CN115895003B - Ablation-resistant polyimide-based structural gradient composite material and preparation method thereof - Google Patents
Ablation-resistant polyimide-based structural gradient composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ablation-resistant polyimide-based structural gradient composite material and a preparation method thereof. The method comprises the following specific steps: preparing a polyamic acid solution with certain viscosity by adopting an in-situ polymerization method; and continuously stirring the ablation-resistant filler into homogeneous phase to prepare filler reinforced polyamide acid composite solution, coating the polyamide acid solution and the composite solution with different filler contents on a flat carrier in a gradient manner, and respectively placing the flat carrier in an oven for imidization treatment to obtain the filler reinforced polyimide-based structure gradient composite material. The method has controllable process and excellent process, and can realize industrial mass production; the product has stable mechanical and thermal properties and good ablation resistance, and can be applied to ablation resistance materials in the aerospace field.
Description
Technical Field
The invention relates to an ablation-resistant polyimide-based structural gradient composite material and a preparation method thereof, in particular to a polyimide-based material with high-content filler composition and a functional gradient structure and a preparation method thereof.
Background
The ablation-resistant material is a functional material, and can be decomposed, melted, evaporated, sublimated and the like under the action of hot air flow in the working environment to absorb a plurality of physical and chemical changes of heat energy, and a large amount of heat energy is taken away through the mass consumption of the material, so that the purposes of heat prevention and heat insulation are achieved. By atmosphere of three types, namely, sublimation type, melting type and carbonization type, according to the main mechanism of action of the materials used. The polymer-based ablation-resistant composite material refers to an ablation-resistant composite material with excellent performance, such as a C/C composite material and a C/phenolic composite material, which is prepared by adding an ablation-resistant filler into a polymer matrix material. The ablation-resistant material has the characteristics of low density and ablation resistance, can be used as an inner insulating layer of a solid engine shell, is an indispensable high-performance matching material in the field of aerospace, is used for replacing traditional materials such as ferrous metal, nonferrous metal and the like, and becomes a main material of a light-weight structure and a heat-resistant structure.
The ablation heat protection mechanism of the polymer matrix composite is approximately: (1) the heat capacity of the material itself absorbs heat; (2) thermal decomposition and carbonization of the matrix material to absorb heat; (3) the melting endotherm of the ablation resistant filler; (4) a "thermal resistance" effect; (5) chemical reaction on the surface of the carbon layer absorbs heat. Therefore, evaluation of ablation resistant materials should be initiated from several aspects: (1) The specific heat capacity is high, and a large amount of heat can be absorbed in the ablation process; (2) the heat conduction coefficient is small, and the heat insulation effect is achieved; (3) The density is low, and the total weight of the manufacturing materials can be reduced to the greatest extent; (4) the ablation rate is small. The ablation-resistant filler is added into the polymer matrix, so that the polymer matrix composite material is mainly used for forming a heat insulation layer, and the properties of low density, low heat conduction, flame resistance and the like are obtained. However, in order to overcome the defects of shrinkage, heat release and the like of the heat insulation layer in the vulcanization process and improve the impact resistance and mechanical strength of the matrix material, on one hand, the use amount of the filler needs to be reasonably controlled, and on the other hand, the interfacial defect between two phases needs to be weakened to the greatest extent by combining factors such as the strength of interaction force and different cohesive energy among polymer molecules; on the other hand, in order to ensure the ablation resistance, the ablation residual rate of the material is improved, the high dosage of the ablation-resistant filler is required to be ensured, and the loss generated under the scouring of high-temperature fuel gas is avoided. How to balance the core problems of the two aspects becomes the key for solving the wide application of the materials in the application field. Polyimide (PI) is used as high-performance special engineering plastic, has stable and excellent physical and chemical properties in a wider temperature range, particularly has high thermal stability and glass transition temperature, and has been widely applied in the aerospace field.
Functionally Graded Materials (FGM) refer to heterogeneous functional composite materials that allow the properties or structure of the material to be continuously or quasi-continuously varied in one or more dimensions by a particular process. Because the interior of the material is continuously changed, no obvious interface layer exists, and the concentration of interface stress can be well avoided. The performance of the gradient material can be continuously changed, and the generation of thermal stress can be avoided, so that the gradient material is firstly used for solving the problem of thermal protection of the high-speed aerospace craft. When a space shuttle accelerates in the atmosphere, supersonic airflow will rub strongly against the aircraft surface, which may be up to 2100K; while the low-temperature hydrogen fuel is stored on the other side, the temperature difference inside and outside the aircraft is as high as 1600K, and huge thermal stress can be generated. Conventional materials cannot withstand such severe thermo-mechanical loads, and gradient materials can meet this requirement. The current researchers' design of ablation gradient resistant materials have focused more on the regulation and design of interlayer material properties. CN107791636a discloses a multilayer heat-resistant and ablation-resistant composite and a preparation method thereof. The composite material consists of an inner bearing layer carbon fiber reinforced polyimide resin composite material layer and an outer heat insulation layer glass fiber reinforced methyl phenyl silicon composite material layer; the two layers are bonded by an adhesive. The invention has the advantages that the inner layer material has good chemical corrosion resistance, excellent high temperature resistance, high strength and large bearing capacity, can effectively protect under high pressure, and solves the defects in the mechanical properties of protective materials such as motor car shells, airplane shells and the like; the outer layer material has excellent high temperature resistance, anti-scouring, anti-ablation, excellent mechanical property and good dielectric property. However, the obvious interface defect in the two-layer structure can be bonded only through the third component, and under extreme conditions, the defect of the interface can be gradually amplified, and the effectiveness of the material cannot be well protected. CN112830760B also discloses a thermal-insulation and high-temperature-resistant aerogel gradient composite material and a preparation method thereof, ethanol and deionized water are used as solvents, a silicon source is fully dissolved, an acidic catalyst is used, inorganic fibers are used as fiber reinforcements, final gel of the gradient composite material is prepared by sol-gel, aging and solvent replacement methods, and finally the thermal-insulation and high-temperature-resistant aerogel gradient composite material is obtained through supercritical carbon dioxide drying treatment. The method aims at the fiber reinforced gradient composite material, and meanwhile, the preparation process conditions are harsh, so that the difficulty in realizing industrialized mass production is high. In addition, researchers are more concerned with the engineering and optimization of equipment to produce such materials. CN101215182a discloses a soaking method chemical vapor infiltration technology based on preparing a C/C composite material, which adopts a method that high-concentration reaction gas and inert shielding gas or low-concentration reaction gas are respectively introduced into the inner and outer surfaces of a prefabricated part, different reaction gas concentrations of the inner and outer surfaces are utilized, and gas flow along a preset direction is controlled, a significant reaction gas concentration gradient is formed along the radial direction of the prefabricated part, and different deposition rates of different reaction gas concentrations under the same temperature condition are utilized, so as to obtain the C/C composite material with density gradient distribution of high density outside and low density inside. Although the patent realizes the density gradient distribution of the material with high density along the radial direction and low density along the inner and outer directions, the density difference is realized through different soaking amounts, the density of the reinforcement body is uniform and consistent, the preparation time is long, and the cost is high.
Disclosure of Invention
The invention aims to expand the application of a filler reinforced polyimide-based composite material in the aspect of ablation resistance in the aerospace field, and simultaneously effectively improve the filler dosage and good phase interface compatibility in a nano modified polymer-based composite material prepared by a traditional in-situ polymerization method, so as to provide an ablation-resistant polyimide-based structural gradient composite material.
The technical scheme of the invention is that the ablation-resistant polyimide-based structural gradient composite material is characterized in that the material is formed by coating three layers, namely an upper layer, a middle layer and a lower layer, wherein a first layer (closest to a carrier side) is pure polyimide resin, and the thickness of the first layer is 0.015-0.050 mm; the second layer is a high-content filler modified polyimide composite material, the filler content is 10% -90%, and the thickness is 0.10-0.30 mm; the third layer is pure polyimide resin or low-content filler modified polyimide composite material, the filler content is 0-5%, and the thickness is 0.015-0.15 mm.
Preferably, the filler is a reinforcing fiber (preferably carbon fiber, high silica fiber and its braid), and an inorganic filler system (preferably oxides); among them, the oxide-based inorganic filler is preferably zirconia, alumina, and an alkali hydroxide thereof or a rare earth-based filler (i.e., a lanthanoid oxide of the periodic table). More preferably, the filler is carbon fiber, high silica fiber or CeO 2 Or Al 2 O 3 。
The invention also provides a method for preparing the ablation-resistant polyimide-based structural gradient composite material, which comprises the following specific steps:
(1) First layer pure PI resin matrix
Preparing PAA solution with the mass concentration of 10-40%; coating the prepared PAA on a carrier to prepare a matrix layer, putting the matrix layer into a high-temperature oven for step heating and drying treatment, and dehydrating and cyclizing to obtain a pure PI resin matrix;
(2) Second layer high content filler modified PI composite material
Adding filler into the PAA solution prepared in the step (1), and stirring by ultrasonic until the filler is in a uniform state to prepare a high-content filler modified PAA composite solution with the filler mass content of 10-90%; coating the prepared composite solution on the first pure PI resin matrix layer prepared in the step (1) for 1-5 times, placing the first pure PI resin matrix layer into a high-temperature oven for step heating and drying treatment, and dehydrating and cyclizing to obtain a high-content filler modified PI composite material;
(3) Third layer low-content filler modified PI composite material
Adding filler into the PAA solution prepared in the step (1), and stirring by ultrasonic until the filler is in a uniform state to prepare a low-content filler modified PAA composite solution with the filler mass content of 0-5%; and coating the prepared PAA composite solution modified by the low-content filler on a second layer of high-content filler modified PI composite material, and placing the second layer of high-content filler modified PI composite material into a high-temperature oven for step heating and drying treatment, and dehydrating and cyclizing to obtain the ablation-resistant polyimide-based structural gradient composite material.
Preferably, the thickness of the pure PI resin matrix layer in the step (1) is 0.015 mm-0.050 mm; the parameters of the step temperature rise are as follows: the temperature rising rate is 0.5-3 ℃/min, the temperature rising is carried out from 40-50 ℃ to 85-120 ℃ for 50-70min, the temperature rising is carried out to 130-140 ℃ for 50-70min, the temperature rising is carried out to 160-170 ℃ for 50-70min, the temperature rising is carried out to 185-215 ℃ for 50-70min, and the temperature rising is carried out to 280-320 ℃ for 50-70min.
Preferably, the thickness of the high-content filler modified PI composite material layer in the step (2) is 0.10 mm-0.30 mm; the parameters of the step temperature rise are as follows: the temperature rising rate is 0.5-3 ℃/min, the temperature rising is carried out from 40-50 ℃ to 90-110 ℃ for 50-70min, the temperature rising is carried out to 130-140 ℃ for 50-70min, the temperature rising is carried out to 160-180 ℃ for 50-70min, the temperature rising is carried out to 190-220 ℃ for 50-70min, and the temperature rising is carried out to 300-330 ℃ for 50-70min.
Preferably, the thickness of the low-content filler modified PI composite material layer in the step (3) is 0.015-0.15 mm; the parameters of the step temperature rise are as follows: the temperature rising rate is 0.5-3 ℃/min, the temperature is raised from 40-50 ℃ to 90-120 ℃ and kept for 50-70min, the temperature is raised to 190-220 ℃ and kept for 50-70min, and the temperature is raised to 280-330 ℃ and kept for 50-70min.
The preparation method of the PAA solution with the mass concentration of 10% -40% in the first layer of pure PI resin matrix refers to the patent 'preparation method of polyimide hybrid film with high modulus and low thermal expansion coefficient' (ZL 200810236233.6), a certain amount of diamine monomer and polar solvent are added, ultrasonic stirring is carried out, after the diamine monomer and polar solvent are completely dissolved, dianhydride with the same molar amount is added in 3-7 batches, and continuous stirring reaction is carried out for a certain time, thus obtaining Polyimide (PAA) solution with stable performance.
The invention has controllable experimental operation process and mild implementation condition, and can realize mass production. Provides a simple and feasible method for preparing the high-content filler reinforced polymer-based ablation-resistant composite material. The structure gradient composite material prepared by the method has controllable structure and stable product performance.
The beneficial effects are that:
1. the gradient structure composite material prepared by the method has the filler content up to 80%, the appearance of the product is complete, and the filler is uniformly dispersed in the PI matrix.
2. The material shows better flexibility and stable mechanical and thermal stability.
3. The thermal decomposition test shows that the material has higher ablation solid residue rate in different environments, and has more ideal ablation resistance.
Drawings
FIG. 1 is a schematic structural diagram of a gradient composite wherein the first layer is pure polyimide resin closest to the carrier side, the second layer is a high filler modified polyimide composite, and the third layer is either pure polyimide resin or a low filler modified polyimide composite;
FIG. 2 is an SEM image of example 1; wherein the left side is a surface, and the right side is a section;
FIG. 3 is a graph of the bending characteristics of the material of example 1;
FIG. 4 is a graph of TGA data for example 1 in two atmospheres, with the upper line representing nitrogen and the lower line representing air.
Detailed Description
Example 1
Firstly, self-made 4.5g of PAA solution with 30% solid content is selected and coated on a glass carrier, and the PAA solution is placed in a blast drying oven for heating and imidization, wherein the heating rate is 0.5 ℃/min (100 ℃ C. Multiplied by 60min,140 ℃ C. Multiplied by 60min,170 ℃ C. Multiplied by 60min,200 ℃ C. Multiplied by 60min,280 ℃ C. Multiplied by 60 min), and a first pure PI resin matrix layer of the structural gradient material with the thickness of 0.05mm is obtained.
To a PAA solution having a solid content of 30%, cerium oxide (CeO) was added 2 ) 28.761g of modified PAA composite solution with the filler mass content of 80.5% is prepared, and is coated on a first layer of pure PI resin layer in 2 batches, and is placed in a forced air drying oven for heating imidization, wherein the heating rate is 0.5 ℃/min (100 ℃ multiplied by 60min,140 ℃ multiplied by 60min,170 ℃ multiplied by 60min,200 ℃ multiplied by 60min,320 ℃ multiplied by 60 min), and the preparation of a second layer of high-content filler reinforced PI composite material layer of the structural gradient material is completed, so that a two-layer composite material of the structural gradient material is obtained, and the thickness of the second layer is 0.1mm.
Adding CeO into PAA solution with solid content of 30% 2 5.4237g of modified PAA composite solution with the filler mass content of 5% is prepared, coated on two layers of composite layers, placed in a blast drying oven for heating and imidization, the heating rate is 0.5 ℃/min (100 ℃ multiplied by 60min,200 ℃ multiplied by 60min,320 ℃ multiplied by 60 min),completing the preparation of the low-content filler reinforced PI composite material layer of the third layer of the structural gradient material to obtain CeO 2 The PI-based structural gradient composite was reinforced with a third layer having a thickness of 0.015mm. As shown in fig. 1.
The filler mass content of the filler reinforced PI structure gradient composite material prepared in the embodiment reaches 69.3%, the appearance of the finished piece is complete, and the filler is uniformly dispersed in a PI matrix, as shown in figure 2. The material exhibited a good flexibility, the glass transition temperature was maintained around 250 ℃, and stable thermal properties were exhibited, as shown in fig. 3. The residual rates of ablated solids at 800 ℃ in both nitrogen and air atmospheres were 84.31% and 66.60%, respectively, showing the desired ablation resistance characteristics, as shown in fig. 4.
Example 2
Firstly, self-made PAA solution with the solid content of 40% is selected to be coated on a glass carrier, the glass carrier is placed in a blast drying oven for heating and imidization, the heating rate is 1.5 ℃/min (85 ℃ C. Multiplied by 50min,130 ℃ C. Multiplied by 50min,160 ℃ C. Multiplied by 50min,185 ℃ C. Multiplied by 50min,290 ℃ C. Multiplied by 50 min), and a first pure PI resin matrix layer of the structural gradient material with the thickness of 0.015mm is obtained.
Adding zirconia powder into PAA solution with solid content of 40%, preparing 75.65g of modified PAA composite solution with filler mass content of 90%, coating the modified PAA composite solution on a first layer of pure PI resin layer in 5 batches, heating and imidizing in a blast drying box at a heating rate of 1.5 ℃/min (90 ℃ multiplied by 70min,130 ℃ multiplied by 70min,160 ℃ multiplied by 70min,220 ℃ multiplied by 70min and 330 ℃ multiplied by 70 min), and preparing a second layer of high-content filler reinforced PI composite material layer of the structural gradient material, thereby obtaining a two-layer composite material of the structural gradient material, wherein the thickness of the second layer is 0.3mm.
2.325g of PAA solution with the solid content of 40% is coated on the two composite layers, the composite layers are placed in a forced air drying oven for heating imidization, the heating rate is 1.5 ℃/min (90 ℃ C. Multiplied by 50min,190 ℃ C. Multiplied by 50min,280 ℃ C. Multiplied by 50 min), the preparation of a pure PI resin layer of a third layer of the structural gradient material is completed, and the zirconia reinforced PI-based structural gradient composite material is obtained, wherein the thickness of the third layer is 0.02mm.
The filler mass content of the filler reinforced PI structure gradient composite material prepared in the embodiment reaches 85%, the appearance of the finished piece is complete, and the filler is uniformly dispersed in the PI matrix. The material also shows better flexibility, the glass transition temperature is maintained at about 280 ℃, and stable thermal performance is shown. The residual rates of the ablation solids at 800 ℃ in two atmospheres of nitrogen and air are 93.70% and 83.61%, respectively, and the ideal ablation resistance is shown.
Example 3
Firstly, self-made PAA solution with the solid content of 10% is selected to be coated on a glass carrier, the glass carrier is placed in a blast drying box for heating imidization, the heating rate is 1 ℃/min (110 ℃ C. Multiplied by 70min,135 ℃ C. Multiplied by 70min,165 ℃ C. Multiplied by 70min,215 ℃ C. Multiplied by 70min,320 ℃ C. Multiplied by 70 min), and the first pure PI resin matrix layer of the structural gradient material with the thickness of 0.03mm is obtained.
And immersing a carbon fiber fabric in a PAA solution with the solid content of 10%, preparing 20.32g of modified PAA composite solution with the filler mass content of 10%, coating the modified PAA composite solution on a first layer of pure PI resin layer at one time, heating and imidizing in a blast drying box at the heating rate of 1 ℃/min (110 ℃ for 50min,130 ℃ for 50min,180 ℃ for 50min,210 ℃ for 50min and 300 ℃ for 50 min), and preparing a second layer of high-content filler reinforced PI composite material layer of the structural gradient material, thereby obtaining a two-layer composite material of the structural gradient material, wherein the thickness of the second layer is 0.2mm.
And immersing a carbon fiber fabric in a PAA solution with the solid content of 10%, preparing 15.313g of modified PAA composite solution with the filler mass content of 3%, superposing the modified PAA composite solution on two layers of composite layers, placing the composite layers in a blast drying oven, heating for imidization at the heating rate of 1 ℃/min (110 ℃ for 70min,210 ℃ for 70min and 330 ℃ for 70 min), and preparing a third layer of low-content filler reinforced PI composite material layer of the structural gradient material, thereby obtaining the carbon fiber reinforced PI-based structural gradient composite material, wherein the thickness of the third layer is 0.015mm.
The filler-reinforced PI structure gradient composite material prepared in the embodiment has the filler mass content of 5%, the appearance of the finished piece is complete, and the filler is compatible with a PI matrix interface. The material has better flexibility, the glass transition temperature is maintained at about 260 ℃, and stable thermal performance is shown. The residual rate of the ablation solids at 800 ℃ in two atmospheres of nitrogen and air is 65.47% and 23%, respectively, and the ideal ablation resistance is shown.
Example 4
Firstly, self-made 3g of PAA solution with 20% of solid content is selected and coated on a glass carrier, and the glass carrier is placed in a forced air drying oven for heating imidization, wherein the heating rate is 0.5 ℃/min (90 ℃ C. Multiplied by 65min,140 ℃ C. Multiplied by 65min,170 ℃ C. Multiplied by 65min,190 ℃ C. Multiplied by 65min,300 ℃ C. Multiplied by 65 min), and a first pure PI resin matrix layer of the structural gradient material with the thickness of 0.02mm is obtained.
Adding high silica fiber into PAA solution with solid content of 20%, preparing 21.5423g modified PAA composite solution with filler mass content of 50%, coating the modified PAA composite solution on a first layer of pure PI resin layer in batches, heating and imidizing in a blast drying box at a heating rate of 2 ℃/min (100 ℃ multiplied by 65min,140 ℃ multiplied by 65min,175 ℃ multiplied by 65min,190 ℃ multiplied by 65min,310 ℃ multiplied by 65 min), and preparing a second layer of high-content filler reinforced PI composite material layer of the structural gradient material, thereby obtaining a two-layer composite material of the structural gradient material, wherein the thickness of the second layer is 0.15mm.
And adding high silica fiber into the PAA solution with the solid content of 20%, preparing 10.37g of modified PAA composite solution with the filler mass content of 2%, coating the modified PAA composite solution on two layers of composite layers, heating and imidizing the two layers of composite layers in a blast drying box at the heating rate of 2 ℃/min (120 ℃ for 70min,220 ℃ for 70min and 300 ℃ for 70 min), and preparing a third layer of low-content filler reinforced PI composite material layer of the structural gradient material, thus obtaining the high silica fiber reinforced PI-based structural gradient composite material, wherein the thickness of the third layer is 0.1mm.
The filler mass content of the filler reinforced PI structure gradient composite material prepared in the embodiment reaches 72.1%, the appearance of the finished piece is complete, and the filler is uniformly dispersed in the PI matrix. The material has better flexibility, the glass transition temperature is maintained at about 320 ℃, and stable thermal performance is shown. The residual rate of the ablated solid at 800 ℃ in two atmospheres of nitrogen and air is 89.25% and 75.70%, respectively, showing ideal ablation resistance.
Example 5
Firstly, self-made 10g of PAA solution with 25% of solid content is selected and coated on a glass carrier, and the glass carrier is placed in a forced air drying oven for heating imidization, wherein the heating rate is 0.5 ℃/min (120 ℃ C. 55min,135 ℃ C. 55min,165 ℃ C. 55min,210 ℃ C. 55min,310 ℃ C. 55 min), and the first pure PI resin matrix layer of the structural gradient material with the thickness of 0.04mm is obtained.
To a PAA solution having a solids content of 25%, alumina (Al 2 O 3 ) 61.6667g of modified PAA composite solution with 60% of filler mass content is prepared, and is coated on a first layer of pure PI resin layer in batches, and is placed in a blast drying box for heating imidization, wherein the heating rate is 3 ℃/min (95 ℃ X55 min,135 ℃ X55 min,165 ℃ X55 min,215 ℃ X55 min and 315 ℃ X55 min), so that the preparation of a second layer of high-content filler reinforced PI composite material layer of the structural gradient material is completed, and a two-layer composite material of the structural gradient material is obtained, wherein the thickness of the second layer is 0.25mm.
Adding Al into PAA solution with solid content of 25% 2 O 3 18.325g of modified PAA composite solution with the filler mass content of 4% is prepared, and is coated on two composite layers, and is placed in a blast drying box for heating imidization, the heating rate is 3 ℃/min (115 ℃ for 65min,215 ℃ for 65min and 290 ℃ for 65 min), and the preparation of a third low-content filler reinforced PI composite material layer of the structural gradient material is completed, so that Al is obtained 2 O 3 The PI-based structural gradient composite material was reinforced with a third layer having a thickness of 0.15mm.
The filler mass content of the filler reinforced PI structure gradient composite material prepared in the embodiment reaches 74.3%, the appearance of the finished piece is complete, and the filler is uniformly dispersed in the PI matrix. The material has better flexibility, the glass transition temperature is maintained at about 300 ℃, and stable thermal performance is shown. The residual rates of the ablation solids at 800 ℃ in two atmospheres of nitrogen and air are 83.37% and 60.41%, respectively, and the ideal ablation resistance is shown.
Claims (4)
1. The ablation-resistant polyimide-based structural gradient composite material is characterized by being formed by coating three layers of upper layer, middle layer and lower layer, wherein the first layer is pure polyimide resin, and the thickness of the first layer is equal to that of the second layerThe degree is 0.015 mm-0.050 mm; the second layer is a high-content filler modified polyimide composite material, the filler content is 10% -90%, and the thickness is 0.10-0.30 mm; the third layer is pure polyimide resin or low-content filler modified polyimide composite material, the filler content is 0-5%, and the thickness is 0.015-0.15 mm; wherein the filler is carbon fiber, high silica fiber and CeO 2 Or Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following specific steps:
(1) First layer pure PI resin matrix
Preparing PAA solution with the mass concentration of 10-40%; coating the prepared PAA on a carrier to prepare a matrix layer, putting the matrix layer into a high-temperature oven for step heating and drying treatment, and dehydrating and cyclizing to obtain a pure PI resin matrix;
(2) Second layer high content filler modified PI composite material
Adding filler into the PAA solution prepared in the step (1), and stirring by ultrasonic until the filler is in a uniform state to prepare a high-content filler modified PAA composite solution with the filler mass content of 10-90%; coating the prepared composite solution on the first pure PI resin matrix layer prepared in the step (1) for 1-5 times, placing the first pure PI resin matrix layer into a high-temperature oven for step heating and drying treatment, and dehydrating and cyclizing to obtain a high-content filler modified PI composite material;
(3) Third layer low-content filler modified PI composite material
Adding filler into the PAA solution prepared in the step (1), and stirring by ultrasonic until the filler is in a uniform state to prepare a low-content filler modified PAA composite solution with the filler mass content of 0-5%; and coating the prepared PAA composite solution modified by the low-content filler on a second layer of high-content filler modified PI composite material, and placing the second layer of high-content filler modified PI composite material into a high-temperature oven for step heating and drying treatment, and dehydrating and cyclizing to obtain the ablation-resistant polyimide-based structural gradient composite material.
2. The ablation-resistant polyimide-based structural gradient composite material according to claim 1, wherein the thickness of the pure PI resin matrix layer in step (1) is 0.015mm to 0.050mm; the parameters of the step temperature rise are as follows: the temperature rising rate is 0.5-3 ℃/min, the temperature rising is carried out from 40-50 ℃ to 85-120 ℃ for 50-70min, the temperature rising is carried out to 130-140 ℃ for 50-70min, the temperature rising is carried out to 160-170 ℃ for 50-70min, the temperature rising is carried out to 185-215 ℃ for 50-70min, and the temperature rising is carried out to 280-320 ℃ for 50-70min.
3. The ablation-resistant polyimide-based structural gradient composite material according to claim 1, wherein the thickness of the high-content filler modified PI composite material layer in the step (2) is 0.10mm to 0.30mm; the parameters of the step temperature rise are as follows: the temperature rising rate is 0.5-3 ℃/min, the temperature rising is carried out from 40-50 ℃ to 90-110 ℃ for 50-70min, the temperature rising is carried out to 130-140 ℃ for 50-70min, the temperature rising is carried out to 160-180 ℃ for 50-70min, the temperature rising is carried out to 190-220 ℃ for 50-70min, and the temperature rising is carried out to 300-330 ℃ for 50-70min.
4. The ablation-resistant polyimide-based structural gradient composite material according to claim 1, wherein the thickness of the low-content filler modified PI composite material layer in the step (3) is 0.015mm to 0.15mm; the parameters of the step temperature rise are as follows: the temperature rising rate is 0.5-3 ℃/min, the temperature is raised from 40-50 ℃ to 90-120 ℃ and kept for 50-70min, the temperature is raised to 190-220 ℃ and kept for 50-70min, and the temperature is raised to 280-330 ℃ and kept for 50-70min.
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