CN117603495A - Heat-proof and insulation integrated hybrid resin matrix composite with gradient change of porosity and preparation method thereof - Google Patents

Heat-proof and insulation integrated hybrid resin matrix composite with gradient change of porosity and preparation method thereof Download PDF

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CN117603495A
CN117603495A CN202311590750.4A CN202311590750A CN117603495A CN 117603495 A CN117603495 A CN 117603495A CN 202311590750 A CN202311590750 A CN 202311590750A CN 117603495 A CN117603495 A CN 117603495A
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resin
heat
porosity
composite material
hybrid resin
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牛波
李昕桐
顾隆祯
张汉霖
齐浩文
蔡宏祥
龙东辉
曹宇
张亚运
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East China University of Science and Technology
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Abstract

The invention relates to a heat-proof and insulation integrated hybrid resin matrix composite material with gradient change of porosity and a preparation method thereof, organic-inorganic hybrid resin is selected as a matrix, and resin solutions with gradually increased volume fractions of 5-8 resins are designed by adding pore-forming solvents with different volume fractions; adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into an orthogonal three-way fiber preform, and curing and drying; and then, sequentially injecting the rest resin solution into the orthogonal three-way fiber preform from low to high according to the resin volume fraction through a multiple-cycle glue injection-curing-drying process to prepare the heat-proof integrated hybrid resin matrix composite material with low surface porosity and high internal porosity and gradient change of the porosity. Compared with the prior art, the composite material can realize multiple functions of low density, low heat conductivity, ablation resistance and the like under a single structure, and can be applied to heat protection materials of aerospace craft.

Description

Heat-proof and insulation integrated hybrid resin matrix composite with gradient change of porosity and preparation method thereof
Technical Field
The invention relates to the technical field of resin-based thermal protection materials, in particular to an anti-heat insulation integrated hybrid resin-based composite material with gradient change of porosity and a preparation method thereof.
Background
The heat protection material is a basic stone for guaranteeing the safe service of the aerospace craft in an extreme environment, wherein the resin-based heat protection material has the highest maturity, the lowest cost and the shortest preparation period at present. The resin-based composite material with low porosity has good ablation resistance, but has higher heat conductivity, and can not meet the long-term heat insulation requirement of a spacecraft with high Mach long-term flight characteristics. The resin-based composite material with high porosity has low heat conductivity but poor ablation resistance. Therefore, the development of low density-low thermal conductivity-ablation resistant integrated resin matrix composites is an urgent need in this field.
Disclosure of Invention
The invention aims to provide an anti-heat insulation integrated hybrid resin matrix composite with gradient change of porosity and a preparation method thereof, and the composite has low density, low heat conductivity and ablation resistance.
The aim of the invention can be achieved by the following technical scheme: a preparation method of an anti-heat insulation integrated hybrid resin matrix composite with gradient change of porosity comprises the following steps:
s1: organic-inorganic hybrid resin is selected as a matrix, and resin solutions with gradually increased volume fractions of 5-8 hybrid resins are prepared by adding pore-forming solvents with different volume fractions;
s2: injecting the resin solution with the lowest resin volume fraction into the orthogonal three-way fiber preform, and curing and drying;
s3: and sequentially injecting the rest resin solution into the orthogonal three-way fiber preform from low to high according to the resin volume fraction, and curing and drying after each injection to finally prepare the heat-proof integrated hybrid resin matrix composite material with gradient change of porosity.
Compared with the traditional resin, the organic-inorganic hybrid resin has excellent high-temperature resistance and higher carbon residue rate, and is beneficial to improving the ablation resistance of the heat protection material. The added pore-forming solvent can volatilize in the resin curing process, so that the resin forms a porous structure, and the thermal conductivity and the density of the thermal protection material are reduced.
Preferably, the resin solution is injected into the orthogonal three-way fiber preform using an oscillating vacuum and oscillating pressure assisted RTM process.
Further preferably, the preparation method of the heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity comprises the following steps:
(1) Organic-inorganic hybrid resin is selected as a matrix, and resin solutions with volume fractions gradually increased by 5-8 hybrid resins are designed by adding pore-forming solvents with different volume fractions.
(2) An orthogonal three-way fiber preform having isotropic characteristics is selected.
(3) And (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, and curing and drying. And then, the residual resin solution is injected into the fiber preform from low to high according to the resin volume fraction in sequence through a plurality of circulating glue injection, curing and drying processes. The heat-proof and heat-insulating integrated hybrid resin matrix composite material with low surface porosity and high internal porosity and gradient change of porosity is prepared.
In the glue injection-curing-drying process, the first glue injection time is preferably 8-10 h, and the subsequent glue injection time is decreased by 30-40 min each time.
In the glue injection-curing-drying process, preferably, each curing time is 12-24 hours, the primary curing temperature is 90-110 ℃, and the subsequent curing temperature is increased by 2-5 ℃ each time. The drying time is 12-24 h each time, the primary drying temperature is 120-130 ℃, and the subsequent drying temperature is increased by 2-5 ℃ each time.
Further preferably, in the oscillation vacuum and oscillation pressure assisted RTM process, the vacuum value of the vacuum pump is not a constant value but an alternating value, the vacuum value of the vacuum pump is set to be not lower than-0.085 MPa, the vacuum alternating amplitude is set to be 4-12%, and the alternating frequency is 0.2-0.9 Hz.
Further preferably, in the oscillation vacuum and oscillation pressure assisted RTM process, the pressure inside the resin container is not a constant value, but an alternating pressure, the pressure inside the resin container is set to be 0.6-1.5 MPa, the alternating amplitude of the pressure is 4% -12% and the pressure value inside the container is set, and the alternating frequency is 0.2-0.9 Hz.
The invention adopts an oscillating vacuum and oscillating pressure assisted RTM process, firstly injects the solution with the lowest resin volume fraction into an orthogonal three-way fiber preform, and carries out solidification and drying treatment. And then, the residual resin solution is injected into the fiber preform from low to high according to the resin volume fraction in sequence through a plurality of circulating glue injection, curing and drying processes. The heat-proof and heat-insulating integrated hybrid resin matrix composite material with low surface porosity and high internal porosity and gradient change of porosity can be prepared. The porosity is reduced only on the surface of the material contacting with heat flow, and the ablation resistance of the material can be improved on the basis of not affecting the heat conductivity and density of the whole material, so that the low density-low heat conductivity-ablation resistance integrated function of the resin-based heat protection material is realized.
Preferably, the organic-inorganic hybrid resin in step S1 includes a silicone hybrid phenolic resin, a polycarbosilane hybrid phenolic resin, and a silicone hybrid polyimide.
Preferably, the pore-forming solvent in step S1 includes ethanol, isopropanol, cyclohexane, ethylene glycol, and ethyl acetate.
Preferably, the volume of the pore-forming solvent in the step S1 accounts for 60% -70% of the total volume of the resin and the pore-forming solvent, and 4% -6% of the pore-forming solvent is designed in a decreasing manner each time, and resin solutions with the volume fractions of other 4-7 kinds of hybrid resins gradually increasing are designed.
Preferably, the time for injecting the resin solution for the first time is 8-10 hours, and the time for injecting the subsequent glue is decreased for 30-40 minutes each time.
Preferably, each time of curing is 12-24 hours, the first curing temperature is 90-110 ℃, and the subsequent curing temperature is increased by 2-5 ℃ each time; the drying time is 12-24 h each time, the primary drying temperature is 120-130 ℃, and the subsequent drying temperature is increased by 2-5 ℃ each time.
Preferably, the types of the orthogonal three-way fiber preform in the step S2 include quartz fiber, carbon fiber, silicon carbide fiber and mullite fiber.
Preferably, the density of the orthogonal three-way fiber preform is 0.4g/cm 3 ～0.7g/cm 3 Within the range.
The heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity is prepared by adopting the preparation method.
An application of a heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity is provided, wherein the composite material is used for heat protection of an aerospace vehicle.
The resin-based composite material prepared by the invention can realize multiple functions of low density, low heat conductivity, ablation resistance and the like under a single structure, and can be applied to heat protection materials of aerospace craft.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides an anti-heat insulation integrated hybrid resin matrix composite with gradient change of porosity and a preparation method thereof, which can solve the problems that the traditional resin matrix thermal protection material cannot have low density, low thermal conductivity and ablation resistance.
2. The invention adopts the orthogonal three-way fiber preform, so that the composite material can show isotropy, and has excellent comprehensive performance in all directions; meanwhile, the orthogonal three-way fiber preform has higher rigidity, so that deformation and shrinkage of the composite material in the process of multiple glue injection, curing and drying can be avoided, and the heat insulation and ablation resistance of the material are improved.
3. According to the invention, organic-inorganic hybrid resin is selected as a matrix, and resin solutions with gradually increased volume fractions of 5-8 resins are designed by adding pore-forming solvents with different volume fractions. And sequentially injecting the resin solution into the fiber preform from low to high according to the resin volume fraction through a plurality of circulating glue injection, curing and drying processes. The resin with low resin volume fraction can fill the whole fiber preform, and as the resin volume fraction increases, the injection depth is gradually reduced, so that the resin-based composite material with low surface porosity and high internal porosity and gradient change of porosity can be obtained. The ablation resistance of the material can be improved on the basis of not affecting the heat conductivity and density of the whole material. Thereby realizing the integrated functions of low density, low heat conductivity and ablation resistance of the resin-based heat protection material.
4. The invention adopts the RTM technology assisted by oscillation vacuum and oscillation pressure, can more uniformly immerse the resin into the fiber preform, and is beneficial to improving the ablation resistance of the thermal protection material; meanwhile, the glue injection time is gradually decreased, and the curing and drying temperatures are gradually increased, so that the resin-based composite material with gradient change of porosity can be formed.
Drawings
FIG. 1 is a schematic diagram of a preparation process of an anti-heat insulation integrated hybrid resin matrix composite with gradient change of porosity;
FIG. 2 is a schematic structural view of the heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
As shown in figure 1, organic-inorganic hybrid resin is selected as a matrix, and 5-8 resin solutions with gradually increased volume fractions are designed by adding pore-forming solvents with different volume fractions. An orthogonal three-way fiber preform having isotropic characteristics is selected. And (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, and curing and drying. And then, the residual resin solution is injected into the fiber preform from low to high according to the resin volume fraction in sequence through a plurality of circulating glue injection, curing and drying processes. The heat-proof and insulation integrated hybrid resin matrix composite with low surface porosity and high internal porosity and gradient change porosity is prepared as shown in figure 2.
The following describes in detail specific embodiments.
Example 1
Step 1: and selecting an organosilicon hybridized phenolic resin as a matrix, wherein the organosilicon hybridized phenolic resin is prepared according to patent ZL 201911266938.7. Ethanol is selected as a pore-forming solvent;
step 2: the volume of the pore-forming solvent was set to be 60% of the total volume of the resin and pore-forming agent. And designing other 4 resin solutions with the volume fractions of pore-forming solvents decreasing by 4 percent in sequence, wherein the other 4 resin solutions comprise 56 percent, 52 percent, 48 percent and 44 percent.
Step 3: selecting density of 0.4g/cm 3 Is a three-way quartz fiber.
Step 4: and (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, setting the vacuum value of a vacuum pump to be-0.085 MPa, setting the vacuum value of the vacuum alternating amplitude to be 4%, and setting the alternating frequency to be 0.2Hz. The pressure of the container is set to be 0.6MPa, the alternating amplitude of the pressure is set to be 4 percent, the pressure value of the container is set, the alternating frequency is 0.2Hz, and the glue injection time is 8 hours.
Step 5: placing the mold after glue injection in a 90 ℃ oven for curing for 12 hours; then, the mixture was demolded and dried in an oven at 120℃for 12 hours.
Step 6: and (3) circulating the glue injection, curing and drying processes, and sequentially injecting the rest resin solution into the fiber preform from low to high according to the resin volume fraction. The subsequent glue injection time is decreased for 30min each time, the subsequent curing temperature is increased by 2 ℃ each time, and the subsequent drying temperature is increased by 2 ℃ each time.
Example 2
Step 1: and selecting polycarbosilane hybridized phenolic resin as a matrix, wherein the polycarbosilane hybridized phenolic resin is prepared according to patent ZL 202111389268.5. Isopropanol is selected as a pore-forming solvent;
step 2: the volume of the pore-forming solvent was set to be 65% of the total volume of the resin and pore-forming agent. And designing other 6 resin solutions with volume fractions of pore-forming solvents decreasing by 5% in sequence, wherein the other 6 resin solutions comprise 60%, 55%, 50%, 45%, 40% and 35%.
Step 3: selecting density of 0.5g/cm 3 Is a three-way orthogonal carbon fiber.
Step 4: and (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, setting a vacuum value of a vacuum pump to-0.09 MPa, setting a vacuum value of 8% of vacuum alternating amplitude, and setting the alternating frequency to be 0.7Hz. The pressure of the container is set to be 1.0MPa, the alternating amplitude of the pressure is 8 percent, the pressure value of the container is set, the alternating frequency is 0.7Hz, and the glue injection time is 9 hours.
Step 5: placing the mold after glue injection in a baking oven at 100 ℃ for curing for 16 hours; then, the mixture was demolded and dried in an oven at 125℃for 16 hours.
Step 6: and (3) in the circulating glue injection, curing and drying process, sequentially injecting the rest resin solution into the fiber preform from low to high according to the resin volume fraction. The subsequent glue injection time is reduced for 35min each time, the subsequent curing temperature is increased by 3 ℃ each time, and the subsequent drying temperature is increased by 3 ℃ each time.
Example 3
Step 1: and an organosilicon hybridized polyimide is selected as a matrix, and the organosilicon hybridized polyimide resin is prepared according to patent ZL 201811097472.8. Ethylene glycol is selected as a pore-forming solvent;
step 2: the volume of the pore-forming solvent was set to be 70% of the total volume of the resin and pore-forming agent. And the volume fraction of the pore-forming solvent is designed to be reduced by 6 percent in sequence to form other 7 resin solutions, including 63 percent, 56 percent, 49 percent, 42 percent, 35 percent, 28 percent and 21 percent.
Step 3: selecting a density of 0.7g/cm 3 Is used as a fiber reinforcement.
Step 4: and (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, setting a vacuum value of a vacuum pump to be-0.095 MPa, setting a vacuum value of the vacuum alternating amplitude to be 12%, and setting the alternating frequency to be 0.9Hz. The pressure of the container is set to be 1.5MPa, the alternating amplitude of the pressure is 12 percent, the pressure value of the container is set, the alternating frequency is 0.9Hz, and the glue injection time is 10 hours.
Step 5: placing the mold after glue injection in a baking oven at 110 ℃ for curing for 24 hours; then, the mixture was demolded and dried in an oven at 130℃for 24 hours.
Step 6: and (3) in the circulating glue injection, curing and drying process, sequentially injecting the rest resin solution into the fiber preform from low to high according to the resin volume fraction. The subsequent glue injection time is decreased by 40min each time, the subsequent curing temperature is increased by 5 ℃ each time, and the subsequent drying temperature is increased by 5 ℃ each time.
Comparative example 1
Step 1: and selecting an organosilicon hybridized phenolic resin as a matrix, wherein the organosilicon hybridized phenolic resin is prepared according to patent ZL 201911266938.7. Ethanol is selected as a pore-forming solvent;
step 2: the volume of the pore-forming solvent was set to be 60% of the total volume of the resin and pore-forming agent.
Step 3: selecting density of 0.4g/cm 3 Is a three-way quartz fiber.
Step 4: and (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, setting the vacuum value of a vacuum pump to be-0.085 MPa, setting the vacuum value of the vacuum alternating amplitude to be 4%, and setting the alternating frequency to be 0.2Hz. The pressure of the container is set to be 0.6MPa, the alternating amplitude of the pressure is set to be 4 percent, the pressure value of the container is set, the alternating frequency is 0.2Hz, and the glue injection time is 8 hours.
Step 5: placing the mold after glue injection in a 90 ℃ oven for curing for 12 hours; then, the mixture was demolded and dried in an oven at 120℃for 12 hours.
Comparative example 2
Step 1: and an organosilicon hybridized polyimide is selected as a matrix, and the organosilicon hybridized polyimide resin is prepared according to patent ZL 201811097472.8. No pore-forming solvent is added;
step 2: selecting a density of 0.7g/cm 3 Is used as a fiber reinforcement.
Step 3: and (3) adopting an oscillating vacuum and oscillating pressure assisted RTM process, firstly injecting the solution with the lowest resin volume fraction into the fiber preform, setting a vacuum value of a vacuum pump to be-0.095 MPa, setting a vacuum value of the vacuum alternating amplitude to be 12%, and setting the alternating frequency to be 0.9Hz. The pressure of the container is set to be 1.5MPa, the alternating amplitude of the pressure is 12 percent, the pressure value of the container is set, the alternating frequency is 0.9Hz, and the glue injection time is 10 hours.
Step 4: placing the mold after glue injection in a baking oven at 110 ℃ for curing for 24 hours; then, the mixture was demolded and dried in an oven at 130℃for 24 hours.
Table 1 shows a summary of the properties of the heat-shielding integrated hybrid resin-based composites with gradient porosity obtained in examples 1-3 and the resin-based composites obtained in comparative examples 1-2. The density test method adopts GB 1463-2005, the thermal conductivity test method adopts GBT 10295-2008, and the linear ablation rate test method adopts GJB 323B-2018.
TABLE 1
It can be found from comparative examples 1 and 1 that designing the resin-based thermal protection material to have a structure with gradient change in porosity can greatly improve ablation resistance on the basis of less influence on thermal conductivity than a uniform porous resin-based composite material.
It can be found from comparative examples 3 and 2 that the heat insulation performance can be greatly improved on the basis of less influence on the ablation resistance performance compared with the dense resin matrix composite material by designing the resin matrix heat protection material to have a structure with gradient change of porosity.
The material obtained by the invention has low density, low heat conductivity and low linear ablation rate, and has wide application prospect in the thermal protection material of the aerospace craft.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1. The preparation method of the heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity is characterized by comprising the following steps of:
s1: organic-inorganic hybrid resin is selected as a matrix, and resin solutions with gradually increased volume fractions of 5-8 hybrid resins are prepared by adding pore-forming solvents with different volume fractions;
s2: injecting the resin solution with the lowest resin volume fraction into the orthogonal three-way fiber preform, and curing and drying;
s3: and sequentially injecting the rest resin solution into the orthogonal three-way fiber preform from low to high according to the resin volume fraction, and curing and drying after each injection to finally prepare the heat-proof integrated hybrid resin matrix composite material with gradient change of porosity.
2. The method for preparing the heat-insulating integrated hybrid resin-based composite material with gradient change of porosity according to claim 1, wherein the resin solution is injected into the orthogonal three-way fiber preform by adopting an oscillating vacuum and oscillating pressure assisted RTM process.
3. The method for preparing the heat-insulating integrated hybrid resin matrix composite with gradient change of porosity according to claim 2, wherein in the oscillating vacuum and oscillating pressure assisted RTM process, a vacuum pump vacuum value is set to be not lower than-0.085 MPa, a vacuum alternating amplitude is set to be 4-12%, and an alternating frequency is 0.2-0.9 Hz;
in the oscillation vacuum and oscillation pressure assisted RTM process, the pressure of the resin container is set to be 0.6-1.5 MPa, the alternating amplitude of the pressure is set to be 4-12 percent, the pressure value of the container is set, and the alternating frequency is 0.2-0.9 Hz.
4. The method for preparing the heat-insulating integrated hybrid resin-based composite material with gradient porosity according to claim 1, wherein the organic-inorganic hybrid resin in the step S1 comprises an organosilicon hybrid phenolic resin, a polycarbosilane hybrid phenolic resin and an organosilicon hybrid polyimide.
5. The method for preparing the heat-proof and heat-insulating integrated hybrid resin-based composite material with gradient change of porosity according to claim 1, wherein the pore-forming solvent in the step S1 comprises ethanol, isopropanol, cyclohexane, ethylene glycol and ethyl acetate.
6. The method for preparing the heat-insulating integrated hybrid resin matrix composite with gradient porosity according to claim 1, wherein the volume of the pore-forming solvent in the step S1 is 60% -70% of the total volume of the resin and the pore-forming solvent, and 4% -6% of the resin solution with the volume fraction of the other 4-7 hybrid resins gradually increased is designed in each decreasing manner.
7. The method for preparing the heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity according to claim 1, wherein the time for injecting the resin solution for the first time is 8-10 h, and the time for injecting the subsequent glue is decreased by 30-40 min each time.
8. The method for preparing the heat-proof and heat-insulating integrated hybrid resin matrix composite material with gradient change of porosity according to claim 1, wherein each curing time is 12-24 h, the primary curing temperature is 90-110 ℃, and the subsequent curing temperature is increased by 2-5 ℃ each time; the drying time is 12-24 h each time, the primary drying temperature is 120-130 ℃, and the subsequent drying temperature is increased by 2-5 ℃ each time.
9. The method for preparing the heat-insulating integrated hybrid resin-based composite material with gradient porosity according to claim 1, wherein the types of the orthogonal three-way fiber preform in the step S2 include quartz fibers, carbon fibers, silicon carbide fibers and mullite fibers; the density of the orthogonal three-way fiber preform is 0.4g/cm 3 ～0.7g/cm 3 Within the range.
10. An anti-heat insulation integrated hybrid resin matrix composite with gradient change of porosity, which is characterized by being prepared by the preparation method of any one of claims 1-9.
CN202311590750.4A 2023-11-27 2023-11-27 Heat-proof and insulation integrated hybrid resin matrix composite with gradient change of porosity and preparation method thereof Pending CN117603495A (en)

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