An organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation and its preparation method and application

Abstract

The present invention relates to an organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation, as well as its preparation method and application. The material comprises an inner layer of low-density composite material and a surface high-density organic-inorganic hybrid composite material. The inner layer of low-density composite material comprises a micron-porous pure phenolic aerogel as a matrix and a quartz fiber preform as a reinforcement, while the surface high-density organic-inorganic hybrid composite material comprises an organic-inorganic hybrid nanoporous phenolic aerogel as a matrix and a carbon fiber preform as a reinforcement. Compared with the prior art, the organic-inorganic hybrid thermal protection material prepared by the present invention has the advantages of low linear ablation rate, lightweight thermal insulation, and low residue generation during ablation in a discrete interval gas ablation environment. It can be applied to internal insulation structures such as gas pipelines and valve cavities of attitude and orbit control engines with discrete interval startup.

Description

Technical Field

[0001] The present invention relates to the technical field of thermal protection materials, and in particular to an organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation, and a preparation method and application thereof. Background Art

[0002] The attitude and orbit control engine is a power device for controlling the attitude and orbit of an aircraft that is started at discrete intervals. It is the core execution system that ensures the maneuverability of the aircraft. This engine has the characteristics of multiple discrete interval starts, high gas flow temperature, and high gas pressure, and its service environment is extremely harsh. Internal insulation structures such as gas pipelines and nozzles are in direct contact with high-temperature and high-pressure gas flows and need to have ablation resistance and heat insulation properties. In addition, during the discrete interval ablation process, traditional resin-based internal insulation materials are subjected to the action of high-temperature gas flows, and will undergo continuous cracking and carbonization reactions. The carbonized layer is easily flushed by subsequent pulsed gas flows and easily produces residues, which in turn causes valve blockage. Therefore, the development of thermal protection materials that are ablation-resistant, heat-insulating, and not prone to producing residues during ablation is an urgent need in this field. Summary of the Invention

[0003] The purpose of the present invention is to provide an organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation and its preparation method and application, the material has the advantages of low density, low thermal conductivity, ablation resistance and the like.

[0004] The object of the present invention can be achieved by the following technical solutions: an organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation, comprising an inner layer of low-density composite material and a surface high-density organic-inorganic hybrid composite material;

[0005] The inner layer low-density composite material uses micron-porous pure phenolic aerogel as a matrix and a quartz fiber preform as a reinforcement, while the surface high-density organic-inorganic hybrid composite material uses organic-inorganic hybrid nanoporous phenolic aerogel as a matrix and a carbon fiber preform as a reinforcement.

[0006] In this invention, the organic-inorganic hybrid phenolic resin exhibits superior ablation resistance compared to pure phenolic resin, and forms a molten layer during ablation, preventing the formation of ablation residues. The nanoporous phenolic aerogel particles have excellent stress-buffering properties, mitigating the thermal stress generated during discrete-interval ablation, further preventing the formation of ablation residues.

[0007] Preferably, the thickness of the inner layer low-density composite material is 50% to 80% of the total thickness (i.e., the thickness of the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation), and the thickness of the surface high-density organic-inorganic hybrid composite material is 20% to 50% of the total thickness.

[0008] Preferably, the density of the inner layer low-density composite material is 0.4-0.7 g / cm 3 .

[0009] Preferably, the surface high-density organic-inorganic hybrid composite material has a density of 1.1 to 1.5 g / cm 3 .

[0010] Preferably, a transition layer is formed between the inner low-density composite material and the surface high-density organic-inorganic hybrid composite material.

[0011] Preferably, the pore size of the microporous pure phenolic aerogel is 5 to 30 μm.

[0012] Preferably, the pore size of the nanoporous organic-inorganic hybrid phenolic aerogel is 30 to 100 nm.

[0013] Preferably, the microporous pure phenolic aerogel is made of pure phenolic resin that is thermosetting and has a mass average molecular weight greater than 1000.

[0014] In the present invention, the thermosetting phenolic resin with a large mass average molecular weight is more likely to form micropores during the curing reaction.

[0015] Further preferably, the microporous pure phenolic aerogel uses one or more of ethylene glycol, ethanol, and cyclohexane as solvent.

[0016] More preferably, the solvent accounts for 40% to 70% of the total mass of the pure phenolic resin solution.

[0017] Preferably, the quartz fiber preform is a needle-punched quartz fiber preform.

[0018] Further preferably, the needle-punched quartz fiber preform includes a needle-punched quartz mesh preform and a needle-punched quartz cloth / mesh preform.

[0019] Preferably, the density of the quartz fiber preform is 0.3-0.5 g / cm 3 .

[0020] Preferably, the organic-inorganic hybrid nanoporous phenolic aerogel matrix uses a silicon hybrid phenolic resin obtained by polymerization of thermoplastic phenolic resin and thermoplastic dimethyl polysilane as a raw material.

[0021] Further preferably, the preparation method of the silicon-hybrid phenolic resin comprises the following steps:

[0022] Thermoplastic phenolic resin, thermoplastic dimethyl polysilane, solvent and hexamethylenetetramine are mixed and stirred to obtain silicon hybrid phenolic resin through polymerization reaction.

[0023] More preferably, the polymerization reaction temperature is 45-55°C.

[0024] More preferably, the polymerization reaction time is 20 to 30 hours.

[0025] More preferably, the hexamethylenetetramine accounts for 2-4% of the total mass of the thermoplastic phenolic resin and thermoplastic dimethylpolysilane.

[0026] More preferably, the mass average molecular weight of the thermoplastic phenolic resin is less than 800.

[0027] More preferably, the mass average molecular weight of the thermoplastic dimethylpolysilane is less than 2000.

[0028] In the present invention, the silicon-hybridized phenolic resin obtained by hybridizing thermoplastic phenolic resin with a small mass average molecular weight and thermoplastic dimethyl polysilane is more likely to form nanopores during the curing reaction process.

[0029] Further preferably, the organic-inorganic hybrid nanoporous phenolic aerogel uses one or more of ethylene glycol, ethanol, and cyclohexane as solvent.

[0030] More preferably, the solvent accounts for 50% to 60% of the total mass of the silicon-hybrid phenolic resin solution.

[0031] Preferably, the carbon fiber preform is a braided carbon fiber preform.

[0032] In the present invention, the braided carbon fiber preform has better ablation resistance and surface bonding strength than the needle-punched quartz fiber preform, which is beneficial to improving the ablation resistance of the composite material and preventing the generation of ablation residues.

[0033] Further preferably, the braided structure carbon fiber preform includes a 2.5D carbon fiber preform, an orthogonal three-directional carbon fiber preform, a three-dimensional four-directional carbon fiber preform, and a three-dimensional five-directional carbon fiber preform.

[0034] Preferably, the carbon fiber preform has a density of 1.0 to 1.3 g / cm 3 .

[0035] Preferably, the method for preparing the inner layer low-density composite material comprises the following steps:

[0036] S1: Select a needle-punched quartz fiber preform and a thermosetting phenolic resin solution with added solvent as raw material;

[0037] S2: Thermosetting phenolic resin is injected into the needle-punched quartz fiber preform through the RTM process and cured to obtain an inner layer of low-density composite material.

[0038] Further preferably, the RTM process in step S2 comprises the following steps:

[0039] The needle-punched quartz fiber preform is placed in a mold, and after the mold is closed, a thermosetting phenolic resin solution with added solvent is injected into the mold with an injection pressure of 0.5-0.7 MPa and a curing temperature of 85-95°C.

[0040] Further preferably, in step S2, drying is performed after curing, with a drying temperature of 110 to 130° C. and a drying time of 20 to 30 hours to obtain an inner layer low-density composite material.

[0041] Preferably, the method for preparing the surface high-density organic-inorganic hybrid composite material comprises the following steps:

[0042] S1: Select a braided carbon fiber preform and a solvent-added silicon-hybrid phenolic resin as the raw material;

[0043] S2: Through the RTM process, the silicon-hybrid phenolic resin solution is injected into the woven carbon fiber preform and cured to obtain a surface high-density composite material.

[0044] Further preferably, the RTM process in step S2 comprises the following steps:

[0045] The inner layer low-density composite material and the woven carbon fiber preform are placed in a mold, the woven carbon fiber preform is laid on the surface of the inner layer low-density composite material, and after the mold is closed, a silicon-hybrid phenolic resin solution with added solvent is injected into the woven carbon fiber preform in the mold.

[0046] Further preferably, in the RTM process in step S2, the injection pressure is 0.5-0.7 MPa, and the curing temperature is 85-95°C.

[0047] More preferably, in step S2, the material is dried after curing, with the drying temperature being 110-130° C. and the drying time being 20-30 h to obtain a surface high-density composite material.

[0048] A method for preparing the above-mentioned organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation comprises the following steps:

[0049] Roughening the surface of the inner layer of low-density composite material;

[0050] A surface high-density organic-inorganic hybrid composite material is prepared on the rough surface of the inner low-density composite material to obtain the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation.

[0051] Preferably, the surface of the inner layer of low-density composite material is roughened by an abrasive jetting method.

[0052] Further preferably, the abrasive particles are spherical SiO2 particles with a particle size of 100 to 200 μm.

[0053] More preferably, the abrasive jetting method comprises the following steps:

[0054] S1: Spherical SiO2 particles with a particle size of 100-200 μm are selected as abrasive;

[0055] S2: Spraying SiO2 particles onto the surface of the low-density composite material by means of oscillating pressure to perform surface roughening treatment.

[0056] Further preferably, the abrasive jetting pressure is an oscillating pressure, the set pressure is 0.2-0.6 MPa, the pressure alternating amplitude is 5%-10% of the set pressure value, and the alternating frequency is 0.1-0.5 Hz.

[0057] In the present invention, the use of pressure oscillating at a certain amplitude and frequency is beneficial to improving the roughness of the surface of the low-density composite material.

[0058] Further preferably, the abrasive jetting has a jetting angle of 45 to 90°, a jetting distance of 10 to 30 cm, and a jetting time of 5 to 10 minutes.

[0059] Preferably, the preparation method comprises the following steps:

[0060] First, an inner layer of low-density composite material is prepared using micron-porous pure phenolic aerogel as a matrix and a needle-punched quartz cloth / mesh fiber preform as a reinforcement. Then, the surface of the low-density composite material is roughened by an abrasive jetting method. Finally, a woven carbon fiber preform is laid on the roughened surface of the low-density composite material, and a surface high-density composite material is prepared using organic-inorganic hybrid nanoporous phenolic aerogel as a matrix. Thus, an integrated composite material with low internal density and high surface density is obtained, namely, the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation.

[0061] In this invention, the inner layer of the low-density composite material uses pure phenolic aerogel as the matrix and needle-punched quartz fiber preforms as the reinforcement. Pure phenolic aerogel has lower thermal conductivity than organic-inorganic hybrid phenolic aerogel, and needle-punched quartz fiber preforms have even lower thermal conductivity than other fiber preforms such as carbon fiber. Both contribute to the thermal insulation performance of the inner layer of the low-density composite material.

[0062] In this invention, the inner low-density composite material uses microporous pure phenolic aerogel as its matrix. Compared to nanoporous aerogel, microporous aerogel has greater roughness and larger pore size. This allows the resin solution to better penetrate the inner low-density composite material during the preparation of the surface high-density composite material. This facilitates the formation of a transition layer between the inner low-density composite material and the surface high-density composite material, improving interfacial strength.

[0063] In the present invention, the surface of the low-density composite material is roughened by an abrasive jetting method, which is beneficial to further improve the roughness, thereby being more conducive to forming a transition layer and improving the interface layer strength between the inner low-density composite material and the surface high-density composite material.

[0064] An application of the above-mentioned organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation is to use the material as an insulation material in an attitude and orbit control engine.

[0065] Preferably, the material is used for the gas pipelines and valve chambers of attitude and orbit control engines.

[0066] Further preferably, the inner layer low-density composite material is arranged on the side not in contact with the gas, and the surface high-density organic-inorganic hybrid composite material is arranged on the side in contact with the gas.

[0067] Compared with the prior art, the present invention has the following beneficial effects:

[0068] 1. The present invention proposes an organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation and a preparation method thereof, which can solve the problems of insufficient thermal insulation and ablation resistance of traditional resin-based internal insulation materials used in attitude and orbit control engines, and the easy generation of residues during ablation.

[0069] 2. The present invention adopts an integrated composite material design method with a low-density composite material on the inner layer and a high-density composite material on the surface, which can make the composite material have the integrated functions of low density, low thermal conductivity, ablation resistance, and no residue generation during ablation.

[0070] 3. The inner layer low-density composite material of the present invention adopts micron-porous pure phenolic aerogel as the matrix, which is beneficial to the preparation process of the surface high-density composite material. The resin solution can better penetrate into the inner layer low-density composite material to form a transition layer, thereby improving the interface strength between the low-density composite material and the high-density composite material to ensure that the material does not undergo stratification and damage in the environment of multiple high-temperature and high-pressure gas discrete interval ablation.

[0071] 4. The abrasive jetting process of the present invention uses a pressure oscillating at a certain amplitude and frequency, which is beneficial to improving the surface roughness of the low-density composite material, thereby improving the interface strength between the low-density composite material and the high-density composite material.

[0072] 5. The present invention uses woven carbon fibers as reinforcement and an organic-inorganic hybrid phenolic resin as a matrix to prepare a surface-high-density composite material. Compared to pure phenolic resin, the organic-inorganic hybrid phenolic resin has better ablation resistance and forms a molten layer during the ablation process, which can prevent the formation of ablation residues. The woven carbon fiber preform has superior ablation resistance and surface bonding strength, which helps improve the ablation resistance of the composite material and prevent the formation of ablation residues.

[0073] 6. The organic-inorganic hybrid thermal protection material prepared by the present invention has the advantages of low linear ablation rate, lightweight thermal insulation, and no residue generation during ablation under a discrete interval gas ablation environment. It can be applied to internal insulation structures such as gas pipelines and valve cavities of attitude and orbit control engines with discrete interval starting. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 This is a schematic structural diagram of an organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to the present invention;

[0075] Figure 2 This is a photo of the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0076] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0077] An organic-inorganic hybrid thermal protection material resistant to discrete-interval gas ablation and its preparation method include: first, preparing an inner layer of low-density composite material using microporous pure phenolic aerogel as a matrix and a needle-punched quartz fiber preform as reinforcement; then, roughening the surface of the low-density composite material using abrasive jetting; and finally, preparing a high-density organic-inorganic hybrid composite material on the surface of the low-density composite material. This results in the organic-inorganic hybrid thermal protection material resistant to discrete-interval gas ablation.

[0078] As a preferred solution, the microporous pure phenolic aerogel uses thermosetting pure phenolic resin with a mass average molecular weight greater than 1000 as raw material, and uses one or more of ethylene glycol, ethanol, and cyclohexane as solvent, with the solvent accounting for 40% to 70% of the total solution mass.

[0079] As a preferred solution, the needle-punched quartz fiber preform includes a needle-punched quartz mesh preform and a needle-punched quartz cloth / mesh preform, and the preform density is 0.3-0.5 g / cm 3 .

[0080] As a preferred solution, spherical SiO2 particles with a particle size of 100 to 200 μm are selected as abrasives.

[0081] As a preferred solution, SiO2 particles are sprayed onto the surface of the low-density composite material by means of oscillating pressure to perform surface roughening treatment.

[0082] As a preferred solution, the injection pressure is not a constant value but an oscillating pressure, the set pressure is 0.2-0.6 MPa, the pressure alternating amplitude is 5%-10% of the set pressure value, and the alternating frequency is 0.1-0.5 Hz.

[0083] As a preferred solution, the abrasive jetting has a jetting angle of 45 to 90°, a jetting distance of 10 to 30 cm, and a jetting time of 5 to 10 minutes.

[0084] As a preferred solution, the surface high-density composite material uses a solvent-added silicon-hybridized phenolic resin as a raw material and a braided carbon fiber preform as a reinforcement.

[0085] As a preferred embodiment, in the solvent-added silicon-hybrid phenolic resin solution, the mass average molecular weight of the thermoplastic phenolic resin is less than 800, and the mass average molecular weight of the thermoplastic dimethylpolysilane is less than 2000. The solvent comprises one or more of ethylene glycol, ethanol, and cyclohexane, and the solvent accounts for 50% to 60% of the total solution mass.

[0086] As a preferred solution, the braided carbon fiber preform includes a 2.5D carbon fiber preform, an orthogonal three-directional carbon fiber preform, a three-dimensional four-directional carbon fiber preform, and a three-dimensional five-directional carbon fiber preform, and the preform density is 1.0 to 1.3 g / cm 3 .

[0087] The following describes it in detail with reference to specific embodiments.

[0088] The thermosetting phenolic resin used is 9003-35-4 produced by Zhengzhou Hengtong Chemical Co., Ltd.

[0089] The thermoplastic phenolic resin used was product 65733-76-8 purchased from Huayuan.com.

[0090] The thermoplastic dimethyl polysilane used is product 28883-63-8 produced by Shanghai Aladdin Biochemical Technology Co., Ltd.

[0091] Other reagents, methods, instruments and equipment are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0092] The preparation method of the silicon-hybridized phenolic resin used in the following examples includes the following steps:

[0093] Thermoplastic phenolic resin, thermoplastic dimethyl polysilane, solvent and hexamethylenetetramine were placed in a beaker and stirred for 24 hours at a stirring temperature of 50° C. The mass of hexamethylenetetramine accounted for 3% of the total mass of the thermoplastic phenolic resin and thermoplastic dimethyl polysilane.

[0094] Example 1

[0095] Step 1. Select thermosetting phenolic resin as raw material and ethylene glycol as solvent, with the solvent accounting for 40% of the total solution mass.

[0096] Step 2. Select a needle-punched quartz mesh preform with a density of 0.3g / cm 3 , thickness is 8mm.

[0097] Step 3. Prepare the inner layer of low-density composite material using the RTM process. Place the needle-punched quartz mesh preform in the mold. After closing the mold, inject the phenolic resin solution into the mold at an injection pressure of 0.6 MPa, a curing temperature of 90°C, a drying temperature of 120°C, and a drying time of 24 hours to produce an inner layer of low-density composite material with a thickness of 8 mm.

[0098] Step 4. Roughen the surface of the low-density composite material using abrasive jetting. Spherical SiO2 particles with a particle size of 100 μm were used as the abrasive. The jet pressure was not constant but oscillating, with a set pressure of 0.2 MPa, a pressure alternation amplitude of 5% of the set pressure value, and an alternation frequency of 0.1 Hz. The jet angle was 45°, the jet distance was 10 cm, and the jet time was 5 minutes.

[0099] Step 5. Select thermoplastic phenolic resin and thermoplastic dimethyl polysilane as raw materials, select ethylene glycol as solvent, and the solvent accounts for 50% of the total solution mass to prepare silicon hybrid phenolic resin.

[0100] Step 6. Select a 2.5D carbon fiber preform with a density of 1.0 g / cm 3 , thickness is 2mm.

[0101] Step 7. Using the RTM process as in step 3, a high-density composite material with a thickness of 2 mm is prepared on the surface of the low-density inner layer to obtain an integrated composite material with low internal density and high surface density, namely the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation.

[0102] Example 2

[0103] Step 1. Select thermosetting phenolic resin as raw material and ethanol as solvent, with the solvent accounting for 70% of the total solution mass.

[0104] Step 2. Select a needle-punched quartz cloth / mesh preform with a density of 0.5g / cm 3 , thickness is 7mm.

[0105] Step 3. Prepare the inner layer of low-density composite material using the RTM process. Place the needle-punched quartz mesh preform in the mold. After closing the mold, inject the phenolic resin solution into the mold at an injection pressure of 0.6 MPa, a curing temperature of 90°C, a drying temperature of 120°C, and a drying time of 24 hours to produce an inner layer of low-density composite material with a thickness of 7 mm.

[0106] Step 4. Roughen the surface of the low-density composite material using abrasive jetting. Spherical SiO2 particles with a particle size of 200 μm were used as the abrasive. The jet pressure was not constant but oscillating, set at 0.6 MPa, with a pressure alternation amplitude of 10% of the set pressure value and an alternating frequency of 0.5 Hz. The jet angle was 90°, the jet distance was 30 cm, and the jet time was 10 minutes.

[0107] Step 5. Select thermoplastic phenolic resin and thermoplastic dimethylpolysilane as raw materials, select cyclohexane as solvent, and the solvent accounts for 60% of the total solution mass to prepare silicon hybrid phenolic resin.

[0108] Step 6. Select a three-dimensional five-directional carbon fiber preform with a density of 1.3g / cm 3 , thickness is 3mm.

[0109] Step 7. Using the RTM process as in step 3, a high-density composite material with a thickness of 3 mm is prepared on the surface of the low-density inner layer to obtain an integrated composite material with low internal density and high surface density, namely the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation.

[0110] Example 3

[0111] Step 1. Select thermosetting phenolic resin as raw material and ethanol as solvent, with the solvent accounting for 50% of the total solution mass.

[0112] Step 2. Select a needle-punched quartz mesh preform with a density of 0.4g / cm 3 , thickness is 6mm.

[0113] Step 3. Prepare the inner layer of low-density composite material using the RTM process. Place the needle-punched quartz mesh preform in a mold. After closing the mold, inject the phenolic resin solution into the mold at an injection pressure of 0.6 MPa, a curing temperature of 90°C, a drying temperature of 120°C, and a drying time of 24 hours to produce a 6mm thick inner layer of low-density composite material.

[0114] Step 4. Roughen the surface of the low-density composite material using abrasive jetting. Spherical SiO2 particles with a particle size of 150 μm were used as the abrasive. The jet pressure was not constant but oscillating, set at 0.4 MPa, with a pressure alternating amplitude of 7% of the set pressure value and an alternating frequency of 0.3 Hz. The jet angle was 60°, the jet distance was 20 cm, and the jet time was 7 minutes.

[0115] Step 5. Select thermoplastic phenolic resin and thermoplastic dimethyl polysilane as raw materials, select ethanol as solvent, and the solvent accounts for 55% of the total solution mass to prepare silicon hybrid phenolic resin.

[0116] Step 6. Select an orthogonal triaxial carbon fiber preform with a density of 1.2 g / cm 3 , thickness is 4mm.

[0117] Step 7. Using the RTM process in step 3, a high-density composite material with a thickness of 4 mm is prepared on the surface of the low-density inner layer to obtain an integrated composite material with low internal density and high surface density, namely the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation. The actual photo is as follows: Figure 2 shown.

[0118] Explanation of the attached table

[0119] Table 1 shows the organic-inorganic hybrid thermal protection materials resistant to discrete interval gas ablation obtained in Examples 1-3. Density was tested using the GB 1463-2005 method, and thermal conductivity was tested using the GBT 10295-2008 method. Linear ablation rate was tested using the GJB 323B-2018 method. Each test lasted 3 seconds, with a 5-second interval, for 10 cycles. The line ablation rate, backside temperature, and ablation surface condition were recorded.

[0120] Table 1

[0121]

[0122] It can be seen from the above table that the material obtained by the method of the present invention has the advantages of low density, low thermal conductivity, ablation resistance, and no residue generation during ablation, and has broad application prospects in the internal insulation structure of attitude and orbit control engines.

[0123] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. An organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation, characterized in that: It includes an inner layer low-density composite material and a surface high-density organic-inorganic hybrid composite material; The inner layer low-density composite material has microporous pure phenolic aerogel as a matrix and a quartz fiber preform as a reinforcement, and the surface high-density organic-inorganic hybrid composite material has organic-inorganic hybrid nanoporous phenolic aerogel as a matrix and a carbon fiber preform as a reinforcement; The organic-inorganic hybrid nanoporous phenolic aerogel matrix uses a silicon hybrid phenolic resin obtained by polymerization of thermoplastic phenolic resin and thermoplastic dimethyl polysilane as a raw material, the mass average molecular weight of the thermoplastic phenolic resin is less than 800, the mass average molecular weight of the thermoplastic dimethyl polysilane is less than 2000, and one or more of ethylene glycol, ethanol, and cyclohexane are selected as solvents, and the solvent accounts for 50% to 60% of the total solution mass.

2. The organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to claim 1, characterized in that: The microporous pure phenolic aerogel uses thermosetting pure phenolic resin with a mass average molecular weight greater than 1000 as a raw material, and uses one or more of ethylene glycol, ethanol, and cyclohexane as a solvent, with the solvent accounting for 40% to 70% of the total solution mass.

3. The organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to claim 1, characterized in that: The quartz fiber preform is a needle-punched quartz fiber preform, including a needle-punched quartz mesh preform and a needle-punched quartz cloth / mesh preform. The density of the preform is 0.3-0.5 g / cm 3 .

4. The organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to claim 1, characterized in that: The carbon fiber preform is a woven structure carbon fiber preform, including 2.5D carbon fiber preform, orthogonal three-directional carbon fiber preform, three-dimensional four-directional carbon fiber preform, three-dimensional five-directional carbon fiber preform, and the preform density is 1.0~1.3g / cm 3 .

5. A method for preparing the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to any one of claims 1 to 4, characterized in that: The following steps are involved: Roughening the surface of the inner layer of low-density composite material; A surface high-density organic-inorganic hybrid composite material is prepared on the rough surface of the inner low-density composite material to obtain the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation.

6. The method for preparing the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to claim 5, characterized in that: The surface of the inner layer low-density composite material is roughened by an abrasive jetting method.

7. The method for preparing the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to claim 6, characterized in that: The abrasive is spherical SiO2 particles with a particle size of 100-200 μm.

8. The method for preparing the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to claim 6, characterized in that: The abrasive jetting pressure is an oscillating pressure, the set pressure is 0.2~0.6MPa, the pressure alternating amplitude is 5%~10% of the set pressure value, and the alternating frequency is 0.1~0.5Hz; The abrasive jetting has a jetting angle of 45-90°, a jetting distance of 10-30 cm, and a jetting time of 5-10 min.

9. Use of the organic-inorganic hybrid thermal protection material resistant to discrete interval gas ablation according to any one of claims 1 to 4, characterized in that: The material is used as thermal insulation material in attitude and orbit control engines.

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