CN114538908B - High-temperature ablation-resistant flexible thermal protection coating and preparation method thereof - Google Patents

High-temperature ablation-resistant flexible thermal protection coating and preparation method thereof Download PDF

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CN114538908B
CN114538908B CN202210003897.8A CN202210003897A CN114538908B CN 114538908 B CN114538908 B CN 114538908B CN 202210003897 A CN202210003897 A CN 202210003897A CN 114538908 B CN114538908 B CN 114538908B
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hollow
ceramic micro
nano powder
coating
powder
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CN114538908A (en
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张贺
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CASIC Space Engineering Development Co Ltd
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CASIC Space Engineering Development Co Ltd
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    • D06N2209/06—Properties of the materials having thermal properties

Abstract

The invention discloses a high-temperature ablation resistant flexible thermal protection coating, which comprises the following components of a coating matrix, hollow ultrahigh-temperature ceramic micro-nano powder, hollow oxide ceramic micro-nano powder and a reinforcing auxiliary agent, wherein the mass ratio of the coating matrix to the hollow ultrahigh-temperature ceramic micro-nano powder to the hollow oxide ceramic micro-nano powder to the reinforcing auxiliary agent is 1:0.1 to 0.3:0.2 to 0.6:0.01 to 0.1. The flexible thermal protection coating has better high-temperature ablation resistance, can meet the high-temperature ablation of 50-200 s at 1200-1600 ℃, has lower linear ablation rate, and has the characteristics of low density, low thermal conductivity and low residual stress. The invention also discloses a preparation method of the high-temperature ablation-resistant flexible thermal protection coating, which is simple and convenient to operate and wide in application range, and can be used for preparing and protecting the coating of the large-size complex curved structural member.

Description

High-temperature ablation-resistant flexible thermal protection coating and preparation method thereof
Technical Field
The invention belongs to the technical field of aerospace materials. In particular to a high-temperature ablation resistant flexible thermal protection coating and a preparation method thereof.
Background
The development of the latest spacecrafts at home and abroad is seen, the general development trend of the aerospace composite material is high temperature resistance, light weight, flexibility, low cost and multifunction, and the innovative development of the material microstructure design, the material system and the preparation method plays an indispensable leading role in the development of future aerospace materials.
In particular, in the face of novel flexible body spacecrafts such as inflatable deceleration reentry spacecrafts (IRDT), the traditional rigid thermal protection materials and structures cannot be applied to the application of the spacecrafts, and development of flexible thermal protection materials and technologies for service in ultra-high temperature reentry environments is needed. The flexible thermal protection system of the current inflatable deceleration reentry spacecraft has the performance requirement of stable service at the reentry temperature of 1200 ℃ or below, but the current task requirement and the service environment of 1200-1600 ℃ are met, the service temperature is about 400 ℃, and novel protection materials and structures are needed to be developed to supplement the performance gap. The research of developing the ultra-high temperature ablation protection flexible coating and compositing the ultra-high temperature ablation protection flexible coating on the surface of the flexible ceramic fiber fabric to form a novel ultra-high temperature environment service flexible heat protection system is significant.
The heat insulation in the process of re-entering the atmosphere of the spacecraft is a key technology in the design of the spacecraft, and comprises ablation heat insulation, radiation heat insulation, heat insulation and other technologies. The ablation heat insulation is to protect the component by taking away a large amount of heat through a series of physical and chemical reactions such as pyrolysis heat absorption of the surface ablation material in the ablation process, mass injection effect of pyrolysis gas and reradiation of a surface carbon layer. The heat protection device has the advantages of high heat protection efficiency, reliable operation, strong adaptability along with the change of external heat flow, and the like, is widely used for the heat protection of high heat flow parts of various spacecrafts, and can protect the reentry end surface in a flexible coating mode to play a role in ultrahigh temperature heat protection.
Therefore, development of ultra-high temperature ablation protective flexible coating aiming at the environmental condition of re-entering the atmosphere of the spacecraft is needed to overcome the problems.
Disclosure of Invention
The first object of the invention is to provide a flexible thermal protection coating resistant to high-temperature ablation, which has better high-temperature ablation resistance, lower linear ablation rate, low density, low thermal conductivity and low residual stress.
The second purpose of the invention is to provide a preparation method of the high-temperature ablation resistant flexible thermal protection coating, which is simple to operate and low in cost, and the prepared flexible thermal protection coating has good bonding strength with a matrix and a wide application range, and can be applied to the protection of large-size and complex curved structural members.
A third object of the present invention is to provide a method for producing a protective coating for a spacecraft comprising the use of a flexible thermal protective coating as described above. The flexible thermal protection coating is coated on the outer surface of the spacecraft, and can meet the high-temperature ablation of 50-200 s at 1200-1600 ℃.
In order to achieve the first object, the invention adopts the following technical scheme:
the invention provides a high-temperature ablation resistant flexible thermal protection coating, which comprises the following components of a coating matrix, hollow ultrahigh-temperature ceramic micro-nano powder, hollow oxide ceramic micro-nano powder and a reinforcing auxiliary agent in a mass ratio of 1:0.1 to 0.3:0.2 to 0.6:0.01 to 0.1.
The flexible thermal protection coating provided by the invention is specifically designed for special environmental conditions of the spacecraft reentry into the atmosphere, the optimization of the performance of the flexible thermal protection coating is realized through the selection of raw materials and the limitation of a formula in the preparation process, the mechanical property and the oxygen blocking capability of the flexible thermal protection coating are improved, the flexible thermal protection coating has better high-temperature ablation resistance, the service life of the flexible thermal protection coating is prolonged, and the rigid ablation material and the ablation coating are adopted in the traditional process instead, so that effective ablation protection is formed on the surface of the ceramic fiber fabric, and the flexible thermal protection coating can be folded and stored together with a variable-configuration spacecraft, thereby reducing the emission volume and the emission weight of the spacecraft. Meanwhile, the flexible thermal protection coating has the characteristics of light weight and ultrahigh temperature service resistance, and is different from the traditional light thermal protection coating which is used below 1000 ℃ and has the remarkable characteristic of stable service in an ultrahigh temperature section.
Further, the porosity of the hollow ultra-high temperature ceramic micro-nano powder is 5-45%, and the porosity of the hollow oxide ceramic micro-nano powder is 10-50%.
Further, the reinforcing aid comprises chopped ceramic fibers and/or a reinforcing phase. The chopped ceramic fiber mainly improves the thermal stability, the reinforcing phase mainly improves the mechanical property, and the mass ratio of a limiting coating matrix to a reinforcing auxiliary agent in the preparation of the flexible thermal protection coating is 1:0.01 to 0.1, i.e. the sum of the chopped ceramic fibers and the reinforcing phase accounts for 1 to 10% of the coating matrix, and the proportional relationship of the chopped ceramic fibers and the reinforcing phase is not limited in the present application, as long as the reinforcing aid is ensured to be within a defined range of values, it being understood by those skilled in the art that the reinforcing aid may contain only one of the chopped ceramic fibers or the reinforcing phase.
Further, the chopped ceramic fibers comprise one or more of silicon oxide fibers, aluminum oxide fibers, boron nitride fibers, silicon carbide fibers, basalt fibers or quartz fibers, and the chopped ceramic fibers are added to help improve the capability of the coating to resist ultra-high temperature heat flow scouring during the reentry process of the spacecraft.
Further, the reinforcing phase comprises one or more of wood chips, iron oxide red, carbon black, mica, hydroxyl silicone oil or glass powder, and the addition of the reinforcing phase helps to prolong the anti-ablation time of the coating.
Further, the coating matrix is silicon rubber, and the silicon rubber comprises one of methyl vinyl silicon rubber or methyl phenyl silicon rubber with the viscosity of 6000-7000 cp.
The methyl vinyl silicone rubber is cured in a hydrosilylation mode, wherein the vinyl content is 0.035-0.055mol/100g, and the methyl phenyl silicone rubber is dealcoholized and cured by adopting a silicon hydroxyl group and a silane coupling agent under the catalysis of organic tin, wherein the phenyl content is 5-10%.
Further, the raw materials of the hollow ultra-high temperature ceramic micro-nano powder include, but are not limited to, one or more of zirconium boride, silicon carbide, hafnium carbide, zirconium oxide or tantalum oxide.
According to the technical scheme, hollow ultrahigh-temperature ceramic micro-nano powder is added into a silicone rubber matrix as a filler, so that the ablation resistance of the flexible thermal protection coating is improved, the realization of light weight of the coating and the reduction of the thermal conductivity are facilitated, and the coating density is reduced.
Further, the raw materials of the hollow oxide ceramic micro-nano powder include, but are not limited to, one or more of silicon oxide, aluminum oxide, mullite, boron oxide or basalt.
According to the technical scheme, hollow oxide ceramic micro-nano powder is used as a filler to be added into a silicon rubber matrix, the high temperature resistance of the flexible thermal protection coating is improved, the self-stiffening capacity of the coating in the reentry process of the spacecraft is improved, and the improvement of rigidity in the reentry process is favorable for the improvement of the reliability of the thermal protection system.
The ceramic micro-nano powder raw materials, namely zirconium boride, silicon carbide, hafnium carbide, zirconium oxide, tantalum oxide, silicon oxide, aluminum oxide, mullite, boron oxide and basalt are all commercial products, and can be purchased from commercial sources, the purity is more than or equal to 99.9%, and the granularity is 0.5-5 mu m.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a high-temperature ablation resistant flexible thermal protection coating, which comprises the following steps:
(1) Selecting a raw material of hollow ultra-high temperature ceramic and a raw material of hollow oxide ceramic, respectively mixing the raw materials with a binder through wet ball milling, spray drying, then carrying out inductive plasma spheroidization or plasma sintering on the hollow ultra-high temperature ceramic micro-nano agglomerated powder and the hollow oxide ceramic micro-nano agglomerated powder to obtain hollow ultra-high temperature ceramic micro-nano powder and hollow oxide ceramic micro-nano powder, and carrying out vacuum drying for later use;
(2) Mixing the coating matrix, the hollow ultrahigh-temperature ceramic micro-nano powder, the hollow oxide ceramic micro-nano powder and the reinforcing auxiliary agent according to a formula to obtain high-temperature ablation resistant coating slurry;
(3) And preparing a high-temperature ablation resistant flexible thermal protection coating with the total thickness of 0.2-5 mm on the surface of the substrate by brushing or spraying the coating slurry, and then placing the coating slurry into an oven for drying and curing. Further, in the step (1), the binder is selected from polyvinyl alcohol solution with the concentration of 0.2-2%, and the mass ratio of the raw materials to the binder is 10: 1-20: 1, preparing, wherein the particle size of the hollow ultra-high temperature ceramic micro-nano agglomerated powder and the hollow oxide ceramic micro-nano agglomerated powder is 10-100 um, which is favorable for the dispersion of the powder in the solution, and the condition of inductive plasma spheroidization is as follows: main gas: 30-60 SCFH, auxiliary gas: 3-7 SCFH, powder feeding rate: 2-6 RPM, the conditions of the plasma sintering are as follows: the sintering temperature is 1500-2400 ℃, the sintering time is 12-24 hours, and the substrate in the step (3) is a silicon carbide ceramic fiber fabric, an aluminum oxide ceramic fiber fabric, a carbon fiber fabric, a quartz fiber fabric, a boron nitride fiber fabric and other high Wen Fuyi fiber fabrics.
Further, the drying and curing conditions in the step (3) are that the drying temperature is 200-300 ℃ and the drying time is 12-48 hours.
Further, the drying and curing conditions in the step (3) are that the drying temperature is 60-200 ℃ and the drying time is 5-7d.
In order to achieve the third object, the present invention adopts the following technical scheme:
the invention provides an application of the flexible thermal protection coating as a spacecraft protection coating, wherein the flexible thermal protection coating is coated on the outer surface of a spacecraft, the application environment of the flexible thermal protection coating is 1200-1600 ℃, and the high-temperature ablation resistant time is 50-200 s.
Further, the outer surface of the spacecraft is coated with a flexible heat protection coating with the layer number more than or equal to 1; when the number of layers is more than or equal to 2, the total content of the hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder contained in the coating of each layer is in an increasing trend, and the total content of the outer layer hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder is higher than that of the inner layer.
According to the specific embodiment of the invention, the coating slurry is required to be brushed or sprayed for multiple times to form the flexible thermal protection coating with the number of layers being more than or equal to 1 layer, the thickness of each layer is about 0.2mm according to measurement, a person skilled in the art can select the number of layers for brushing or spraying according to practical application requirements, and the fact that the total content of the hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder in each layer of coating is different, the total content of the hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder near one side of the substrate is less, the total content of the hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder near the outer side is more, the total content shows a trend of increasing from inside to outside, and the components of the hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder of each layer can be the same or different. The ablation gradient structure formed by adopting the design is more beneficial to improving the ablation resistance, has the effects of slowly releasing stress, effectively resisting oxygen and improving mechanical properties, reduces the thermal stress in the heating and cooling processes of the coating, improves the bonding strength between the coating and the matrix, improves the stability of a thermal protection system, and is beneficial to gradient matching of structural functions and reduces the density of the coating by designing the coating into a form that the content of an ultrahigh-temperature area on the surface of the coating is large and the content of one side close to the matrix is small.
The invention takes silicon rubber as a coating matrix, takes hollow ultra-high temperature ceramic and hollow oxide ceramic micro-nano powder prepared by a specific process as a filler, takes chopped ceramic fiber and other reinforcing phases as mechanical property improving materials, forms coating slurry by stirring and dispersing, forms a flexible thermal protection coating with a certain thickness on the surface of a matrix by brushing or spraying, forms an ablation gradient structure by adjusting the component proportion of the slurry, and obtains a uniform and stable flexible thermal protection coating by a curing process.
The beneficial effects of the invention are as follows:
the flexible thermal protection coating provided by the invention has better high-temperature ablation resistance, can meet the high-temperature ablation of 50-200 s at 1200-1600 ℃ when the total thickness of the coating is 0.2-5 mm, has the characteristics of low density, low heat conductivity and low residual stress, further enhances the beneficial effects of the flexible thermal protection coating in the aspect of thermal stress matching in the loading heating and cooling processes after adopting the design of an ablation gradient structure, and simultaneously is beneficial to the realization of light weight of the coating due to the addition of the hollow ultra-high temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder. The invention also discloses a preparation method of the high-temperature ablation resistant flexible thermal protection coating, which is simple and convenient to operate, has the bonding strength of 20MPa with the substrate, has the bonding strength equivalent to that of a thermal spraying coating, has a wide application range, and can be used for preparing and protecting the coating of a large-size and complex curved structural member.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows a schematic diagram of a high temperature ablation resistant flexible thermal protective coating structure provided by the invention.
Detailed Description
In order to further understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise specified, all reagents involved in the examples of the present invention are commercially available products and are commercially available.
Example 1
(1) Zirconium boride and silicon carbide are selected as hollow ultrahigh-temperature ceramic raw material powder, silicon oxide and aluminum oxide are selected as hollow oxide ceramic raw material powder, polyvinyl alcohol is adopted as a particle binder, and the two ceramic raw material powder and the hollow oxide ceramic raw material powder are respectively mixed with the raw material powder. Powder mixing is carried out in a wet ball milling mode to prepare uniform and stable slurry, and then spray drying treatment is carried out on the slurry to prepare the hollow ultra-high temperature ceramic micro-nano agglomerated powder and the hollow oxide ceramic micro-nano agglomerated powder with the particle size of 10-100 mu m. Then preparing hollow ultra-high temperature ceramic micro-nano powder and hollow oxide ceramic micro-nano powder by induction plasma spheroidization (the plasma spheroidization condition is that the main gas is 45SCFH, the auxiliary gas is 4SCFH, and the powder feeding rate is 4 RPM), drying in a vacuum drying oven at 200 ℃ for 3 hours for later use;
(2) Weighing methyl vinyl silicone rubber, curing by adopting a hydrosilylation mode, wherein the viscosity is 6000cP, and the mass ratio of the coating matrix to the hollow ultrahigh-temperature ceramic micro-nano powder to the hollow oxide ceramic micro-nano powder to the reinforcing auxiliary agent is 1:0.19:0.29:0.02, preparing an innermost coating slurry formula, wherein the mass ratio of the chopped ceramic fiber to the reinforcing phase in the reinforcing auxiliary agent is 10:1, the chopped ceramic fiber is silicon carbide fiber, the reinforcing phase comprises wood dust, iron oxide red, carbon black, mica, hydroxyl silicone oil and glass powder, all substances in the reinforcing phase are added in equal proportion, and uniformly mixed by a planetary ball mill to form uniform and stable ablative coating slurry;
(3) The method comprises the steps of brushing 10 layers by a gradient component control method, preparing the contents of hollow ultrahigh-temperature ceramic micro-nano powder and hollow oxide ceramic micro-nano powder in a gradient increasing way of 0.5% of each layer, preparing an ultrahigh-temperature ablation protective flexible coating with the total thickness of 2mm on the surface of a ceramic fiber fabric substrate by utilizing a pneumatic spraying mode, and drying and curing the ultrahigh-temperature ablation protective flexible coating and the ceramic fiber fabric substrate in a blast oven at 300 ℃ for 20 hours.
Example 2
Referring to the preparation steps of example 1, only the raw material powder of the hollow oxide ceramic micro-nano powder is changed into the combination of mullite and boron oxide, the hollow ultra-high temperature ceramic micro-nano powder is obtained by plasma sintering at a sintering temperature of 1800 ℃ for 12 hours, the vacuum drying condition is changed into a drying temperature of 200 ℃ for 2 hours, and the mass ratio of the coating matrix, the hollow ultra-high temperature ceramic micro-nano powder, the hollow oxide ceramic micro-nano powder and the reinforcing auxiliary agent is changed into 1:0.15:0.3:0.03, chopped ceramic fiber is changed into silicon oxide fiber and aluminum oxide fiber according to the proportion of 3:1, mixing, wherein the reinforcing phase is changed into wood dust, iron oxide red, carbon black, mica and hydroxyl silicone oil according to the wood dust: iron oxide red: carbon black: mica: the mass ratio of the hydroxyl silicone oil is 1:2:3:1:1, preparing, namely changing the total thickness of the ultra-high temperature ablation protective flexible coating into 15 layers which are 3mm, gradually increasing the contents of the hollow ultra-high temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder according to the gradient of 0.375% of each layer, drying and curing for 7 days at 70 ℃, and other parameters being the same as those of the embodiment 1.
Example 3
Referring to the preparation steps of example 1, only the vacuum drying condition is changed to the drying temperature of 200 ℃ and the drying time of 4 hours, and the mass ratio of the coating matrix, the hollow ultra-high temperature ceramic micro-nano powder, the hollow oxide ceramic micro-nano powder and the reinforcing auxiliary agent is changed to 1:0.19:0.19: and 0.05, selecting boron nitride fiber as the chopped ceramic fiber, and drying and curing at 200 ℃ for 24 hours, wherein other parameters are the same as those of the embodiment 1.
Example 4
Referring to the preparation steps of example 1, only the raw material powder of the hollow ultra-high temperature ceramic micro-nano powder is changed into the combination of zirconia and tantalum oxide, the raw material powder of the hollow oxide ceramic micro-nano powder is changed into the combination of mullite and basalt, the vacuum drying condition is changed into the drying temperature of 180 ℃, the drying time is 2 hours, and the mass ratio of the coating matrix, the hollow ultra-high temperature ceramic micro-nano powder, the hollow oxide ceramic micro-nano powder and the reinforcing auxiliary agent is changed into 1:0.1:0.3:0.02, the reinforcing phase is changed into wood dust, iron oxide red, carbon black, mica and hydroxyl silicone oil, and the wood dust is used as follows: iron oxide red: carbon black: mica: the mass ratio of the hydroxyl silicone oil is 1:2:3:1:1, preparing, namely changing the total thickness of the ultra-high temperature ablation protective flexible coating into 4 layers which are 0.8mm, gradually increasing the contents of the hollow ultra-high temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder according to the gradient of 0.75% of each layer, drying and curing for 24 hours at 200 ℃, and other parameters being the same as those of the embodiment 1.
Experimental example 1
The flexible thermal protective coatings of examples 1-4 were subjected to ablative assessment tests with reference to the national military standard GJB323B-2018, and the results are shown in table 1. As shown in Table 1, the flexible thermal protection coatings prepared in examples 1-4 have high-temperature ablation resistance of 50-200 s at 1200-1600 ℃, have low linear ablation rate, and have high bonding strength with a substrate, and particularly the flexible thermal protection coating prepared in example 2 can realize high-temperature ablation of 200s at 1600 ℃ on the combination of a proper formula composition and a gradient spraying process.
Figure BDA0003454699780000071
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (9)

1. The application of the flexible thermal protection coating resistant to high-temperature ablation in the aspect of being used as a spacecraft protection coating is characterized in that the flexible thermal protection coating is coated on the outer surface of a spacecraft, the application environment of the flexible thermal protection coating is 1200-1600 ℃, the high-temperature ablation resistant time is 50-200 s, the line ablation rate is 0.005-0.06mm/s, and the total thickness of the flexible thermal protection coating is 0.2-5 mm;
the components of the flexible thermal protection coating comprise a coating matrix, hollow ultrahigh temperature ceramic micro-nano powder, hollow oxide ceramic micro-nano powder and a reinforcing auxiliary agent, wherein the mass ratio of the coating matrix to the hollow ultrahigh temperature ceramic micro-nano powder to the hollow oxide ceramic micro-nano powder to the reinforcing auxiliary agent is 1:0.1 to 0.3:0.2 to 0.6:0.01 to 0.1;
wherein the porosity of the hollow ultra-high temperature ceramic micro-nano powder is 5% -45%, and the porosity of the hollow oxide ceramic micro-nano powder is 10% -50%;
the hollow ultra-high temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder are prepared according to the following method:
selecting a raw material of hollow ultra-high temperature ceramic and a raw material of hollow oxide ceramic, respectively mixing the raw materials with a binder through wet ball milling, spray drying, then carrying out inductive plasma spheroidization or plasma sintering on the hollow ultra-high temperature ceramic micro-nano agglomerated powder and the hollow oxide ceramic micro-nano agglomerated powder to obtain hollow ultra-high temperature ceramic micro-nano powder and hollow oxide ceramic micro-nano powder, and carrying out vacuum drying for later use;
the coating matrix is silicon rubber; the silicone rubber comprises one of methyl vinyl silicone rubber or methyl phenyl silicone rubber with the viscosity of 6000-7000 cp;
the reinforcing aid comprises chopped ceramic fibers and a reinforcing phase;
the chopped ceramic fibers comprise one or more of silicon oxide fibers, aluminum oxide fibers, boron nitride fibers, silicon carbide fibers, basalt fibers or quartz fibers; the reinforcing phase comprises one or more of wood dust, iron oxide red, carbon black, mica, hydroxyl silicone oil or glass powder;
the raw materials of the hollow ultra-high temperature ceramic micro-nano powder comprise one or more of zirconium boride, silicon carbide, hafnium carbide, zirconium oxide or tantalum oxide;
the raw materials of the hollow oxide ceramic micro-nano powder comprise one or more of silicon oxide, aluminum oxide, mullite, boron oxide or basalt;
the outer surface of the spacecraft is coated with a flexible heat protection coating with the layer number more than or equal to 2; when the number of layers is more than or equal to 2, the total content of the hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder contained in the coating of each layer is in an increasing trend, and the total content of the outer layer hollow ultrahigh-temperature ceramic micro-nano powder and the hollow oxide ceramic micro-nano powder is higher than that of the inner layer.
2. The use according to claim 1, wherein the flexible thermal protective coating is prepared by:
(1) Selecting a raw material of hollow ultra-high temperature ceramic and a raw material of hollow oxide ceramic, respectively mixing the raw materials with a binder through wet ball milling, spray drying, then carrying out inductive plasma spheroidization or plasma sintering on the hollow ultra-high temperature ceramic micro-nano agglomerated powder and the hollow oxide ceramic micro-nano agglomerated powder to obtain hollow ultra-high temperature ceramic micro-nano powder and hollow oxide ceramic micro-nano powder, and carrying out vacuum drying for later use;
(2) Mixing the coating matrix, the hollow ultrahigh-temperature ceramic micro-nano powder, the hollow oxide ceramic micro-nano powder and the reinforcing auxiliary agent to obtain high-temperature ablation resistant coating slurry;
(3) And preparing a high-temperature ablation resistant flexible thermal protection coating with the total thickness of 0.2-5 mm on the surface of the substrate by brushing or spraying the coating slurry, and then placing the coating slurry into an oven for drying and curing.
3. The use according to claim 2, wherein the drying and curing conditions in step (3) are a drying temperature of 200 to 300 ℃ and a drying time of 12 to 48 hours.
4. The use according to claim 2, wherein the drying and curing conditions in step (3) are a drying temperature of 60-200 ℃ and a drying time of 5-7d.
5. The use according to claim 2, wherein the binder is selected from polyvinyl alcohol solutions with a concentration of 0.2-2%.
6. The use according to claim 2, wherein the raw materials and the binder are in a mass ratio of 10: 1-20: 1, preparing.
7. The application of claim 2, wherein the particle size of the hollow ultra-high temperature ceramic micro-nano agglomerated powder and the hollow oxide ceramic micro-nano agglomerated powder is 10-100 μm.
8. The use according to claim 2, wherein the conditions for inductive plasma spheroidization are: main gas: 30-60 SCFH, auxiliary gas: 3-7 SCFH, powder feeding rate: 2-6 RPM.
9. The use according to claim 2, wherein the conditions of the plasma sintering are: the sintering temperature is 1500-2400 ℃, and the sintering time is 12-24 h.
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