CN115160730A - High-performance resin-based composite material for heat prevention and insulation and preparation method thereof - Google Patents
High-performance resin-based composite material for heat prevention and insulation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a resin-based composite material for high-performance heat insulation and a preparation method thereof, wherein the composite material comprises 20-80 parts by weight of high-performance heat insulation special resin and 20-80 parts by weight of fiber reinforcement, wherein the high-performance heat insulation special resin consists of propargyl phenolic resin, zirconium polyacetylacetonate, phenyl poly-silicon-acetylene, a silicon-boron-carbon-nitrogen precursor and a series of functional fillers. The composite material prepared by the invention has the advantages of light weight, low thermal conductivity, ablation resistance, oxidation resistance and the like, and can be widely applied to a thermal protection system in an extreme thermal field environment.
Description
Technical Field
The invention belongs to the technical field of resin-based composite materials, and particularly relates to a high-performance resin-based composite material for heat prevention and insulation and a preparation method thereof.
Background
With the rapid development of hypersonic aircraft, higher requirements and challenges are placed on the thermal protection system. The thermal protection system is required to have not only excellent oxidation resistance and ablation resistance, but also excellent low thermal conductivity and high airflow scouring resistance.
The introduction of the ceramifiable component into the resin matrix to modify the resin is an advanced technical means for improving the heat-proof and heat-insulating performance of the resin, and a new idea is provided for the design of a heat protection system. Generally below 600 ℃, the heat is prevented and insulated by virtue of the resin per se; when the temperature rises, the ceramic components in different resins can be subjected to ceramic transformation under different temperature gradients, and a high-temperature phase generated in situ plays a further role in preventing and insulating heat, so that the temperature resistance grade of the system is further improved.
Patent CN 111548599A discloses a micro-ablation phenolic resin and a preparation method thereof, which mainly improves the ablation resistance of the resin by adding phenolic beads, glass beads, nano silicon dioxide, carbon powder and tantalum oxide powder into the phenolic resin. The pottery component added in the patent is single, the density of the resin is reduced by adding the microspheres, and the improvement of the comprehensive performance of the resin is limited. For a thermal protection system for a high-Mach-number hypersonic aircraft, besides higher oxidation resistance and ablation resistance, the resin also needs to have more excellent pneumatic scouring resistance.
In order to solve the problems in the prior art, a resin-based composite material for high-performance heat prevention and insulation and a preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a high-performance resin-based composite material for heat prevention and insulation.
In order to achieve the purpose, the invention provides the following technical scheme: a resin-based composite material for high-performance heat prevention and insulation comprises 20-80 parts by weight of high-performance heat prevention and insulation special resin and 20-80 parts by weight of fiber reinforcement; the high-performance heat-insulation-preventing special resin comprises 60-80 parts by weight of propargyl modified phenolic resin, 10-20 parts by weight of zirconium polyacetylacetonate, 5-15 parts by weight of phenyl poly-silicon acetylene, 1-10 parts by weight of silicon boron carbon nitrogen polymer precursor, 1-5 parts by weight of metal silicon powder, 1-10 parts by weight of nano oxide hollow microspheres, 1-10 parts by weight of silicon oxide coated nano carbon hollow microspheres, 1-5 parts by weight of oxide whiskers and 1-10 parts by weight of oxide polymer ceramic precursor cracking products.
Preferably, the silicon-boron-carbon-nitrogen ceramic precursor is a high molecular polymer which can generate silicon-boron-carbon-nitrogen ceramic after cracking treatment in an inert or vacuum state.
Preferably, the particle size of the metal silicon powder is 10-500 μm.
Preferably, the hollow microspheres of nano oxides are one or more of hollow microspheres of silicon oxide, aluminum oxide, titanium oxide and mullite, wherein the size of the nano microspheres is 10-500nm.
Preferably, the size of the silicon oxide coated nano carbon hollow microsphere is 1-500 mu m, and the thickness of the silicon oxide coated layer is 10-500nm.
Preferably, the oxide whiskers are one or more of alumina, silica, mullite and yttrium aluminum garnet whiskers.
Preferably, the oxide polymer ceramic precursor is a polymer containing poly-X-siloxane, X can be one or more of elements such as aluminum, silicon, yttrium, zirconium, hafnium, tantalum and the like, wherein the cracking temperature is 300-900 ℃, the cracking time is 1-12h, and the cracking atmosphere is vacuum, argon or nitrogen.
Preferably, the preparation method of the high-performance heat-proof and heat-insulation special resin comprises the following steps: (1) Adding a solvent, propargylated phenolic resin, zirconium acetylacetonate, phenyl poly-silicon-acetylene and a silicon-boron-carbon-nitrogen precursor into a reactor, and reacting at 40-80 ℃ for 1-12h to obtain a reaction solution; the solvent is one or more of ethanol, glycol, glycerol, isopropanol, toluene, xylene and n-heptane; (2) Adding oxide ceramic precursor cracking powder and metal silicon powder into the reaction solution to perform ball milling, sanding or mechanical stirring treatment; (3) And (3) after the solvent is removed by reduced pressure distillation, adding oxide whiskers, nano oxide hollow microspheres and silicon oxide coated nano carbon hollow microspheres, and stirring at a high speed to obtain the high-performance resin for heat prevention and insulation.
Preferably, the fiber reinforcement is prepared by one or more of carbon fiber, ceramic fiber and organic fiber through the processes of weaving, knitting, needling, weaving and the like, the thickness is 0.5-200mm, and the density is 100-800kg/m 3 (ii) a The carbon fiber comprises one or more of polyacrylonitrile-based carbon fiber, viscose-based carbon fiber or asphalt-based carbon fiber; the organic fiber comprises one or more of phenolic fiber, aramid fiber and polyimide fiber; the ceramic-based fibers comprise one or more of glass fibers, high silica fibers, alumina fibers, mullite fibers, silicon carbide fibers and silicon nitride fibers.
The invention also aims to provide a preparation method of the resin-based composite material for high-performance heat prevention and insulation.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a resin-based composite material for high-performance heat prevention and insulation comprises the following steps:
(1) Uniformly mixing the high-performance heat-insulation-preventing special resin, a solvent and a catalyst; the content of the solvent is 10-200% of the mass of the high-performance heat-proof and heat-insulating special resin; the catalyst is one or more of toluenesulfonic acid, benzenesulfonic acid, sodium petroleum sulfonate, phenolsulfonic acid and hexamethylenetetramine, wherein the content of the catalyst is 1-25% of the mass of the high-performance heat-insulating resin; (2) Putting the fiber reinforcement into a mold, and completely impregnating the high-performance heat-proof special resin into the fiber reinforcement by adopting a vacuum low-pressure impregnation process; (3) Sealing the mould, carrying out sol-gel reaction for 6-120h at the temperature of 80-200 ℃, and cooling to room temperature after the reaction is finished; (4) And (4) drying the composite material obtained in the step (3) at the temperature of 60-150 ℃ for 3-60h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The propargylated phenolic resin, the zirconium polyacetylacetonate, the phenyl poly-silicon-acetylene and the silicon boron carbon nitrogen precursor added in the invention all have crosslinkable reactive groups, can be crosslinked in the reaction process and complete the modification of the resin, and the resin can generate oxidation-resistant and ablation-resistant components such as SiC, zrC, siBCN and the like at a high temperature, thereby effectively improving the comprehensive performance of the resin matrix.
(2) Through the regulation and control of the resin concentration, the catalyst dosage and the sol-gel reaction process parameters, the resin is subjected to phase separation in the gel process and forms a nano-network structure, and the three-dimensional gel network forms nano-scale air holes after the solvent is volatilized and solidified, so that the air holes can limit the convective heat transfer of gas, and the thermal conductivity and the density of the resin are effectively reduced. In addition, the resin also introduces nano hollow ceramic microspheres and silicon oxide modified carbon hollow microspheres, so that the density and the thermal conductivity of the resin are further reduced.
(3) The oxide ceramic precursor cracking product has the advantages of high sintering activity, high specific surface area, low density and the like, can perform carbon thermal reduction reaction at high temperature to generate a carbide ceramic phase, can reduce the temperature of the composite material in a pneumatic thermal environment by performing carbon thermal reduction reaction to obtain endothermic reaction, and can effectively prevent air from entering gas such as CO generated in the reaction process, thereby improving the heat insulation performance.
Drawings
FIG. 1 is a graph of the static thermal examination back temperature change of a quartz lamp made of a composite material in an embodiment 2;
FIG. 2 is an SEM photograph of the composite material of example 2.
Detailed Description
The following will present a preferred embodiment of the present invention, and clearly and completely describe the technical solution of the present invention. The embodiments in the following examples can be further combined or replaced, and the examples are only for describing the preferred embodiments of the present invention, and do not limit the concept and scope of the present invention, and those skilled in the art can make various changes and modifications to the technical solution of the present invention without departing from the design concept of the present invention, and all fall within the protection scope of the present invention.
Example 1
The high-performance heat-proof and heat-insulating special resin is prepared by the following steps:
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 10Kg of zirconium acetylacetonate, 5Kg of phenyl polysilacetylene and 1Kg of silicon-boron-carbon-nitrogen precursor are added into a reactor and reacted for 4 hours at 40 ℃ to obtain a reaction solution A.
(2) Adding 1Kg of alumina ceramic precursor cracking powder (the cracking process is 300 ℃/3h, the cracking atmosphere is N) 2 Gas) and 1Kg of metal silicon powder with the particle size of 10 mu m are subjected to ball milling treatment, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3h.
(3) And (3) distilling the ball-milled resin under reduced pressure to remove the solvent, adding 1Kg of alumina whiskers, 1Kg of silica hollow microspheres with the particle size of 20nm and 1Kg of silica coated carbon hollow microspheres with the particle size of 10 microns, stirring at a high speed for 1h at a stirring speed of 200RPM/min, and thus obtaining the high-performance heat-proof special resin.
The resin-based composite material for heat prevention and insulation is prepared by the following steps:
(1) Uniformly mixing more than 2Kg of prepared high-performance heat-proof and insulation special resin, 0.5Kg of glycol solution and 0.2Kg of toluenesulfonic acid;
(2) The density of the mixture is 500kg/m, the size of the mixture is 120mm multiplied by 15mm 3 The high silica fiber needled felt is put into a mould, and the heat-proof special resin is completely impregnated into the fiber reinforcement by adopting a vacuum low-pressure impregnation process;
(3) Sealing the mould, carrying out sol-gel reaction for 6 hours at the temperature of 100 ℃, and cooling to room temperature after the reaction is finished;
(4) And (4) drying the composite material obtained in the step (3) at 100 ℃ for 24h.
The comprehensive performance of the composite material is tested, and the density of the composite material is 710kg/m 3 The room temperature thermal conductivity is 0.046W/m.K, and the heat release rate is 91 KW.m -2 The back temperature of the quartz lamp at 1200 ℃ after being statically heated and examined for 10min is 120℃。
Example 2
The high-performance heat-proof and heat-insulating special resin is prepared by the following steps:
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 12Kg of zirconium acetylacetonate, 8Kg of phenyl poly-silicon acetylene and 2Kg of silicon-boron-carbon-nitrogen precursor were added into a reactor and reacted at 80 ℃ for 10 hours to obtain a reaction solution A.
(2) Adding 1Kg of alumina ceramic precursor cracking powder (the cracking process is 300 ℃/3h, the cracking atmosphere is N) 2 Gas) and 1Kg of metal silicon powder with the particle size of 10 mu m are subjected to ball milling treatment, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3h.
(3) And (3) distilling the ball-milled resin under reduced pressure to remove the solvent, adding 1Kg of alumina whiskers, 1Kg of silica hollow microspheres with the particle size of 20nm and 1Kg of silica coated carbon hollow microspheres with the particle size of 10 microns, stirring at a high speed for 1h at a stirring speed of 200RPM/min, and thus obtaining the high-performance heat-proof special resin.
The resin-based composite material for heat prevention and insulation is prepared by the following steps:
(1) Uniformly mixing over 2Kg of prepared high-performance heat-proof and heat-insulation special resin, 0.5Kg of glycol solution and 0.2Kg of toluenesulfonic acid;
(2) The density of the mixture is 500kg/m, the size of the mixture is 120mm multiplied by 15mm 3 The high silica fiber needled felt is put into a mould, and the heat-proof special resin is completely impregnated into the fiber reinforcement by adopting a vacuum low-pressure impregnation process;
(3) Sealing the mould, carrying out sol-gel reaction for 6 hours at the temperature of 100 ℃, and cooling to room temperature after the reaction is finished;
(4) And (4) drying the composite material obtained in the step (3) at 100 ℃ for 24h.
The comprehensive performance of the composite material is tested, and the density of the composite material is 770kg/m 3 The room temperature thermal conductivity is 0.049W/m.K, and the heat release rate is 97 KW.m -2 And the back temperature of the quartz lamp is 125 ℃ after the quartz lamp is statically heated and examined for 10min at 1200 ℃.
Example 3
The high-performance heat-proof and heat-insulating special resin is prepared by the following steps:
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 12Kg of zirconium acetylacetonate, 8Kg of phenyl polysilacetylene and 2Kg of silicon-boron-carbon-nitrogen precursor are added into a reactor and reacted for 10 hours at 80 ℃ to obtain a reaction solution A.
(2) Adding 1Kg of alumina ceramic precursor cracking powder (the cracking process is 300 ℃/3h, the cracking atmosphere is N) into the reaction solution A 2 Gas) and 1Kg of metal silicon powder with the particle size of 10 mu m are subjected to ball milling treatment, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3h.
(3) And (3) distilling the ball-milled resin under reduced pressure to remove the solvent, adding 1Kg of alumina whiskers, 1.5Kg of silicon oxide hollow microspheres with the particle size of 20nm and 1.5Kg of silicon oxide coated carbon hollow microspheres with the particle size of 10 microns, stirring at a high speed for 1h at a stirring speed of 200RPM/min, and thus obtaining the high-performance heat-proof and insulation special resin.
The resin-based composite material for heat prevention and insulation is prepared by the following steps:
(1) Uniformly mixing over 2Kg of prepared high-performance heat-proof and heat-insulation special resin, 0.5Kg of glycol solution and 0.2Kg of toluenesulfonic acid;
(2) The size of the powder is 120mm multiplied by 15mm, the density is 300kg/m 3 The carbon fiber needled felt is put into a mould, and the heat-proof special resin is completely impregnated into the fiber reinforcement by adopting a vacuum low-pressure impregnation process;
(3) Sealing the mould, carrying out sol-gel reaction for 6 hours at the temperature of 100 ℃, and cooling to room temperature after the reaction is finished;
(4) And (4) drying the composite material obtained in the step (3) at 100 ℃ for 24h.
The comprehensive performance of the composite material is tested, and the density of the composite material is 470kg/m 3 The room temperature thermal conductivity is 0.031W/m.K, and the heat release rate is 82 KW.m -2 And the back temperature of the quartz lamp is 105 ℃ after the quartz lamp is statically heated and examined for 10min at 1200 ℃.
Example 4
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 12Kg of zirconium acetylacetonate, 8Kg of phenyl poly-silicon acetylene and 2Kg of silicon-boron-carbon-nitrogen precursor were added into a reactor and reacted at 80 ℃ for 10 hours to obtain a reaction solution A.
(2) 1Kg of alumina and 1Kg of hafnium oxide ceramic precursor cracking powder (the cracking process is 600 ℃/3h, the cracking atmosphere is N) are added into the reaction solution A 2 Gas) and 1Kg of metal silicon powder with the particle size of 10 mu m are subjected to ball milling treatment, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3h.
(3) And (3) distilling the ball-milled resin under reduced pressure to remove the solvent, adding 1Kg of alumina whiskers, 1.5Kg of silica hollow microspheres with the granularity of 20nm and 1.5Kg of silica coated carbon hollow microspheres with the granularity of 10 microns, stirring at a high speed, and stirring for 1h at the stirring speed of 200RPM/min to obtain the high-performance heat-proof special resin.
The resin-based composite material for heat prevention and insulation is prepared by the following steps:
(1) Uniformly mixing more than 2Kg of prepared high-performance heat-proof and insulation special resin, 0.5Kg of glycol solution and 0.2Kg of toluenesulfonic acid;
(2) The density of the mixture is 300kg/m, the size of the mixture is 120mm multiplied by 15mm 3 The carbon fiber needled felt is put into a mould, and the heat-proof special resin is completely impregnated into the fiber reinforcement by adopting a vacuum low-pressure impregnation process;
(3) Sealing the mould, carrying out sol-gel reaction for 6 hours at the temperature of 100 ℃, and cooling to room temperature after the reaction is finished;
(4) And (4) drying the composite material obtained in the step (3) at 100 ℃ for 24h.
The comprehensive performance of the composite material is tested, and the density of the composite material is 570kg/m 3 The room temperature thermal conductivity is 0.039W/mK, and the heat release rate is 86KW m -2 And the back temperature of the quartz lamp is 109 ℃ after the quartz lamp is statically heated and examined for 10min at 1200 ℃.
See Table 1 for the overall performance parameters of the composites prepared in examples 1-4.
TABLE 1 comprehensive Property parameters of modified resin-based composite materials for thermal insulation prevention
Referring to fig. 1 and 2, compared to example 1, in example 2, the content of the ablation-resistant components of silicon boron carbon nitride and phenyl poly-silicon acetylene is increased, and after the reaction temperature and the reaction time are properly increased, the density and the thermal conductivity of the composite material are slightly increased, but still maintained at relatively low levels. However, the mass ablation rate and the line ablation rate were significantly improved as compared with those in example 1. In example 3, the carbon fiber needled felt with low density is adopted, and the silicon oxide and the carbon hollow microspheres are introduced, so that the density and the thermal conductivity of the composite material are obviously reduced, and although the ablation resistance of the composite material is weakened to a certain extent, the ablation resistance is still kept at a relatively high level. Compared with the example 3, in the example 4, the hafnium oxide ceramic precursor cracking powder is added, so that the ablation resistance of the composite material is further enhanced under the condition that the composite material keeps low density and low thermal conductivity.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The resin-based composite material for high-performance heat prevention and insulation is characterized by comprising 20-80 parts by weight of high-performance heat prevention and insulation special resin and 20-80 parts by weight of fiber reinforcement;
the high-performance heat-proof special resin comprises 60-80 parts by weight of propargyl modified phenolic resin, 10-20 parts by weight of zirconium polyacetylacetonate, 5-15 parts by weight of phenyl poly-silicon acetylene, 1-10 parts by weight of silicon boron carbon nitrogen polymer ceramic precursor, 1-5 parts by weight of metallic silicon powder, 1-10 parts by weight of nano-oxide hollow microspheres, 1-10 parts by weight of silicon oxide coated nano-carbon hollow microspheres, 1-5 parts by weight of oxide whiskers and 1-10 parts by weight of oxide polymer ceramic precursor cracking products.
2. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the precursor of the SiBN-C ceramic is a high molecular polymer which can generate SiBN-C ceramic after cracking treatment under an inert or vacuum state.
3. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the particle size of the metal silicon powder is 10-500 μm.
4. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the hollow microspheres of nano-oxides are one or more of hollow microspheres of silicon oxide, aluminum oxide, titanium oxide and mullite, wherein the size of the nano-microspheres is 10-500nm.
5. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the silica-coated nanocarbon hollow microspheres have a size of 1-500 μm and a thickness of 10-500nm.
6. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the oxide whiskers are one or more of alumina, silica, mullite and yttrium aluminum garnet whiskers.
7. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the oxide polymer ceramic precursor is a polymer containing poly-X-siloxane, X can be one or more of aluminum, silicon, yttrium, zirconium, hafnium, tantalum and other elements, wherein the cracking temperature is 300-900 ℃, the cracking time is 1-12h, and the cracking atmosphere is vacuum, argon or nitrogen.
8. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the preparation method of the special resin for high-performance heat prevention and insulation comprises the following steps:
(1) Adding a solvent, propargylated phenolic resin, zirconium acetylacetonate, phenyl poly-silicon-acetylene and a silicon-boron-carbon-nitrogen precursor into a reactor, and reacting for 1-12h at 40-80 ℃ to obtain a reaction solution; the solvent is one or more of ethanol, glycol, glycerol, isopropanol, toluene, xylene and n-heptane;
(2) Adding oxide ceramic precursor cracking powder and metal silicon powder into the reaction solution to perform ball milling, sand milling or mechanical stirring treatment;
(3) And (3) after the solvent is removed by reduced pressure distillation, adding oxide whiskers, nano-oxide hollow microspheres and silicon oxide coated nano-carbon hollow microspheres, and stirring at a high speed to obtain the high-performance resin for heat prevention and insulation.
9. The resin-based composite material for high-performance heat prevention and insulation as claimed in claim 1, wherein the fiber reinforcement is prepared from one or more of carbon fiber, ceramic fiber and organic fiber by knitting, needling, weaving and other processes, and has a thickness of 0.5-200mm and a density of 100-800kg/m 3 (ii) a The carbon fiber comprises one or more of polyacrylonitrile-based carbon fiber, viscose-based carbon fiber or asphalt-based carbon fiber; the organic fiber comprises one or more of phenolic fiber, aramid fiber and polyimide fiber; the ceramic-based fibers comprise one or more of glass fibers, quartz fibers, high silica fibers, alumina fibers, mullite fibers, silicon carbide fibers and silicon nitride fibers.
10. The method for preparing the resin-based composite material for high-performance heat prevention and insulation according to any one of claims 1 to 9, characterized by comprising the following steps:
(1) Uniformly mixing the high-performance heat-insulation-preventing special resin, a solvent and a catalyst; the content of the solvent is 10-200% of the mass of the high-performance heat-proof and heat-insulating special resin; the catalyst is one or more of toluenesulfonic acid, benzenesulfonic acid, sodium petroleum sulfonate, phenolsulfonic acid and hexamethylenetetramine, wherein the content of the catalyst is 1-25% of the mass of the resin;
(2) Putting the fiber reinforcement into a mold, and completely impregnating the high-performance heat-proof special resin into the fiber reinforcement by adopting a vacuum low-pressure impregnation process;
(3) Sealing the mould, carrying out sol-gel reaction for 6-120h at the temperature of 80-200 ℃, and cooling to room temperature after the reaction is finished;
(4) And (4) drying the composite material obtained in the step (3) at the temperature of 60-150 ℃ for 3-60h.
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Citations (11)
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