprises 6-15 parts by mass, the hexadecyl trimethyl ammonium bromide comprises 0.5-2 parts by mass and the propylene oxide comprises 1-6 parts by mass.
Further, the step (2) comprises the following steps: subjecting the ZrO obtained in step (1) to 2 Mixing the particle aerogel with the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor and a cross-linking agent, fully stirring, pouring into a mould, and vacuum impregnating to ensure that the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor and the ZrO 2 Fully contacting and wetting the particle aerogel, and then carrying out hydrothermal reaction to obtain composite wet gel; after the composite wet gel is aged, the ZrO is obtained by supercritical drying 2 A composite aerogel precursor.
Furthermore, the weight average molecular weight of the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor is 5000-8000g/mol.
Further, the ZrO 2 The mass ratio of the granular aerogel to the ceramic precursor is (1-15): (1-10).
Further, the ZrO 2 The mixing and stirring time of the granular aerogel and the ceramic precursor is 1-3 h.
Further, the hydrothermal reaction is carried out for 1-6h at the temperature of 150-200 ℃.
Further, the pyrolysis temperature in the step (3) is 800-1400 ℃, and the pyrolysis is carried out under the protection of nitrogen.
According to another aspect of the invention, the reinforced thermal insulation zirconium dioxide composite ceramic aerogel is obtained by the preparation method.
The invention has the beneficial effects that:
according to the enhanced thermal insulation zirconium dioxide composite ceramic aerogel and the preparation method thereof, a two-phase ceramic aerogel three-dimensional network structure is constructed, and the technical bottlenecks that the existing particle aerogel is agglomerated at high temperature and the thermal insulation performance is reduced are effectively solved. With ZrO 2 The particle aerogel is used as a matrix material, a ceramic precursor of polyborosilazane or polycarbosilane is introduced as a binding phase through vacuum impregnation, and after supercritical drying and high-temperature cracking, the ceramic precursor is converted into Si-B-C-N or Si-C ceramic aerogel to be bound on ZrO 2 The surface of the particle aerogel forms a three-dimensional structure material with two phases of ceramic aerogel. In the composite ceramic aerogel, the matrix material and the bonding phase have higher compatibility and interface bonding force, and can play a role in stress transfer. Under the condition of cracking, the ceramic precursor is coated on ZrO 2 The network structure of the ceramic aerogel can be regulated and controlled by changing the cracking temperature on the surface of the particle aerogel. After the three-dimensional network structure is constructed, the composite ceramic aerogel has certain strength, and meanwhile, the phase interface can also effectively transfer load, so that the material is endowed with good mechanical properties; meanwhile, the multi-level pore structure of the two-phase aerogel endows the material with good heat insulation performance.
With conventional ZrO 2 Compared with the particle aerogel, the reinforced heat-insulation zirconium dioxide composite ceramic aerogel disclosed by the invention has a macroscopic block structure, can bear 5.32Mpa of compressive strength, and has the heat conductivity as low as 0.0437 W.m -1 K -1 The composite material has excellent mechanical property and good high-temperature heat-insulating property, and has important application prospect in the fields of civil use, military, aerospace and the like.
Drawings
FIG. 1 is a view showing three-dimensional network structure ZrO fabricated in examples 1 to 3 of the present invention 2 Composite aerogel precursor and enhanced thermal insulation ZrO prepared in examples 4-5 2 Compression performance curve of composite ceramic aerogelA drawing;
FIG. 2 is a view showing enhanced thermal insulation ZrO prepared in examples 1 to 3 of the present invention 2 A nitrogen adsorption-desorption and pore size distribution curve chart of the composite ceramic aerogel;
FIG. 3 is a view of the enhanced thermal insulation ZrO prepared in example 4 of the present invention 2 A nitrogen adsorption-desorption and pore size distribution curve chart of the composite ceramic aerogel;
FIG. 4 is a view of the enhanced thermal insulation ZrO prepared in example 5 of the present invention 2 A nitrogen adsorption-desorption and pore size distribution curve chart of the composite ceramic aerogel;
FIG. 5 shows three-dimensional network structure ZrO prepared in examples 1 to 3 of the present invention 2 Composite aerogel precursor and enhanced thermal insulation ZrO prepared in examples 4-5 2 Thermogravimetric curve of the composite ceramic aerogel;
FIG. 6 shows the heat-insulated ZrO prepared in (a) example 6, (b) example 7 and (c) example 4 of the present invention 2 SEM image of composite ceramic aerogel;
FIG. 7 is a preparation mechanism diagram of the invention and the enhanced thermal insulation ZrO prepared in example 5 2 TEM images of composite ceramic aerogels;
FIG. 8 is a graph of enhanced thermal insulation ZrO prepared in example 5 of the present invention 2 Scanning and distributing the element surface of the composite ceramic aerogel; wherein (a) is a general diagram, (b) is a Zr element distribution, (C) is a Si element distribution, and (d) is a C element distribution.
Detailed Description
The invention is described in further detail below by way of specific examples and comparative examples:
example 1
(1) Preparation of ZrO by sol-gel process 2 Particle aerogel: adding 8.9g of zirconyl chloride octahydrate into 100mL of 80% ethanol water solution by mass percent, and stirring for 1h at room temperature until the materials are uniformly mixed; adding 0.712g of hexadecyl trimethyl ammonium bromide in the stirring process until the solution becomes clear and transparent, adding 5.3g of cross-linking agent propylene oxide, uniformly stirring, pouring into a mould, and standing to obtain wet gel; aging the wet gel in absolute ethyl alcohol, and performing supercritical drying to obtain ZrO 2 A particulate aerogel.
(2) Three-dimensional network structure ZrO 2 Preparing a composite aerogel precursor: dissolving 0.76g of polyborosilazane in tetrahydrofuran, stirring for 3 hours to fully dissolve the polyborosilazane, and taking 0.608g of ZrO obtained in step (1) 2 Vacuum-dipping the particle aerogel into polyborosilazane, adding 0.74g of divinylbenzene, stirring for 1h, transferring into a polytetrafluoroethylene lining hydrothermal kettle, vacuumizing for 1h, and heating to 180 ℃ for heat treatment for 6h to obtain composite wet gel; soaking the composite wet gel in an ethanol solution for aging for 2 days, and then performing supercritical drying for 6 hours to obtain ZrO with a three-dimensional network structure 2 A composite aerogel precursor. Wherein the polyborosilazane has a weight average molecular weight of 8000g/mol.
Example 2
Preparation of ZrO of three-dimensional network Structure according to the method of example 1 2 A composite aerogel precursor differing only in the ZrO in step (2) 2 The mass of the particulate aerogel was 0.76g.
Example 3
Preparation of ZrO with three-dimensional network Structure according to the method of example 1 2 A composite aerogel precursor differing only in the ZrO in step (2) 2 The mass of the particulate aerogel was 0.912g.
Example 4
Preparation of ZrO of three-dimensional network Structure according to the method of example 2 2 Compounding the aerogel precursor, and then performing the step (3);
(3) Enhanced thermal insulation ZrO 2 Preparing the composite ceramic aerogel: zrO of the three-dimensional network structure obtained in the step (2) 2 The composite aerogel precursor is subjected to pyrolysis for 1h at 1200 ℃ under the protection of nitrogen to obtain the enhanced heat insulation ZrO 2 Composite ceramic aerogel.
Example 5
(1) Preparation of ZrO by sol-gel process 2 Particle aerogel: adding 6g of zirconyl chloride octahydrate into 100mL of 80% ethanol water solution by mass percent, and stirring for 1h at room temperature until the materials are uniformly mixed; adding 0.5g of hexadecyl trimethyl ammonium bromide in the stirring process until the solution becomes clear and transparent, adding 6g of cross-linking agent propylene oxide, uniformly stirring, pouring into a mould, standingObtaining a wet gel; aging the wet gel in absolute ethyl alcohol, and performing supercritical drying to obtain ZrO 2 A particulate aerogel.
(2) ZrO with three-dimensional network structure 2 Preparing a composite aerogel precursor: dissolving 0.756g of polycarbosilane in 7.558g of tetrahydrofuran, stirring for 1h to fully dissolve the polycarbosilane, and taking 0.756g of ZrO obtained in step 1) 2 Vacuum-dipping the particle aerogel into polycarbosilane, adding 0.65g of divinylbenzene, stirring for 3 hours, transferring into a polytetrafluoroethylene lining hydrothermal kettle, vacuumizing for 1 hour, and then heating to 150 ℃ for heat treatment for 5 hours to obtain composite wet gel; soaking the composite wet gel in an ethanol solution for aging for 2 days, and then performing supercritical drying for 6 hours to obtain ZrO with a three-dimensional network structure 2 A composite aerogel precursor. Wherein the weight average molecular weight of the polycarbosilane is 5000g/mol.
(3) Enhanced thermal insulation ZrO 2 Preparing the composite ceramic aerogel: zrO of the three-dimensional network structure obtained in the step (2) 2 The composite aerogel precursor is subjected to pyrolysis for 1h under the nitrogen protection condition of 1200 ℃ to obtain the enhanced heat insulation ZrO 2 Composite ceramic aerogel.
Example 6
Preparation of ZrO of three-dimensional network Structure according to the method of example 2 2 Compounding the aerogel precursor, and then performing the step (3);
(3) Enhanced thermal insulation ZrO 2 Preparing the composite ceramic aerogel: zrO of the three-dimensional network structure obtained in the step (2) 2 The composite aerogel precursor is subjected to pyrolysis for 1h under the protection of nitrogen at 800 ℃ to obtain the enhanced heat insulation ZrO 2 Composite ceramic aerogel.
Example 7
Preparation of ZrO of three-dimensional network Structure according to the method of example 2 2 Compounding the aerogel precursor, and then performing the step (3);
(3) Enhanced thermal insulation ZrO 2 Preparing the composite ceramic aerogel: zrO of the three-dimensional network structure obtained in the step (2) 2 The composite aerogel precursor is subjected to pyrolysis for 1h under the protection of nitrogen at 1000 ℃ to obtain the enhanced heat insulation ZrO 2 Composite ceramic aerogel.
Example 8
Preparation of ZrO of three-dimensional network Structure according to the method of example 2 2 Compounding the aerogel precursor, and then performing the step (3);
(3) Enhanced thermal insulation ZrO 2 Preparing the composite ceramic aerogel: zrO of the three-dimensional network structure obtained in the step (2) 2 The composite aerogel precursor is subjected to pyrolysis for 1h under the protection of nitrogen at 1400 ℃ to obtain the enhanced heat insulation ZrO 2 Composite ceramic aerogel.
Example 9
(1) Preparation of ZrO by sol-gel Process 2 And (3) particle aerogel: 15g of zirconyl chloride octahydrate is added into 100mL of 80% ethanol water solution by mass, and stirred for 1h at room temperature until the mixture is uniform. Adding 2g of hexadecyl trimethyl ammonium bromide in the stirring process until the solution becomes clear and transparent, adding 1g of cross-linking agent propylene oxide, uniformly stirring, pouring into a mould, and standing to obtain wet gel; aging the wet gel in absolute ethyl alcohol, and performing supercritical drying to obtain ZrO 2 A particulate aerogel.
(2) Three-dimensional network structure ZrO 2 Preparing a composite aerogel precursor: dissolving 0.756g of polycarbosilane in 7.558g of tetrahydrofuran, stirring for 1h to fully dissolve the polycarbosilane, and taking 0.756g of ZrO obtained in step 1) 2 Vacuum-dipping the particle aerogel into polycarbosilane, adding 0.65g of divinylbenzene, stirring for 2 hours, transferring into a polytetrafluoroethylene lining hydrothermal kettle, vacuumizing for 1 hour, and heating to 200 ℃ for heat treatment for 1 hour to obtain composite wet gel; soaking the composite wet gel in an ethanol solution for aging for 2 days, and then performing supercritical drying for 6 hours to obtain ZrO with a three-dimensional network structure 2 A composite aerogel precursor. Wherein the weight average molecular weight of the polycarbosilane is 7000g/mol.
(3) Enhanced thermal insulation ZrO 2 Preparing the composite ceramic aerogel: zrO of the three-dimensional network structure obtained in the step (2) 2 The composite aerogel precursor is subjected to pyrolysis for 1h under the nitrogen protection condition of 1200 ℃ to obtain the enhanced heat insulation ZrO 2 Composite ceramic aerogel.
And (4) performance test results:
the compression strength of the material is measured by a mechanical testing machine (FL 5504),FIG. 1 is a view showing three-dimensional network-structured ZrO fabricated in examples 1 to 3 of the present invention 2 Composite aerogel precursor and enhanced thermal insulation ZrO prepared in examples 4-5 2 Graph of compression performance of composite ceramic aerogel. From the test results, the mechanical properties of the ceramic aerogel are remarkably enhanced compared with the aerogel precursor after pyrolysis. The organic matter is gradually decomposed along with the rise of the temperature, the ceramic material is subjected to ceramic transformation, and the ceramic precursor polymer is gradually transformed from the organic matter to ceramic materials such as SiBCN, siC and the like, so that the internal structure of the aerogel is gradually compact, the porosity is gradually reduced, and the mechanical strength is gradually increased. Example 4 and example 5 separately yield SiBCN/ZrO at a pyrolysis temperature of 1200 ℃ 2 And SiC/ZrO 2 The maximum values of the compressive strength of the composite aerogel are 5.32MPa and 4.71MPa respectively, so that the composite aerogel obtained by using polyborosilazane as a precursor binder has higher mechanical strength.
The ceramic aerogel sample is tested by a Beijing Behcard instruments science and technology limited 3H-2000PS1 type specific surface area and aperture tester. Before testing, the aerogel sample is dried for 3h at 150 ℃ under vacuum condition, so as to remove impurities adsorbed on the sample and water molecules in the air. FIG. 2 shows three-dimensional network structure ZrO prepared in examples 1 to 3 of the present invention 2 The composite aerogel precursor has (a) a nitrogen adsorption-desorption curve and (b) a pore size distribution curve chart. As can be seen from FIG. 2, all the samples had H 3 The IV-type isotherm of the hysteresis loop indicates that the material has a mesoporous structure. Example 2 had the highest specific surface area of 812.646m 2 g -1 The average pore diameter was 17.046nm. Thus, the preceramic binder and ZrO 2 The specific surface area of the particle aerogel is the highest when the mass ratio of the particle aerogel is 1. FIGS. 3 and 4 are the enhanced thermal insulation ZrO produced in examples 4 and 5 of the present invention, respectively 2 The nitrogen adsorption-desorption curve (a) and the pore size distribution curve chart (b) of the composite ceramic aerogel, and as can be seen from fig. 3 and 4, the N of the ceramic composite aerogel obtained after cracking the sample at 1200 ℃ 2 Adsorption/desorption isotherm is still H 3 Type IV isotherms of hysteresis loops, surface samplesThe product still has a mesoporous structure, and table 1 lists BET specific surface area values of examples 1-5, and it can be clearly seen from the results that the specific surface area of the sample after ceramization is reduced significantly, and the density is increased, which indicates that the internal pore structure of the aerogel after ceramization is densified, which is mutually corroborated with mechanical properties.
The samples were subjected to thermal stability analysis using a thermogravimetric analyzer (TG/DTA, Q600) at a ramp rate of 20 ℃/min from room temperature to 1000 ℃ in a nitrogen atmosphere. FIG. 5 is a schematic view of three-dimensional network-structured ZrO fabricated in examples 1 to 3 of the present invention 2 Composite aerogel precursor and enhanced thermal insulation ZrO prepared in examples 4-5 2 The thermogravimetric curves of the composite ceramic aerogels show that for examples 1-3, the samples had a small mass loss at 180 ℃, which is mainly caused by the volatilization of moisture, residual solvent and low molecular weight substances. When the temperature is 180-550 ℃, the precursor organic matter begins to decompose, and the decomposition speed reaches the maximum when the temperature is higher than 550 ℃, which indicates that a large amount of molecular chain breakage and rearrangement occur in the system, the hydrocarbon component is rapidly decomposed, a large amount of micromolecular gas is released, and ceramic transformation occurs. When the temperature is higher than 700 ℃, the pyrolysis speed of the composite aerogel precursor is slowed down, and finally the ceramic composite aerogel is formed. In contrast, the thermogravimetric curve mass loss of examples 4 and 5 is very small, mainly because the two samples have been subjected to thermal cracking treatment to form the ceramic composite aerogel, so that almost no decomposition of organic matters occurs, and further shows that the ceramic composite aerogel obtained by the present invention has good high-temperature thermal stability.
The samples were tested for thermal conductivity using a thermal conductivity tester (TC 3000E, XIA TECH, CHN) with an operating current ranging from 0 to 10mA. The thermal conductivity values for examples 1-3 ranged from 0.0344 to 0.0358W m -1 K -1 Example 4 thermal conductivity 0.0437W m -1 K -1 Example 5 thermal conductivity 0.053W m -1 K -1 The corresponding results are shown in Table 1. It can be seen that the aerogel without pyrolysis has a lower thermal conductivity, while the ceramic aerogel formed after pyrolysis has an increased thermal conductivity, mainly due to the bonding of the aerogel during the ceramization processThe reason for the densification of the structure. But in general, the obtained composite ceramic aerogel still has good heat insulation performance.
TABLE 1
The sample was subjected to morphology analysis by means of an ultra-high resolution thermal field emission scanning electron microscope model SM-7800F, electronic Co., ltd., japanese (Japan) and FIG. 6 shows that the heat-insulating ZrO prepared in example 6 (a), example 7 (b) and example 4 (c) of the present invention 2 SEM image of composite ceramic aerogel. As can be seen from fig. 6, as the cracking temperature is increased, the pore structure of the composite aerogel becomes gradually dense, which indicates that the ceramization transformation is more complete, but the ceramization product is still highly porous, and the composite ceramic aerogel retains the pore structure of the mesoporous material.
The transmission morphology analysis of example 5 is performed by using a Transmission Electron Microscope (TEM) of FEVTECNAIG2F 20 model, fig. 7 is a preparation mechanism diagram of the present invention and a TEM morphology diagram of example 5, and the corresponding surface scanning element distribution diagrams are fig. 8, wherein (a), (b) and (C) are Zr element, si element and C element, respectively. From the results, zrO 2 The ceramic particles are uniformly distributed in the amorphous SiC ceramic matrix.
Enhanced thermal insulation ZrO prepared for the remaining examples 2 The mechanical property, specific surface area, density, thermal conductivity, morphology and the like of the composite ceramic aerogel are researched, and results similar to those of the composite ceramic aerogel are obtained.
Although the preferred embodiments of the present invention have been described, the present invention is not limited to the above-mentioned embodiments, which are only illustrative and not restrictive, and those skilled in the art can make various modifications without departing from the spirit and scope of the present invention, which falls within the protection scope of the present invention.
Claims (10)
1. A preparation method of a reinforced thermal insulation zirconium dioxide composite ceramic aerogel is characterized by comprising the following steps:
(1) Taking zirconium oxychloride octahydrate as a raw material, cetyl trimethyl ammonium bromide as a dispersing agent and propylene oxide as a cross-linking agent, and preparing ZrO by a sol-gel method and supercritical drying 2 A particulate aerogel;
(2) Subjecting the ZrO to 2 Putting the particle aerogel into a mould, introducing a polyborosilazane ceramic precursor or a polycarbosilane ceramic precursor through vacuum impregnation, and obtaining ZrO with a three-dimensional network structure through hydrothermal reaction and supercritical drying 2 A composite aerogel precursor; the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor is used as a bonding phase to bond the ZrO 2 The particle aerogel is bonded into a blocky structure;
(3) Subjecting the ZrO to 2 Performing pyrolysis on the composite aerogel precursor to form enhanced heat-insulation ZrO 2 Composite ceramic aerogel.
2. The preparation method of the enhanced thermal insulation zirconium dioxide composite ceramic aerogel according to claim 1, wherein the step (1) comprises the following steps: adding zirconyl chloride octahydrate into an ethanol water solution, and stirring at room temperature until the zirconyl chloride octahydrate and the ethanol water solution are uniformly mixed; adding cetyl trimethyl ammonium bromide in the stirring process until the solution becomes clear and transparent, adding epoxypropane, stirring uniformly, pouring into a mould, and standing to obtain wet gel; aging the wet gel in absolute ethyl alcohol, and performing supercritical drying to obtain the ZrO 2 A particulate aerogel.
3. The preparation method of the enhanced thermal insulation zirconium dioxide composite ceramic aerogel according to claim 2, wherein the zirconium oxychloride octahydrate is 6 to 15 parts by mass, the cetyltrimethylammonium bromide is 0.5 to 2 parts by mass, and the propylene oxide is 1 to 6 parts by mass.
4. The preparation method of the enhanced thermal insulation zirconium dioxide composite ceramic aerogel according to claim 1, wherein the step (2) comprises the steps of: subjecting the obtained product in step (1) toZrO 2 Mixing the particle aerogel with the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor and a cross-linking agent, fully stirring, pouring into a mould, and vacuum impregnating to ensure that the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor and the ZrO 2 Fully contacting and wetting the particle aerogel, and then carrying out hydrothermal reaction to obtain composite wet gel; after the composite wet gel is aged, the ZrO is obtained by supercritical drying 2 A composite aerogel precursor.
5. The preparation method of the enhanced thermal insulation zirconium dioxide composite ceramic aerogel according to claim 4, wherein the weight average molecular weight of the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor is 5000-8000g/mol.
6. The preparation method of the thermal insulation reinforced zirconium dioxide composite ceramic aerogel according to claim 4, wherein the ZrO is prepared by using the method 2 The mass ratio of the granular aerogel to the ceramic precursor is (1-15): (1-10).
7. The preparation method of the thermal insulation-enhanced zirconium dioxide composite ceramic aerogel according to claim 4, wherein the ZrO 2 is 2 The mixing and stirring time of the granular aerogel and the ceramic precursor is 1-3 h.
8. The preparation method of the enhanced thermal insulation zirconium dioxide composite ceramic aerogel according to claim 4, wherein the hydrothermal reaction is carried out at 150-200 ℃ for 1-6h.
9. The method for preparing the enhanced thermal insulation zirconium dioxide composite ceramic aerogel according to claim 1, wherein the pyrolysis temperature in the step (3) is 800-1400 ℃ and the pyrolysis is performed under the protection of nitrogen.
10. A reinforced thermal insulating zirconia composite ceramic aerogel obtained by the production method according to any one of claims 1 to 9.
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