CN115160730B - High-performance heat-proof resin matrix composite material and preparation method thereof - Google Patents
High-performance heat-proof resin matrix composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a resin-based composite material for high-performance heat-proof and insulation and a preparation method thereof, wherein the composite material comprises 20-80 parts by weight of high-performance heat-proof and insulation special resin and 20-80 parts by weight of fiber reinforcement, and the high-performance heat-proof and insulation special resin consists of propargylated phenolic resin, zirconium acetylacetonate, phenyl polysiliconylacetylene, 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 heat conduction, 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 heat-proof resin-based composite material and a preparation method thereof.
Background
With the rapid development of hypersonic aircrafts, higher demands and challenges are placed on the thermal protection systems. The thermal protection system is required to have not only excellent oxidation resistance and ablation resistance, but also excellent low thermal conductance and high airflow scouring resistance.
The introduction of the ceramic component into the resin matrix to modify the resin is an advanced technical means for improving the heat insulation performance of the resin, which provides a new idea for the design of a heat protection system. The heat insulation is usually carried out by means of the resin itself at a temperature below 600 ℃; after the temperature is raised, the ceramic-forming components in different resins are subjected to ceramic-forming conversion under different temperature gradients, and the high-temperature phase generated in situ is relied on to play a role in further heat insulation, so that the temperature resistance level of the system is further improved.
Patent CN 111548599A discloses a micro-ablative phenolic resin and a preparation method thereof, wherein the anti-ablative capability of the resin is improved by adding phenolic microbeads, glass microbeads, nano silicon dioxide, carbon powder and tantalum oxide powder into the phenolic resin. The components which can be vitrified and added in the patent are single, the density of the resin is reduced by adding the microspheres, and the comprehensive performance of the resin is improved only. For the heat protection system for the hypersonic speed aircraft with high Mach number, the resin needs to have more excellent pneumatic scouring resistance besides higher oxidation resistance and ablation resistance.
In order to solve the problems in the prior art, we propose a resin matrix composite for high-performance heat insulation and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a resin-based composite material for high-performance heat insulation.
In order to achieve the above purpose, the present invention provides the following technical solutions: a resin-based composite material for high-performance heat insulation comprises 20-80 parts by weight of high-performance heat 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 propargylated modified phenolic resin, 10-20 parts by weight of zirconium acetylacetonate, 5-15 parts by weight of phenyl polysilane 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 refers to a high polymer which can generate silicon-boron-carbon-nitrogen ceramic after being subjected to cracking treatment in an inert or vacuum state.
Preferably, the granularity of the metal silicon powder is 10-500 mu m.
Preferably, the nano oxide hollow microsphere is one or more of silicon oxide, aluminum oxide, titanium oxide and mullite hollow microsphere, wherein the size of the nano microsphere 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 coating layer is 10-500nm.
Preferably, the oxide whisker is one or more of aluminum oxide, silicon oxide, mullite and yttrium aluminum garnet whisker.
Preferably, the oxide high polymer ceramic precursor is a high polymer containing poly-X-oxygen alkane, 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.
Preferably, the preparation method of the high-performance heat-proof special resin comprises the following steps: (1) Adding a solvent, propargylated phenolic resin, zirconium acetylacetonate, phenyl polysilylacetylene 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, and performing ball milling, sanding or mechanical stirring treatment; (3) And (3) after the solvent is removed by reduced pressure distillation, adding the oxide whisker, the nano oxide hollow microsphere and the silicon oxide coated nano carbon hollow microsphere to perform high-speed stirring, thus obtaining the high-performance heat-proof resin.
Preferably, the fiber reinforcement is prepared from one or more of carbon fiber, ceramic fiber and organic fiber through the processes of braiding, knitting, needling, weaving and the like, and has the thickness of 0.5-200mm, density of 100-800kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the 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 fiber comprises one or more of glass fiber, high silica fiber, alumina fiber, mullite fiber, silicon carbide fiber and silicon nitride fiber.
The invention also aims to provide a preparation method of the resin-based composite material for high-performance heat insulation.
In order to achieve the above purpose, the present invention provides the following technical solutions: the preparation method of the resin-based composite material for high-performance heat insulation comprises the following steps:
(1) Uniformly mixing the high-performance heat-proof special resin, the solvent and the catalyst; the content of the solvent is 10% -200% of the mass of the high-performance heat-proof special resin; the catalyst is one or more of toluene sulfonic acid, benzene sulfonic acid, sodium petroleum sulfonate, phenol sulfonic acid and hexamethylenetetramine, wherein the content of the catalyst is 1-25% of the mass of the high-performance heat-proof resin; (2) Placing the fiber reinforcement in a mould, 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 mold, performing sol-gel reaction at 80-200deg.C for 6-120 hr, and cooling to room temperature after the reaction is completed; (4) And (3) drying the composite material obtained in the step (3) at 60-150 ℃ for 3-60h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The propargylated phenolic resin, the zirconium acetylacetonate, the phenyl polysilicate 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 finish the modification of the resin, can generate oxidation-resistant and ablation-resistant components such as SiC, zrC, siBCN and the like at a high temperature state, and effectively improves the comprehensive performance of a resin matrix.
(2) Through the regulation and control of the concentration of the resin, the dosage of the catalyst and the technological parameters of the sol-gel reaction, the resin is subjected to phase separation in the gel process and forms a nano-network structure, the three-dimensional gel network forms nano-scale air holes after the solvent volatilizes and solidifies, the air holes can limit the convective heat transfer of gas, and the thermal conductivity and density of the resin are effectively reduced. In addition, the resin is introduced with nano hollow ceramic microspheres and silica modified carbon hollow microspheres, so that the density and the thermal conductivity of the resin are further reduced.
(3) The cracking product of the oxide ceramic precursor has the advantages of high sintering activity, high specific surface area, low density and the like, carbothermic reaction can be carried out at high temperature to generate carbide ceramic phase, the carbothermic reaction is an endothermic reaction, the temperature of the composite material in a aerodynamic thermal environment can be reduced, and gases such as CO and the like generated in the reaction process can effectively block air from entering, so that the heat insulation performance is improved.
Drawings
FIG. 1 is a graph showing the static heat check back temperature change of a quartz lamp of the composite material in embodiment 2;
fig. 2 is an SEM photograph of the composite material in example 2.
Detailed Description
The following will give a preferred embodiment of the present invention, and a clear and complete description of the technical solution of the present invention will be given. The embodiments in the following examples may be further combined or replaced, and the examples are merely illustrative of the preferred embodiments of the present invention and not intended to limit the spirit and scope of the present invention, and various changes and modifications made by those skilled in the art to which the present invention pertains without departing from the spirit of the present invention.
Example 1
The preparation method comprises the following steps of:
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 10Kg of zirconium acetylacetonate, 5Kg of phenyl polysilylacetylene and 1Kg of silicon boron carbon nitrogen precursor are added into a reactor to react for 4 hours at 40 ℃ to obtain a reaction solution A.
(2) 1Kg of oxidation was added to the reaction solution AAluminum ceramic precursor cracking powder (cracking process 300 ℃/3h, cracking atmosphere N) 2 Gas), 1Kg of metal silicon powder with granularity of 10 mu m, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3 hours.
(3) And (3) carrying out reduced pressure distillation on the ball-milled resin to remove the solvent, adding 1Kg of aluminum oxide whisker, 1Kg of silicon oxide hollow microsphere with 20nm granularity and 1Kg of silicon oxide coated carbon hollow microsphere with 10 microns granularity, stirring at a high speed, and stirring for 1h at a stirring speed of 200RPM/min to obtain the high-performance heat-proof special resin.
The resin-based composite material for heat insulation is prepared by the following steps:
(1) Uniformly mixing 2Kg of the high-performance heat-proof special resin prepared above, 0.5Kg of ethylene glycol solution and 0.2Kg of toluene sulfonic acid;
(2) The size is 120mm multiplied by 15mm, and the density is 500kg/m 3 The high silica fiber needled felt is put into a mould, and the heat-proof special resin is completely immersed into the fiber reinforcement by adopting a vacuum low-pressure immersion process;
(3) Sealing the mold, performing a sol-gel reaction at 100 ℃ for 6 hours, and cooling to room temperature after the reaction is finished;
(4) And (3) drying the composite material obtained in the step (3) at 100 ℃ for 24 hours.
The composite material was tested for its overall properties and had a density of 710kg/m 3 The thermal conductivity at room temperature is 0.046W/m.K, and the heat release rate is 91 KW.m -2 The back temperature after static heating and checking for 10min by a quartz lamp at 1200 ℃ is 120 ℃.
Example 2
The preparation method comprises the following steps of:
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 12Kg of zirconium acetylacetonate, 8Kg of phenyl polysilylacetylene and 2Kg of silicon boron carbon nitrogen precursor are added into a reactor to react for 10 hours at 80 ℃ to obtain a reaction solution A.
(2) 1Kg of alumina ceramic precursor cracking powder (cracking process 300) was added to the reaction solution AAt the temperature of 3 ℃ and the cracking atmosphere of N 2 Gas), 1Kg of metal silicon powder with granularity of 10 mu m, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3 hours.
(3) And (3) carrying out reduced pressure distillation on the ball-milled resin to remove the solvent, adding 1Kg of aluminum oxide whisker, 1Kg of silicon oxide hollow microsphere with 20nm granularity and 1Kg of silicon oxide coated carbon hollow microsphere with 10 microns granularity, stirring at a high speed, and stirring for 1h at a stirring speed of 200RPM/min to obtain the high-performance heat-proof special resin.
The resin-based composite material for heat insulation is prepared by the following steps:
(1) Uniformly mixing 2Kg of the high-performance heat-proof special resin prepared above, 0.5Kg of ethylene glycol solution and 0.2Kg of toluene sulfonic acid;
(2) The size is 120mm multiplied by 15mm, and the density is 500kg/m 3 The high silica fiber needled felt is put into a mould, and the heat-proof special resin is completely immersed into the fiber reinforcement by adopting a vacuum low-pressure immersion process;
(3) Sealing the mold, performing a sol-gel reaction at 100 ℃ for 6 hours, and cooling to room temperature after the reaction is finished;
(4) And (3) drying the composite material obtained in the step (3) at 100 ℃ for 24 hours.
The comprehensive performance of the composite material is tested, and the density of the composite material is 770kg/m 3 The thermal conductivity at room temperature is 0.049W/m.K, and the heat release rate is 97 KW.m -2 The back temperature after static heating and checking for 10min by a quartz lamp at 1200 ℃ is 125 ℃.
Example 3
The preparation method comprises the following steps of:
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 12Kg of zirconium acetylacetonate, 8Kg of phenyl polysilylacetylene and 2Kg of silicon boron carbon nitrogen precursor are added into a reactor to react for 10 hours at 80 ℃ to obtain a reaction solution A.
(2) 1Kg of alumina ceramic precursor cracking powder (cracking process is 300 ℃/3h, cracking atmosphere is N) is added into the reaction solution A 2 Qi, 1KAnd g, performing ball milling treatment on the metal silicon powder with the granularity of 10 mu m, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3 hours.
(3) And (3) carrying out reduced pressure distillation on the resin subjected to ball milling to remove the solvent, adding 1Kg of aluminum oxide whisker, 1.5Kg of silicon oxide hollow microspheres with 20nm granularity and 1.5Kg of silicon oxide coated carbon hollow microspheres with 10 microns granularity, stirring at a high speed, and stirring at a stirring speed of 200RPM/min for 1h to obtain the high-performance heat-proof special resin.
The resin-based composite material for heat insulation is prepared by the following steps:
(1) Uniformly mixing 2Kg of the high-performance heat-proof special resin prepared above, 0.5Kg of ethylene glycol solution and 0.2Kg of toluene sulfonic acid;
(2) The size is 120mm multiplied by 15mm, and the density is 300kg/m 3 The carbon fiber needled felt of (2) is put into a mould, and the heat-proof special resin is fully immersed into the fiber reinforcement by adopting a vacuum low-pressure immersion process;
(3) Sealing the mold, performing a sol-gel reaction at 100 ℃ for 6 hours, and cooling to room temperature after the reaction is finished;
(4) And (3) drying the composite material obtained in the step (3) at 100 ℃ for 24 hours.
The composite material was tested for its overall properties and had a density of 470kg/m 3 The thermal conductivity at room temperature is 0.031W/mK, and the heat release rate is 82 KW.m -2 The back temperature after static heating and checking for 10min by a quartz lamp at 1200 ℃ is 105 ℃.
Example 4
(1) 30Kg of xylene, 60Kg of propargylated phenolic resin, 12Kg of zirconium acetylacetonate, 8Kg of phenyl polysilylacetylene and 2Kg of silicon boron carbon nitrogen precursor are added into a reactor to react for 10 hours at 80 ℃ to obtain a reaction solution A.
(2) 1Kg of aluminum oxide and 1Kg of hafnium oxide ceramic precursor cracking powder (the cracking process is 600 ℃/3h, and the cracking atmosphere is N) are added into the reaction solution A 2 Gas), 1Kg of metal silicon powder with granularity of 10 mu m, wherein the ball milling rotating speed is 200RPM/min, and the ball milling time is 3 hours.
(3) And (3) carrying out reduced pressure distillation on the resin subjected to ball milling to remove the solvent, adding 1Kg of aluminum oxide whisker, 1.5Kg of silicon oxide hollow microspheres with 20nm granularity and 1.5Kg of silicon oxide coated carbon hollow microspheres with 10 microns granularity, stirring at a high speed, and stirring at a stirring speed of 200RPM/min for 1h to obtain the high-performance heat-proof special resin.
The resin-based composite material for heat insulation is prepared by the following steps:
(1) Uniformly mixing 2Kg of the high-performance heat-proof special resin prepared above, 0.5Kg of ethylene glycol solution and 0.2Kg of toluene sulfonic acid;
(2) The size is 120mm multiplied by 15mm, and the density is 300kg/m 3 The carbon fiber needled felt of (2) is put into a mould, and the heat-proof special resin is fully immersed into the fiber reinforcement by adopting a vacuum low-pressure immersion process;
(3) Sealing the mold, performing a sol-gel reaction at 100 ℃ for 6 hours, and cooling to room temperature after the reaction is finished;
(4) And (3) drying the composite material obtained in the step (3) at 100 ℃ for 24 hours.
The composite material was tested for its overall properties and had a density of 570kg/m 3 The thermal conductivity at room temperature is 0.039W/mK, and the heat release rate is 86 KW.m -2 The back temperature after static heating and checking for 10min by a quartz lamp at 1200 ℃ is 109 ℃.
The composite materials prepared in examples 1-4 have the overall performance parameters shown in Table 1.
TABLE 1 comprehensive performance parameters of modified resin matrix composites for thermal insulation
Referring to fig. 1 and 2, the contents of the ablation resistant components silicon boron carbon nitrogen and phenyl polysilylacetylene are increased in example 2 compared with example 1, 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 a relatively low level. However, the quality ablation rate and the line ablation rate were significantly improved over those in example 1. In example 3, a low-density carbon fiber needled felt is adopted, and silicon oxide and carbon hollow microspheres are introduced, so that the density and the thermal conductivity of the composite material are obviously reduced, and the ablation resistance of the composite material is still kept at a relatively high level although the ablation resistance is weakened to a certain extent. Compared with example 3, the hafnium oxide ceramic precursor cracking powder is added in example 4, so that the ablation resistance of the composite material is further enhanced under the condition of keeping low density and low thermal conductivity.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The resin-based composite material for high-performance heat insulation is characterized by comprising 20-80 parts by weight of high-performance heat 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 propargylated modified phenolic resin, 10-20 parts by weight of zirconium acetylacetonate, 5-15 parts by weight of phenyl polysilicosane, 1-10 parts by weight of silicon boron carbon nitrogen polymer ceramic 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 whisker and 1-10 parts by weight of oxide polymer ceramic precursor cracking product;
the oxide polymer ceramic precursor in the oxide polymer ceramic precursor cracking product is a polymer containing poly-X-oxygen alkane, X is one or more of aluminum, silicon, yttrium, zirconium, hafnium and tantalum, wherein the cracking temperature is 300-900 ℃, the cracking time is 1-12h, and the cracking atmosphere is vacuum, argon or nitrogen.
2. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the silicon-boron-carbon-nitrogen high-molecular ceramic precursor is a high-molecular polymer capable of generating silicon-boron-carbon-nitrogen ceramic after being subjected to cracking treatment in an inert or vacuum state.
3. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the granularity of the metal silicon powder is 10-500 μm.
4. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the nano-oxide hollow microspheres are one or more of silica, alumina, titania and mullite hollow microspheres, and the size of the nano-microspheres is 10-500nm.
5. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the size of the silica-coated nano carbon hollow microsphere is 1-500 μm, and the thickness of the silica coating layer is 10-500nm.
6. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the oxide whisker is one or more of alumina, silica, mullite and yttrium aluminum garnet whisker.
7. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the preparation method of the high-performance heat insulation special resin comprises the following steps:
(1) Adding a solvent, propargylated phenolic resin, zirconium acetylacetonate, phenyl polysilylacetylene and a silicon boron carbon nitrogen polymer ceramic 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 an oxide polymer ceramic precursor cracking product and metal silicon powder into the reaction solution for ball milling, sanding or mechanical stirring treatment;
(3) And (3) after the solvent is removed by reduced pressure distillation, adding the oxide whisker, the nano oxide hollow microsphere and the silicon oxide coated nano carbon hollow microsphere to perform high-speed stirring, thus obtaining the high-performance heat-proof resin.
8. The resin-based composite material for high-performance heat insulation according to claim 1, wherein the fiber reinforcement is prepared from one or more of carbon fiber, ceramic fiber and organic fiber through braiding, knitting, needling or weaving, and has a thickness of 0.5-200mm and a density of 100-800kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the 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 fiber comprises one or more of glass fiber, quartz fiber, high silica fiber, alumina fiber, mullite fiber, silicon carbide fiber and silicon nitride fiber.
9. A method for preparing a resin-based composite material for high-performance heat insulation according to any one of claims 1 to 8, comprising the steps of:
(1) Uniformly mixing the high-performance heat-proof special resin, the solvent and the catalyst; the content of the solvent is 10% -200% of the mass of the high-performance heat-proof special resin; the catalyst is one or more of toluene sulfonic acid, benzene sulfonic acid, sodium petroleum sulfonate, phenol sulfonic acid and hexamethylenetetramine, wherein the content of the catalyst is 1-25% of the mass of the high-performance heat-proof special resin;
(2) Placing the fiber reinforcement in a mould, 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 mold, performing sol-gel reaction at 80-200deg.C for 6-120 hr, and cooling to room temperature after the reaction is completed;
(4) And (3) drying the composite material obtained in the step (3) at 60-150 ℃ for 3-60h.
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| CN101125908A (en) * | 2006-08-14 | 2008-02-20 | 中国科学院化学研究所 | Heat-resistant substrate resin and preparation method thereof |
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