CN114853470B - Enhanced thermal insulation zirconium dioxide composite ceramic aerogel and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of ceramic materials, and discloses a reinforced heat-insulating zirconia composite ceramic airgel and a preparation method thereof. Firstly, zirconium oxychloride octahydrate is used as a raw material and cetyltrimethylammonium bromide is used as a dispersed agent, propylene oxide as cross-linking agent, ZrO ₂ particle airgel was prepared by sol-gel method and supercritical drying; then ZrO ₂ particle airgel was put into the mold, and polyborosilicate nitrogen was introduced by vacuum impregnation Alkane ceramic precursor or polycarbosilane ceramic precursor, the ZrO ₂ composite airgel precursor with a three-dimensional network structure is obtained through hydrothermal reaction and supercritical drying; finally, the ZrO ₂ composite airgel precursor is pyrolyzed to form a reinforced Thermal insulation _ZrO2 composite ceramic airgel. The high-strength heat-insulating zirconia composite ceramic airgel obtained in the invention has excellent mechanical properties and good high-temperature heat insulation performance, and can be used as a high-quality structural material with important application prospects in civil, military, aerospace and other fields.

Description

A kind of enhanced thermal insulation zirconia composite ceramic airgel and its preparation method

technical field

The invention belongs to the technical field of ceramic materials, and in particular relates to a composite ceramic airgel material and a preparation method thereof.

technical background

The pore size of airgel materials is smaller than the mean free path of air, which limits gas convection during heat conduction, and thus exhibits extremely low thermal conductivity. The ZrO ₂ particle airgel has a multi-level structure. The primary particles are connected as small units to form secondary particles, and the secondary particles are cross-linked to form dendritic clusters. There are pores with a diameter of about 20nm between the clusters. At high temperature, the high specific surface area of the aerogel increases the surface energy. In order to achieve a stable state, the primary particles in contact with each other will appear necking phenomenon to reduce the surface free energy. This will destroy the nanopore structure inside the airgel, and the cluster phenomenon will become more and more obvious. After the heat treatment temperature is higher than 800°C, the skeleton structure will collapse, the density will increase significantly, and the thermal conductivity will also rise sharply. The typical characteristics of airgel are light and porous, it can be considered that its thermal insulation performance has failed, and granular aerogels cannot be directly used as structural materials in chemical and other fields.

Contents of the invention

The present invention aims at the technical deficiencies of existing granular airgel materials in terms of high temperature resistance and mechanical properties, and provides a _ZrO2 composite ceramic airgel with enhanced heat insulation and its preparation method, using _ZrO2 granular airgel as a matrix Materials, using the ceramic precursor of polyborosilazane or polycarbosilane as a binder, the ZrO ₂ composite airgel precursor is obtained through hydrothermal reaction and supercritical drying; and then the enhanced thermal insulation ZrO ₂ is formed by pyrolysis Composite ceramic airgel; the airgel material endows ZrO ₂ particle airgel with good structural mechanics, and can effectively improve the high temperature stability of ZrO ₂ airgel; while having high temperature stability and excellent mechanical properties, It can also be used as a structural material directly in industrial manufacturing to achieve high-strength heat insulation.

In order to solve the above technical problems, the present invention is achieved through the following technical solutions:

According to one aspect of the present invention, a kind of preparation method of reinforced thermal insulation zirconia composite ceramic airgel is provided, comprising the following steps:

(1) Using zirconium oxychloride octahydrate as raw material, cetyltrimethylammonium bromide as dispersant, and propylene _oxide as crosslinking agent, ZrO2 particle gas was prepared by sol-gel method and supercritical drying gel;

( ₂ ) Put the ZrO2 particle airgel into a mold, introduce polyborosilazane ceramic precursor or polycarbosilane ceramic precursor by vacuum impregnation, and obtain a three-dimensional network structure through hydrothermal reaction and supercritical drying ZrO ₂ composite airgel precursor; the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor is used as a bonding phase to bond the ZrO ₂ particle airgel into a block structure;

(3) The ZrO ₂ composite airgel precursor is pyrolyzed to form an enhanced thermal insulation ZrO ₂ composite ceramic airgel.

Further, the step (1) includes the following steps: adding zirconium oxychloride octahydrate into the aqueous ethanol solution, stirring at room temperature until uniformly mixed; adding cetyltrimethylammonium bromide during the stirring process until the solution becomes It is clear and transparent, after adding propylene oxide and stirring evenly, it is poured into a mold, and left standing to obtain a wet gel; after the wet gel is aged in absolute ethanol, the ZrO ₂ particle airgel is obtained by supercritical drying.

Further, the zirconium oxychloride octahydrate is 6-15 parts by mass, the cetyltrimethylammonium bromide is 0.5-2 parts by mass, and the propylene oxide is 1-6 parts by mass.

Further, step ( ₂ ) comprises the steps of: combining the ZrO particle airgel obtained in step (1) with the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor, crosslinking agent Stir well after mixing, pour into a mold, make the _{polyborosilazane} ceramic precursor or the polycarbosilane ceramic precursor fully contact and wet with the ZrO2 particle airgel by vacuum impregnation, and then carry out hydrothermal reaction to obtain a composite wet gel; after the composite wet gel is aged, the ZrO ₂ composite airgel precursor is obtained by supercritical drying.

Further, the weight average molecular weight of the polyborosilazane ceramic precursor or the polycarbosilane ceramic precursor is 5000-8000g/mol.

Further, the mass ratio of the ZrO ₂ particle airgel to the ceramic precursor is (1-15):(1-10).

Further, the mixing and stirring time of the ZrO ₂ particle airgel and the ceramic precursor is 1-3 hours.

Further, the condition of the hydrothermal reaction is to react at 150-200°C for 1-6h.

Further, the temperature of the pyrolysis in step (3) is 800-1400°C, and it is carried out under the condition of nitrogen protection.

According to another aspect of the present invention, there is provided a reinforced thermal insulation zirconia composite ceramic airgel obtained by the above preparation method.

The beneficial effects of the present invention are:

The enhanced heat-insulating zirconia composite ceramic airgel and the preparation method thereof of the present invention construct a two-phase ceramic airgel three-dimensional network structure, and effectively solve the technical bottlenecks of high-temperature agglomeration and heat-insulation performance degradation of existing particle airgel. Using ZrO2 particle airgel as the matrix material, the ceramic precursor of _{polyborosilazane} or polycarbosilane was introduced by vacuum impregnation as the bonding phase. After supercritical drying and high temperature cracking, the ceramic precursor was transformed into Si-BCN Or Si-C ceramic airgel is bonded to the surface of ZrO ₂ particle airgel to form a three-dimensional structure material with both phases being ceramic airgel. In the composite ceramic airgel, the matrix material and the binder phase have high compatibility and interfacial bonding force, which can play the role of stress transmission. Under cracking conditions, ceramic precursors are coated on the surface of ZrO ₂ particle airgel, and the network structure of ceramic airgel can be adjusted by changing the cracking temperature. After the construction of the three-dimensional network structure, the composite ceramic airgel has a certain strength, and at the same time, the phase interface can also effectively transfer the load, endowing the material with good mechanical properties; at the same time, the multi-level porous structure of the two-phase airgel endows the material with good thermal insulation performance .

Compared with the traditional _ZrO2 particle aerogel, the enhanced thermal insulation zirconia composite ceramic aerogel of the present invention has a macro block structure, can withstand a compressive strength of 5.32Mpa, and a thermal conductivity as low as 0.0437W ·m ^-1 K ^-1 , with excellent mechanical properties and good high-temperature heat insulation performance, has important application prospects in civil, military, aerospace and other fields.

Description of drawings

Fig. ₁ is the three-dimensional network structure ZrO2 composite airgel precursor prepared in Example 1-3 of the present invention and the compression performance curve of the enhanced heat insulation ZrO2 composite ceramic airgel prepared in Example 4-5 _;

Fig. ₂ is (a) nitrogen adsorption-desorption and (b) pore size distribution curve diagram of the reinforced thermal insulation ZrO composite ceramic airgel prepared in Examples 1-3 of the present invention;

Fig. 3 is (a) nitrogen adsorption-desorption and (b) pore size distribution curve diagram of the reinforced thermal insulation ZrO composite ceramic airgel prepared in Example ₄ of the present invention;

Fig. 4 is the (a) nitrogen adsorption-desorption and (b) pore size distribution curve diagram of the reinforced thermal insulation ZrO composite ceramic airgel prepared in Example ₅ of the present invention;

Fig. 5 is the thermogravimetric curve of the three _- dimensional network structure ZrO composite airgel precursor prepared in Example 1-3 of the present invention and the enhanced heat insulation ZrO composite ceramic airgel prepared in Example 4-5 _;

Fig. 6 is the SEM figure of the present invention (a) embodiment 6, (b) embodiment 7 and (c) embodiment ₄ prepared reinforced insulation ZrO composite ceramic airgel;

Fig. 7 is the preparation mechanism diagram of the present invention and the TEM diagram of the reinforced heat _- insulating ZrO2 composite ceramic airgel prepared in Example 5;

Fig. 8 is the element surface scanning distribution diagram of the reinforced thermal insulation ZrO2 composite ceramic airgel prepared in Example ₅ of the present invention; wherein (a) is the general diagram, (b) is the distribution of Zr elements, and (c) is the distribution of Si elements , (d) is the C element distribution.

detailed description

Below by specific embodiment and comparative example the present invention will be described in further detail:

Example 1

( ₁ ) Preparation of ZrO2 particle airgel by sol-gel method: add 8.9g zirconium oxychloride octahydrate to 100mL 80% by mass ethanol aqueous solution, stir at room temperature for 1h until uniformly mixed; Add 0.712g of cetyltrimethylammonium bromide until the solution becomes clear and transparent, add 5.3g of cross-linking agent propylene oxide and stir evenly, pour it into the mold, and leave it to obtain a wet gel; After aging in ethanol, ZrO2 particle aerogels _were obtained by supercritical drying.

( ₂ ) Preparation of three-dimensional network structure ZrO2 composite airgel precursor: dissolve 0.76g polyborosilazane in tetrahydrofuran, stir for 3h to fully dissolve, take 0.608g of ZrO2 particles obtained in step ( ₁ ) The airgel was vacuum impregnated into polyborosilazane, then added 0.74g of divinylbenzene, stirred for 1h, transferred to a polytetrafluoroethylene-lined hydrothermal kettle, vacuumed for 1h, and then heated to 180°C for 6h. A composite wet gel is obtained; the composite wet gel is soaked in ethanol solution for aging for 2 days, and then supercritically dried for 6 hours to obtain a ZrO ₂ composite airgel precursor with a three-dimensional network structure. Wherein, the weight average molecular weight of polyborosilazane is 8000 g/mol.

Example 2

The ZrO ₂ composite airgel precursor with a three-dimensional network structure was prepared according to the method in Example 1, the only difference being that the mass of the ZrO ₂ particle airgel in step (2) was 0.76 g.

Example 3

The ZrO ₂ composite airgel precursor with a three-dimensional network structure was prepared according to the method in Example 1, the only difference being that the mass of the ZrO ₂ particle airgel in step (2) was 0.912 g.

Example 4

According to the method for embodiment ₂ , prepare the ZrO of three-dimensional network structure Composite airgel precursor, carry out step (3) afterwards;

(3) Preparation of ZrO ₂ composite ceramic airgel with enhanced thermal insulation: the ZrO ₂ composite airgel precursor with three-dimensional network structure obtained in step (2) was pyrolyzed at 1200 ° C for 1 h under the condition of nitrogen protection, and the reinforced insulation was obtained. Thermal _ZrO2 composite ceramic airgel.

Example 5

( ₁ ) Preparation of ZrO2 particle airgel by sol-gel method: add 6g of zirconium oxychloride octahydrate to 100mL of 80% by mass ethanol aqueous solution, stir at room temperature for 1h until uniform; 0.5g of cetyltrimethylammonium bromide until the solution becomes clear and transparent, add 6g of cross-linking agent propylene oxide and stir evenly, pour it into the mold, and let it stand to obtain a wet gel; the wet gel is dissolved in absolute ethanol After aging, ZrO2 particle aerogels _were obtained by supercritical drying.

(2) Preparation of three-dimensional network structure ZrO ₂ composite airgel precursor: Dissolve 0.756g of polycarbosilane in 7.558g of tetrahydrofuran, stir for 1h to fully dissolve, take 0.756g of ZrO ₂ particles obtained in step 1) The gel was vacuum-impregnated into polycarbosilane, then added 0.65g of divinylbenzene, stirred for 3 hours, transferred to a polytetrafluoroethylene-lined hydrothermal kettle, vacuumed for 1 hour, and then heated to 150°C for 5 hours to obtain a composite wet Gel; the composite wet gel was soaked in ethanol solution for aging for 2 days, and then supercritically dried for 6 hours to obtain a three-dimensional network structure ZrO ₂ composite airgel precursor. Wherein, the weight average molecular weight of polycarbosilane is 5000 g/mol.

(3) Preparation of enhanced thermal insulation ZrO ₂ composite ceramic airgel: the three-dimensional network structure ZrO ₂ composite airgel precursor obtained in step (2) was pyrolyzed at 1200 ° C for 1 h under nitrogen protection to obtain enhanced thermal insulation ZrO ₂ composite ceramic airgel.

Example 6

According to the method for embodiment ₂ , prepare the ZrO of three-dimensional network structure Composite airgel precursor, carry out step (3) afterwards;

(3) Preparation of ZrO ₂ composite ceramic airgel with enhanced thermal insulation: the precursor of ZrO ₂ composite airgel with a three-dimensional network structure obtained in step (2) was pyrolyzed at 800°C for 1 hour under nitrogen protection to obtain enhanced thermal insulation _ZrO2 composite ceramic airgel.

Example 7

According to the method for embodiment ₂ , prepare the ZrO of three-dimensional network structure Composite airgel precursor, carry out step (3) afterwards;

(3) Preparation of ZrO ₂ composite ceramic airgel with enhanced thermal insulation: the ZrO ₂ composite airgel precursor with three-dimensional network structure obtained in step (2) was pyrolyzed at 1000°C under nitrogen protection for 1 hour to obtain enhanced thermal insulation _ZrO2 composite ceramic airgel.

Example 8

According to the method for embodiment ₂ , prepare the ZrO of three-dimensional network structure Composite airgel precursor, carry out step (3) afterwards;

(3) Preparation of ZrO ₂ composite ceramic airgel with enhanced thermal insulation: the ZrO ₂ composite airgel precursor with three-dimensional network structure obtained in step (2) was pyrolyzed at 1400°C under nitrogen protection for 1 hour to obtain enhanced thermal insulation _ZrO2 composite ceramic airgel.

Example 9

(1) Preparation of ZrO ₂ particle airgel by sol-gel method: 15g of zirconyl chloride octahydrate was added to 100mL of 80% by mass ethanol aqueous solution, stirred at room temperature for 1h until uniformly mixed. Add 2g of cetyltrimethylammonium bromide until the solution becomes clear and transparent during the stirring process, add 1g of crosslinking agent propylene oxide and stir evenly, pour it into the mold, and let it stand to obtain a wet gel; After aging in absolute ethanol, ZrO2 particle aerogels _were obtained by supercritical drying.

(2) Preparation of three-dimensional network structure ZrO ₂ composite airgel precursor: Dissolve 0.756g of polycarbosilane in 7.558g of tetrahydrofuran, stir for 1h to fully dissolve, take 0.756g of ZrO ₂ particles obtained in step 1) The gel was vacuum-impregnated into polycarbosilane, then added 0.65g of divinylbenzene, stirred for 2 hours, transferred to a polytetrafluoroethylene-lined hydrothermal kettle, vacuumed for 1 hour, and then heated to 200°C for 1 hour to obtain a composite wet Gel; the composite wet gel was soaked in ethanol solution and aged for 2 days, and then dried by supercritical for 6 hours to obtain a three-dimensional network structure ZrO ₂ composite airgel precursor. Wherein, the weight average molecular weight of polycarbosilane is 7000 g/mol.

(3) Preparation of enhanced thermal insulation ZrO ₂ composite ceramic airgel: the three-dimensional network structure ZrO ₂ composite airgel precursor obtained in step (2) was pyrolyzed at 1200 ° C for 1 h under nitrogen protection to obtain enhanced thermal insulation ZrO ₂ composite ceramic airgel.

Performance test results:

Adopt mechanical testing machine (FL5504) to measure the compressive strength of material, Fig. ₁ is the ZrO of three-dimensional network structure prepared by the embodiment of the present invention Composite airgel precursor and embodiment 4-5 prepare the enhanced heat-insulating ZrO ₂ Compression performance curves of composite ceramic airgel. It can be seen from the test results that after pyrolysis, the mechanical properties of the ceramic airgel are significantly enhanced compared with the airgel precursor. This is because as the temperature rises, the organic matter gradually decomposes, the material undergoes ceramic transformation, and the ceramic precursor polymer gradually changes from organic matter to SiBCN, SiC and other ceramic materials, making the internal structure of the airgel gradually denser and the porosity gradually reduced. , so the mechanical strength gradually increases. In Example 4 and Example 5, SiBCN/ZrO ₂ and SiC/ZrO ₂ composite aerogels were respectively obtained at a cracking temperature of 1200°C, and the maximum compressive strengths were 5.32MPa and 4.71MPa respectively. The composite airgel obtained with silazane as the precursor binder has higher mechanical strength.

The ceramic airgel samples were tested with a 3H-2000PS1 specific surface area and pore diameter tester from Beijing Best Instrument Technology Co., Ltd. Before the test, the airgel sample was dried under vacuum at 150°C for 3 hours, so as to remove the impurities adsorbed on the sample and the water molecules in the air. Fig. 2 is (a) nitrogen adsorption-desorption curve and (b) pore size distribution curve of the three-dimensional network structure ZrO ₂ composite airgel precursor prepared in Examples 1-3 of the present invention. It can be seen from Fig. 2 that all the samples have type IV isotherms of H ₃ hysteresis loop, indicating that the material has a mesoporous structure. Example 2 has the highest specific surface area of 812.646m ² g ^-1 and an average pore diameter of 17.046nm. It can be seen that the specific surface area is the highest when the mass ratio of ceramic precursor binder to ZrO2 particle airgel is ₁ :1, and a three-dimensional composite airgel with good pore structure is obtained. Fig. 3 and Fig. 4 are the (a) nitrogen adsorption-desorption curve and (b) pore size distribution curve figure of (a) nitrogen adsorption-desorption curve and (b) pore size distribution curve of the prepared reinforced heat insulation ZrO of the embodiment ₅ of the present invention and embodiment 5 respectively, by Fig. 3 It can be seen from Figure 4 that the _N2 adsorption/desorption isotherm of the ceramic composite airgel obtained after the sample was pyrolyzed at 1200 °C is still a type IV isotherm with a _H3 hysteresis loop, and the surface sample still has a mesoporous structure, Table 1 The BET specific surface area values of Examples 1-5 are listed, and it can be clearly seen from the results that the specific surface area of the sample after ceramization decreases significantly, and the density increases, indicating that the internal pore structure of the airgel becomes dense after ceramization, which is consistent with The mechanical properties confirm each other.

Using a thermogravimetric analysis instrument (TG/DTA, Q600) in a nitrogen atmosphere at a heating rate of 20 °C/min, from room temperature to 1000 °C, the thermal stability of the sample was analyzed. Fig. ₅ is the thermogravimetric curve of the three _- dimensional network structure ZrO2 composite airgel precursor prepared by the embodiment 1-3 of the present invention and the reinforced heat insulation ZrO2 composite ceramic airgel prepared by the embodiment 4-5, by the thermogravimetric curve It can be seen that for Examples 1-3, when the sample is at 180°C, there is a small amount of mass loss, which is mainly caused by the volatilization of moisture, residual solvents and low molecular weight substances. When the temperature is 180-550°C, the precursor organic matter begins to decompose, and the decomposition rate reaches the maximum when the temperature is higher than 550°C, indicating that a large number of molecular chains are broken and rearranged in the system, and the hydrocarbon components are decomposed rapidly, releasing a large number of small molecules. gas, a ceramic transformation occurs. When the temperature is higher than 700 °C, the pyrolysis rate of the composite airgel precursor slows down, and finally the ceramic composite airgel is formed. In contrast, the mass loss of the thermogravimetric curves of Example 4 and Example 5 is very small, which is mainly due to the fact that these two samples have been subjected to thermal cracking to form a ceramic composite airgel, so there is almost no decomposition of organic matter. , and further shows that the ceramic composite airgel obtained in the present invention has good high temperature thermal stability.

Use a thermal conductivity measuring instrument (TC 3000E, XIA TECH, CHN) to test the thermal conductivity of the sample, and the working current range is 0-10mA. The thermal conductivity of Examples 1-3 ranges from 0.0344-0.0358W m ^-1 K ^-1 , the thermal conductivity of Example 4 is 0.0437W m ^-1 K ^-1 , and the thermal conductivity of Example 5 is ^0.053W m ^-1 K -1 ¹ , and the corresponding results are listed in Table 1. It can be seen that the thermal conductivity of the airgel without pyrolysis is lower, and the thermal conductivity of the ceramic airgel formed after pyrolysis is increased, which is mainly due to the fact that the airgel is ceramicized during the The reason for the denser structure. But overall, the obtained composite ceramic airgel still has good thermal insulation performance.

Table 1

Adopt SM-7800F type ultra-high resolution thermal field emission scanning electron microscope of Japan Electronics Co., Ltd. to carry out morphology analysis on the sample, and Fig. 6 shows (a) embodiment 6 of the present invention, (b) embodiment 7 and (c) embodiment 4 SEM images of the fabricated _ZrO2 composite ceramic airgel with enhanced thermal insulation. It can be seen from Figure 6 that with the increase of the cracking temperature, the pore structure of the composite airgel becomes denser, indicating that the ceramic transformation is more complete, but the ceramic products are still highly porous, and the composite ceramic airgel retains mesoporous materials. pore structure.

Adopt FEVTECNAIG2F 20 type transmission electron microscope (TEM) to carry out transmission topography analysis to embodiment 5, Fig. 7 is the TEM topography diagram of preparation mechanism diagram of the present invention and embodiment 5, corresponding surface scanning element distribution diagram is Fig. 8, wherein (a) (b) (c) are Zr element Si element and C element respectively. From the results, it can be seen that the _ZrO2 ceramic particles are uniformly distributed in the amorphous SiC ceramic matrix.

The mechanical properties, specific surface area, density, thermal conductivity, and morphology of the reinforced heat-insulating ZrO ₂ composite ceramic airgel prepared in the remaining examples were studied, and results similar to those mentioned above were obtained.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above-mentioned specific implementation, and the above-mentioned specific implementation is only illustrative and not restrictive. Under the inspiration of the invention, without departing from the gist of the invention and the scope of protection of the claims, many forms of specific changes can be made, and these all belong to the scope of protection 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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