Polymer precursor ceramic inverse opal structure and preparation method and application thereof

Abstract

The invention discloses a polymer precursor ceramic inverse opal structure and a preparation method and application thereof in the field of aerospace thermal protection materials. Polystyrene microspheres are synthesized through a dispersion polymerization method, and a stacked opal template is prepared through self-assembly; dipping a liquid mixture containing a polymer precursor and a photoinitiator or a thermosetting agent into the template, and curing by adopting an ultraviolet curing or high-pressure thermocuring method to obtain a polymer precursor / template complex; and finally, performing high-temperature pyrolysis in an inert atmosphere to convert the polymer precursor into polymer precursor ceramic, and removing the template, thereby obtaining the three-dimensional inverse opal photonic crystal structure material with the regular periodic aperture. Through the design of the inverse opal structure of the polymer precursor ceramic, the reflectivity of the polymer precursor ceramic from visible light to near-infrared band is effectively improved, the thermal protection threshold is effectively improved, and the thermal protection material is multifunctional through the temperature resistance characteristic of the polymer precursor ceramic.

Description

Technical Field

[0001] The present invention relates to the field of aerospace thermal protection materials, and in particular to a polymer precursor ceramic inverse opal structure, a preparation method and an application thereof. Background Art

[0002] With the continuous development of aerospace industry, how to ensure the safe operation of spacecraft has become a research focus of the aerospace industry. Spacecraft are directly impacted by solar thermal radiation in the space environment, and materials with extremely high thermal protection performance and high-temperature stability are required to ensure the safe operation of spacecraft. On this basis, it is necessary to consider lightweighting during launch and multifunctionality during operation. Traditional spacecraft thermal protection usually uses a multi-layer structure composed of a variety of materials such as ablative layers, thermal insulation layers, and heat dissipation layers to achieve thermal protection. However, due to the large differences in material properties, this multi-layer structure is prone to defects at the interface and has poor connection stability, which is not conducive to long-term service. Currently, commonly used thermal protection materials can be divided into three categories: heat capacity absorption type, radiation type, and mass ejection type. However, traditional metal or ceramic thermal protection materials have a single function and are heavy, which makes it difficult to meet the spacecraft's demand for lightweight and multifunctional integrated thermal protection materials.

[0003] Photonic crystals are superstructures formed by periodic arrangements of dielectric materials, offering controllable properties regarding light. By manipulating structural parameters, the material's reflectivity for specific wavelengths can be enhanced, reducing heat accumulation on the surface and effectively raising the thermal protection threshold. The inverse opal structure is one of the most studied and most mature structures in three-dimensional photonic crystals. Opal templates are self-assembled from colloidal microspheres filled with a precursor solution; removal of the template yields the complete inverse opal structure. In recent years, polymer-derived ceramics (PDCs) have become a hot topic of research. Derived from liquid-added polymer precursors, PDCs combine the high-temperature stability and molecular-level composition control of traditional ceramics with the designability of micro- and nanostructures, making them ideal for photonic crystal fabrication. By tailoring the structural dimensions to enhance the PDCs' reflectivity in the concentrated solar radiation wavelength range (400 nm to 2500 nm), the thermal protection threshold can be effectively increased, building on the PDCs' excellent high-temperature stability. In addition, PDCs have good temperature-resistance characteristics, which can realize real-time monitoring of ambient temperature on the basis of thermal protection, realizing the multifunctionality of aerospace thermal protection materials. Summary of the Invention

[0004] In response to the problems of poor stability and single function of existing thermal protection materials, the present invention utilizes the liquid molding advantages of PDCs and proposes a polymer precursor ceramic inverse opal structure and its preparation method and application.

[0005] The technical solution of the present invention is as follows: polystyrene microspheres are synthesized by dispersion polymerization and self-assembled to form a stacked opal template; a liquid mixture containing a polymer precursor and a photoinitiator or thermosetting agent is impregnated into the template and cured using ultraviolet light curing or high-pressure heat curing to form a polymer precursor / template complex; finally, high-temperature pyrolysis is performed in an inert atmosphere to convert the polymer precursor into a polymer precursor ceramic, and the template is removed, thereby obtaining a three-dimensional inverse opal photonic crystal structure material with regularly periodic pores. Optionally, a nano-TiO2 coating is deposited on the surface of the prepared ceramic inverse opal to further reduce internal free carbon absorption and improve reflectivity in the visible-to-near-infrared range.

[0006] Based on one of the above-mentioned invention objectives, the present invention provides a method for preparing a polymer precursor ceramic inverse opal structure, comprising the following steps:

[0007] S1. Ultrapure water and anhydrous ethanol were mixed and a dispersant, polyvinylpyrrolidone, was added and stirred uniformly at room temperature by magnetic stirring under a nitrogen atmosphere;

[0008] S2. The reaction monomer styrene and the reaction initiator azobisisobutyronitrile were mixed and stirred evenly at room temperature by magnetic stirring;

[0009] S3. The solution obtained in step S1 and step S2 was added to a container and mixed, and heated in a water bath under a nitrogen atmosphere with stirring, and the reaction was continued for a period of time to obtain a polystyrene colloidal microsphere solution;

[0010] S4. The polystyrene colloidal microsphere solution obtained in step S3 was aliquoted and leveled by centrifugation, and after removing the upper turbid liquid, the polystyrene colloidal microspheres were obtained by vacuum drying at room temperature;

[0011] S5. The polystyrene colloidal microspheres obtained in step S4 are dispersed in ultrapure water and ultrasonically treated to obtain a monodisperse polystyrene colloidal microsphere dispersion;

[0012] S6. The monodisperse polystyrene colloidal microsphere dispersion prepared in step S5 is placed in a container, and a hydrogen peroxide-treated quartz glass is suspended above the container so that the quartz glass is immersed in the monodisperse polystyrene colloidal microsphere dispersion. The quartz glass is vertically deposited in a vacuum drying oven to obtain a polystyrene colloidal microsphere opal film;

[0013] S7. The polymer precursor liquid is mixed with a photoinitiator or a thermosetting agent and stirred under a nitrogen atmosphere by magnetic stirring until the photoinitiator or thermosetting agent is completely dissolved to obtain a precursor mixture;

[0014] S8. The precursor mixture obtained in step S7 is cast on the polystyrene colloidal microsphere opal film obtained in step S6 and cured in a UV solid box or autoclave to obtain a polymer precursor / template complex;

[0015] S9. The polymer precursor / template complex obtained in step S8 is subjected to high-temperature pyrolysis in an atmosphere tube furnace under a nitrogen atmosphere to obtain a polymer precursor ceramic inverse opal structure.

[0016] Based on the second purpose of the above invention, the present application prepares a TiO2 film on the surface of the polymer precursor ceramic inverse opal structure obtained based on the above preparation method by magnetron sputtering.

[0017] Based on the third purpose of the above invention, the present application proposes an application scheme of the polymer precursor ceramic inverse opal structure, that is, applying the above polymer precursor ceramic inverse opal structure to the field of aerospace thermal protection.

[0018] The present invention also includes other steps, equipment, or components that enable the preparation method to proceed normally. These steps, equipment, or components all employ conventional techniques in the art. In addition, steps, equipment, or components not otherwise specified in the present invention all employ conventional techniques in the art. During implementation, appropriate equipment or component models may be selected based on the specific work scenario.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The present invention effectively improves the reflectivity of polymer precursor ceramics in the visible to near-infrared band through the design of the polymer precursor ceramic inverse opal structure, effectively increases the thermal protection threshold, and also realizes the multifunctionalization of thermal protection materials through the temperature resistance characteristics of polymer precursor ceramics.

[0021] (2) The template microspheres in the present invention are polystyrene colloidal microspheres, the particle size of which is controllable and can be completely removed by a high-temperature pyrolysis process, thereby obtaining a complete inverse opal structure.

[0022] (3) The present invention does not require expensive equipment and raw materials during the preparation process, the experimental method is easy to operate, the experimental process is pollution-free, and the temperature and time in the experiment are easy to control. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a SEM photograph of the polystyrene colloidal microspheres prepared in Example 1 observed under a scanning electron microscope.

[0024] Figure 2This is a SEM photograph of the polystyrene colloidal microsphere opal film prepared in Example 1 observed under a scanning electron microscope.

[0025] Figure 3 This is a SEM photograph of the SiCN ceramic inverse opal structure in Example 1 observed under a scanning electron microscope.

[0026] Figure 4 These are the thermal conductivity test results of the SiCN ceramic inverse opal structure in Example 1 tested at different temperatures.

[0027] Figure 5 These are the visible light-near infrared reflectivity test results of the SiCN ceramic inverse opal structure in Example 1, the SiBCN ceramic inverse opal structure in Example 2, the SiBCN-TiO2 ceramic inverse opal structure in Example 3, and the SiCN ceramic flat plate.

[0028] Figure 6 1 is a graph showing the relationship between resistance and temperature of the SiCN ceramic inverse opal structure in Example 1.

[0029] Figure 7 This is a resistance-temperature stability diagram of the SiCN ceramic inverse opal structure in Example 1.

[0030] Figure 8 This is a relationship diagram of the resistance-temperature response cycle diagram of the SiCN ceramic inverse opal structure in Example 1. DETAILED DESCRIPTION

[0031] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. The following examples are only used to illustrate the present invention in detail and are not intended to limit the scope of the present invention in any way.

[0032] Example 1:

[0033] A method for preparing an inverse opal structure of a polymer precursor ceramic (SiCN ceramic):

[0034] 1. Mix 5 ml of ultrapure water with 95 ml of anhydrous ethanol and add 9.802 g of polyvinylpyrrolidone. Stir at 500 rpm under a nitrogen atmosphere with magnetic stirring at room temperature until uniform.

[0035] 2. Mix 20 ml of styrene and 1.089 g of azobisisobutyronitrile and stir magnetically at 500 rpm at room temperature until homogeneous.

[0036] 3. The solutions obtained in step 1 and step 2 were added to a round-bottom flask, mixed, and heated and stirred in a water bath at 70°C and 500 rpm under a nitrogen atmosphere for 12 hours to obtain a polystyrene colloidal microsphere solution;

[0037] 4. The solution prepared in step 3 was divided and leveled and centrifuged at 8000 rpm for 5 min. The upper turbid liquid was removed and vacuum dried at room temperature to obtain polystyrene colloidal microspheres;

[0038] 5. Disperse 0.2 g of polystyrene colloidal microspheres in 19.8 ml of ultrapure water and ultrasonicate to prepare a 1% monodisperse solution of polystyrene colloidal microspheres.

[0039] 6. A monodisperse polystyrene colloidal microsphere dispersion was placed in a beaker and a hydrogen peroxide-treated quartz glass was suspended above it. The dispersion was vertically deposited in a vacuum drying oven at 40°C to obtain a polystyrene colloidal microsphere opal film.

[0040] 7. Mix 10 g of precursor liquid PSN with 0.05 g of photoinitiator Irgacure 819 and stir at 90 °C and 500 rpm in a dark environment under nitrogen atmosphere until homogeneous;

[0041] 8. Casting the mixed solution obtained in step 7 onto the surface of the polystyrene colloidal microsphere opal film obtained in step 6, and photocuring in a UV curing box for 15 minutes to obtain a polymer precursor / template complex;

[0042] 9. The polymer precursor / template complex obtained in step 9 is pyrolyzed in an atmosphere tube furnace under a nitrogen atmosphere to obtain a SiCN ceramic inverse opal structure; the pyrolysis temperature is 1000°C, and the heating rate is 1°C / min before 200°C and 0.5°C / min from 200°C to 1000°C.

[0043] Figure 1 The SEM photograph of the polystyrene colloidal microspheres prepared in this example observed under a scanning electron microscope shows that the polystyrene colloidal microspheres prepared in this example have complete colloidal shapes and uniform particle size distribution, with a particle size of about 1.43 μm.

[0044] Figure 2 The SEM photograph of the polystyrene colloidal microsphere opal film prepared in this example observed under a scanning electron microscope shows that the opal template prepared in this example has a complete microstructure.

[0045] Figure 3 This is a SEM photograph of the SiCN ceramic inverse opal structure in Example 1 observed under a scanning electron microscope. It can be seen that the SiCN ceramic inverse opal sample has a complete structure.

[0046] Example 2:

[0047] A method for preparing an inverse opal structure of a polymer precursor ceramic (SiBCN ceramic):

[0048] 1. Mix 5 ml of ultrapure water with 95 ml of anhydrous ethanol and add 9.802 g of polyvinylpyrrolidone. Stir at 500 rpm under a nitrogen atmosphere with magnetic stirring at room temperature until uniform.

[0049] 2. Mix 20 ml of styrene and 1.089 g of azobisisobutyronitrile and stir magnetically at 500 rpm at room temperature until homogeneous.

[0050] 3. The solutions obtained in step 1 and step 2 were added to a round-bottom flask, mixed, and heated and stirred in a water bath at 70°C and 500 rpm under a nitrogen atmosphere for 12 hours to obtain a polystyrene colloidal microsphere solution;

[0051] 4. The solution prepared in step 3 was divided and leveled and centrifuged at 8000 rpm for 5 min. The upper turbid liquid was removed and vacuum dried at room temperature to obtain polystyrene colloidal microspheres;

[0052] 5. Disperse 0.2 g of polystyrene colloidal microspheres in 19.8 ml of ultrapure water and ultrasonicate to prepare a 1% monodisperse solution of polystyrene colloidal microspheres.

[0053] 6. A monodisperse polystyrene colloidal microsphere dispersion was placed in a beaker and a hydrogen peroxide-treated quartz glass was suspended above it. The dispersion was vertically deposited in a vacuum drying oven at 40°C to obtain a polystyrene colloidal microsphere opal film.

[0054] 7. Mix 10 g of precursor liquid PSNB with 0.045 g of thermosetting agent dicumyl peroxide and stir at 500 rpm under nitrogen atmosphere at room temperature until homogeneous;

[0055] 8. Casting the mixed solution obtained in step 7 onto the surface of the polystyrene colloidal microsphere opal film obtained in step 6, and curing in an autoclave at 120° C. and 2 MPa for 6 h to obtain a polymer precursor / template complex;

[0056] 9. The polymer precursor / template complex obtained in step 9 is pyrolyzed in an atmosphere tube furnace under a nitrogen atmosphere to obtain a SiCN ceramic inverse opal structure; the pyrolysis temperature is 1000°C, and the heating rate is 1°C / min before 200°C and 0.5°C / min from 200°C to 1000°C.

[0057] Example 3:

[0058] A method for preparing an inverse opal structure of a polymer precursor ceramic (SiBCN-TiO2 ceramic):

[0059] 1. Mix 5 ml of ultrapure water with 95 ml of anhydrous ethanol and add 9.802 g of polyvinylpyrrolidone. Stir at 500 rpm under a nitrogen atmosphere with magnetic stirring at room temperature until uniform.

[0060] 2. Mix 20 ml of styrene and 1.089 g of azobisisobutyronitrile and stir magnetically at 500 rpm at room temperature until homogeneous.

[0061] 3. The solutions obtained in step 1 and step 2 were added to a round-bottom flask, mixed, and heated and stirred in a water bath at 70°C and 500 rpm under a nitrogen atmosphere for 12 hours to obtain a polystyrene colloidal microsphere solution;

[0062] 4. The solution prepared in step 3 was leveled and centrifuged at 8000 rpm for 5 min. The supernatant was removed and vacuum dried at room temperature to obtain polystyrene colloidal microspheres.

[0063] 5. Disperse 0.2 g of polystyrene colloidal microspheres in 19.8 ml of ultrapure water and ultrasonicate to prepare a 1% monodisperse solution of polystyrene colloidal microspheres.

[0064] 6. A monodisperse polystyrene colloidal microsphere dispersion was placed in a beaker and a hydrogen peroxide-treated quartz glass was suspended above it. The dispersion was vertically deposited in a vacuum drying oven at 40°C to obtain a polystyrene colloidal microsphere opal film.

[0065] 7. Mix 10 g of precursor liquid PSNB with 0.045 g of thermosetting agent dicumyl peroxide and stir at 500 rpm under nitrogen atmosphere at room temperature until homogeneous;

[0066] 8. Casting the mixed solution obtained in step 7 onto the surface of the polystyrene colloidal microsphere opal film obtained in step 6, and curing in an autoclave at 120° C. and 2 MPa for 6 h to obtain a polymer precursor / template complex;

[0067] 9. The polymer precursor / template complex obtained in step 8 is pyrolyzed in an atmosphere tube furnace under a nitrogen atmosphere to obtain a SiBCN ceramic inverse opal structure; the pyrolysis temperature is 1000°C, and the heating rate is 1°C / min before 200°C and 0.5°C / min from 200°C to 1000°C.

[0068] 10. A layer of TiO2 with a thickness of about 366 nm was prepared on the surface of the SiBCN ceramic inverse opal structure sample obtained in step 9 by magnetron sputtering.

[0069] The above embodiments are only descriptions of preferred implementation modes of the present invention and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should fall within the scope of protection of the present invention.

[0070] Effect experiment 1:

[0071] In this experiment, a laser source is used to emit pulses uniformly on the sample surface to heat the sample uniformly. The corresponding temperature rise process on the sample surface is measured by an infrared detector to obtain a temperature rise and time curve. After fitting with a suitable model, the thermal diffusion coefficient is obtained. The specific heat capacity data is obtained by comparing with the standard sample. Finally, the thermal conductivity data of the sample at different temperatures is calculated by the formula. The results are as follows: Figure 4 , it can be seen that the sample has low thermal conductivity in the temperature range from room temperature to 1100℃ and has good thermal insulation protection ability.

[0072] Effect experiment 2:

[0073] In this experiment, the infrared radiation energy of the sample was measured by an emissivity meter and compared with the standard blackbody radiation energy at the same temperature. The infrared emissivity of the sample was 0.9, and the infrared radiation rate of the sample was calculated to be 405.14W / m 2 , it can be obtained that the sample has good radiation heat dissipation performance.

[0074] Effect experiment three:

[0075] In this experiment, the reflectivity of different samples in the visible to near-infrared band was tested by spectrophotometry. The results are as follows: Figure 5 As shown in the figure, it can be seen that the SiCN ceramic inverse opal structure has a significant reflectivity compared to the SiCN ceramic flat plate, while the SiBCN ceramic inverse opal structure and the SiBCN-TiO2 ceramic inverse opal structure have significantly higher reflectivity in the entire band than the SiCN ceramic flat plate and have obvious reflection peaks in local bands, indicating that the inverse opal structure improves the reflectivity of PDCs and effectively increases the thermal protection threshold.

[0076] Effect experiment 4:

[0077] In this experiment, electrodes were prepared on the surface of the SiCN ceramic inverse opal structure obtained in Example 1 using platinum slurry and platinum wire. The temperature signal output by the circuit was acquired using a LabVIEW system, and the resistance signal output was acquired using a digital multimeter. The LabVIEW system primarily consisted of a DAQ system and an acquisition module for signal acquisition. The thermocouple used for real-time temperature monitoring was a T-type thermocouple, with both temperature and resistance acquisition rates measured once per second.

[0078] Figure 6This is the response relationship between the resistance of the SiCN ceramic inverse opal structure obtained in Example 1 and temperature. It can be seen that as the temperature increases, the resistance of the SiCN ceramic inverse opal structure gradually decreases, indicating that the SiCN ceramic inverse opal structure in Example 1 has a good temperature resistance effect and can realize sensing and monitoring of temperature changes.

[0079] Effect experiment 5:

[0080] Figure 7 3. The experimental results of the resistance temperature cycling experiment of the SiCN ceramic inverse opal structure obtained in Example 1 are shown in the figure. As can be seen from the figure, after 6 cycles, the resistance and temperature of the SiCN ceramic inverse opal structure still maintain the same transformation trend, indicating that the temperature resistance effect of the SiCN ceramic inverse opal structure has good repeatability.

[0081] Effect experiment six:

[0082] Figure 8 1 is the experimental result of the resistance and temperature response stability of the SiCN ceramic inverse opal structure obtained in Example 1. It can be seen from the figure that after 5 hours of insulation at 950°C, the resistance of the SiCN ceramic inverse opal structure remains basically unchanged, indicating that the temperature resistance effect of the SiCN ceramic inverse opal structure has good stability.

[0083] Effect experiments 4 to 6 all used the same SiCN ceramic inverse opal structure sample prepared in Example 1, which is sufficient to demonstrate that the sample has a stable high-temperature temperature sensing function.

Claims

1. A method for preparing a polymer precursor ceramic inverse opal structure, characterized in that: The following steps are involved: S1. Ultrapure water and anhydrous ethanol were mixed and a dispersant, polyvinylpyrrolidone, was added and stirred uniformly at room temperature by magnetic stirring under a nitrogen atmosphere; S2. The reaction monomer styrene and the reaction initiator azobisisobutyronitrile were mixed and stirred evenly at room temperature by magnetic stirring; S3. The solution obtained in step S1 and step S2 was added to a container and mixed, and heated in a water bath under a nitrogen atmosphere with stirring, and the reaction was continued for a period of time to obtain a polystyrene colloidal microsphere solution; S4. The polystyrene colloidal microsphere solution obtained in step S3 was aliquoted and leveled by centrifugation, and after removing the upper turbid liquid, the polystyrene colloidal microspheres were obtained by vacuum drying at room temperature; S5. The polystyrene colloidal microspheres obtained in step S4 are dispersed in ultrapure water and ultrasonically treated to obtain a monodisperse polystyrene colloidal microsphere dispersion; S6. The monodisperse polystyrene colloidal microsphere dispersion prepared in step S5 is placed in a container, and a hydrogen peroxide-treated quartz glass is suspended above the container so that the quartz glass is immersed in the monodisperse polystyrene colloidal microsphere dispersion. The quartz glass is vertically deposited in a vacuum drying oven to obtain a polystyrene colloidal microsphere opal film; S7. The polymer precursor liquid is mixed with a photoinitiator or a thermosetting agent and stirred under a nitrogen atmosphere by magnetic stirring until the photoinitiator or thermosetting agent is completely dissolved to obtain a precursor mixture; S8. The precursor mixture obtained in step S7 is cast on the polystyrene colloidal microsphere opal film obtained in step S6 and cured in a UV solid box or autoclave to obtain a polymer precursor / template complex; S9. The polymer precursor / template complex obtained in step S8 is subjected to high-temperature pyrolysis in an atmosphere tube furnace under a nitrogen atmosphere to obtain a polymer precursor ceramic inverse opal structure.

2. The preparation method according to claim 1, wherein: In step S1, the ratio of ultrapure water, anhydrous ethanol and dispersant is 5:95:9.802, and the unit of the ratio is ml:ml:g; in step S2, the ratio of styrene to initiator is 20:1.089, and the unit of the ratio is ml:g.

3. The preparation method according to claim 1, wherein: In step S3, the reaction time is 12 h, the water bath heating temperature is 70° C., and the stirring speed is 500 r / min; in step S4, the centrifugal speed is 8000 r / min, and the centrifugal time is 5 min.

4. The preparation method according to claim 1, wherein: In step S5, the mass fraction of the polystyrene colloidal microspheres in the prepared monodisperse polystyrene colloidal microsphere dispersion is 0.5% to 1%.

5. The preparation method according to claim 1, wherein: In step S6, the hydrogen peroxide treatment time is 24 hours to 48 hours; the vertical deposition temperature is 40° C. to 60° C., and the deposition time is 24 hours to 72 hours.

6. The preparation method according to claim 1, wherein: In step S7, if a photoinitiator is used, the mass of the photoinitiator is 4% to 6% of the mass of the polymer precursor liquid, and stirring is carried out in a light-proof environment at 90°C to 120°C; if a thermosetting agent is used, the mass of the thermosetting agent is 4% to 5% of the mass of the polymer precursor liquid, and stirring is carried out at room temperature; using a photoinitiator or a thermosetting agent, the stirring time is 1 hour to 2 hours, and the stirring speed is 500 r / min; the polymer precursor liquid is PSN or PSNB.

7. The preparation method according to claim 1, wherein: When a photoinitiator is used in step S7, a UV curing box is used for curing in step S8, and the curing time is 10 minutes to 30 minutes; when a thermosetting agent is used in step S7, a high-pressure reactor is used for curing in step S8, and the curing temperature is 120° C., the curing pressure is 2 MPa to 2.8 MPa, and the curing time is 4 hours to 6 hours; the photoinitiator is Irgacure 819, and the thermosetting agent is diisopropylbenzene peroxide.

8. The preparation method according to claim 1, wherein: In step S9, the pyrolysis temperature is 800°C to 1200°C, and the heating rate of the atmosphere tube furnace is 1°C / min below 200°C and 0.5°C / min in the range of 200°C to 1200°C.

9. A polymer precursor ceramic inverse opal structure, characterized by: The polymer precursor ceramic inverse opal structure is prepared by the preparation method according to any one of claims 1 to 8, and a TiO2 thin film is prepared on the surface of the polymer precursor ceramic inverse opal structure by magnetron sputtering.

10. Use of the polymer precursor ceramic inverse opal structure according to claim 9 in the field of aerospace thermal protection.

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