CN112830760A - Heat-insulating and high-temperature-resistant aerogel gradient composite material and preparation method thereof - Google Patents
Heat-insulating and high-temperature-resistant aerogel gradient composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heat-insulating and high-temperature-resistant aerogel gradient composite material and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of aerogel composite materials, and particularly relates to a heat-insulating and high-temperature-resistant aerogel gradient composite material and a preparation method thereof.
Background
In recent years, with the urgent need of China for strong national defense and military strength, more performance requirements are provided for the technical bottleneck of the high-performance composite material for the national defense and military industry, in particular to the high-end material which can be repeatedly used in the limited environment. When the supersonic aircraft flies at high speed, the temperature of the outer surface of the aircraft can reach 1200 ℃, and the heat generated during high-speed flight is high, so that good heat insulation materials are needed to protect internal precision equipment from being damaged. In addition, the insulation also needs to have a lower density to avoid additional energy losses.
The aerogel is an open pore type solid material which takes gas as a dispersion medium and has nanoporous pores with the pore size concentrated between 1 nm and 100nm, and is a heat insulation solid material with special microstructures such as high specific surface, nanoscale pores, low density and the like. The silicon dioxide aerogel is one of the aerogels with more perfect preparation technology, and is generally accepted and favored by the industry of heat insulation materials due to good physicochemical property and ultralow heat conductivity. But conventional single system SiO2Aerogel materials can only endure 600 ℃ and greatly limit the application range of the materials. In addition, because the pure silicon-based oxide aerogel has high brittleness and is difficult to process, the large-scale industrial application can not be realized basically.
At present, there is a research on a high temperature resistant alumina-silica aerogel heat insulation composite material, for example, a preparation method of a high temperature resistant alumina-silica aerogel heat insulation composite material in chinese patent CN201010300112, which includes the following operation steps: (1) al (Al)2O3Preparing sol; (2) SiO 22Preparing sol; (3) al (Al)2O3-SiO2Preparing sol; (4) preparing reinforced fibers containing SiC coating; (5) mixing the reinforcing fiber felt or fiber prefabricated member containing SiC coating with Al2O3-SiO2Mixing the sol; (6) aging; (7) and (5) drying the supercritical fluid. Al prepared by using the present invention2O3-SiO2The aerogel composite material has the service temperature of 1200 ℃, and simultaneously has good heat-insulating property and mechanical property. For example, Chinese patent CN201710115402Aerogel thermal insulation material and preparation method thereof, and high-temperature-resistant reinforced SiO2Aerogel insulationComprises a carbon foam reinforcement body, a latticed silicon carbide nanowire and SiO2Aerogel, latticed silicon carbide nanowires filling the void spaces inside the segmented carbon foam, SiO2Aerogel is uniformly filled in the carbon foam reinforcement body, and the density is 0.05-0.15g/cm3The porosity is greater than 90%. The carbon foam reinforcement is flexible carbon foam, is obtained by high-temperature pyrolysis of melamine foam, and is provided with latticed silicon carbide nanowires with the diameter of 50-20 nm. Preparing silicon carbide-carbon composite foam by chemical vapor deposition, and preparing SiO by adopting normal pressure drying technology2The aerogel can further obtain high-temperature-resistant foam-reinforced SiO2Aerogel insulation.
Therefore, the research on the heat-insulating and high-temperature-resistant aerogel composite material has important practical significance for the aerospace field in China and has good market prospect.
Disclosure of Invention
The invention aims to provide a heat-insulating and high-temperature-resistant aerogel gradient composite material and a preparation method thereof aiming at the defects of too narrow temperature application range and poor mechanical strength of the existing aerogel heat-insulating material.
The preparation method of the heat-insulating and high-temperature-resistant aerogel gradient composite material comprises the following steps of:
1) preparing a silicon-based hydrolysis solution, mixing a silicon-based solution, ethanol and deionized water according to a volume ratio of 1 (0.2-0.8) to (0.2-0.8), stirring at normal temperature for 60-90min to obtain the silicon-based hydrolysis solution, slowly adding a binary acid solution with the volume equivalent to 5-30% of the volume of the silicon-based hydrolysis solution while stirring in an ice-water bath environment, adding dicyclopentenyloxyethyl acrylate with the mass equivalent to 0.02-0.03% of the mass of the silicon-based hydrolysis solution, and adjusting the pH value to 3-6 to obtain SiO2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain the composite materialTo fiber composite SiO2Initial state gel;
the silicon-based solution is selected from one or more of ethyl orthosilicate, methyl orthosilicate, polysiloxane, methyltriethoxysilane, methyltrimethoxysilane, silsesquioxane and gamma-glycidyl ether oxypropyltrimethoxysilane, and is mixed in any proportion;
the binary acid solution is selected from two of hydrochloric acid, acetic acid, nitric acid, oxalic acid and phosphoric acid in any proportion;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber composite initial gel: SiO obtained in the previous step2-SiO2Uniformly adding a coupling agent between the surface of the gradient fiber composite initial gel and the surface of the new layer of fiber prefabricated member, and then adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Immediately adding the silicon-based hydrolysis solution obtained in the step 1) into the fiber composite initial gel for liquid sealing, placing the fiber composite initial gel into a constant-temperature water bath for programmed heating, and keeping the temperature constant for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement to obtain a gradient combination final-state gel;
5) drying the gradient combination final state gel obtained in the previous step to obtain a heat insulation and high temperature resistant aerogel gradient composite material;
the fiber prefabricated part in the steps 1), 2) and 3) is selected from one or more of aluminum silicate fibers, graphite fibers, superfine high silica fibers, aluminum silicate ceramic fibers, stone carbon fibers, glass fibers, polycrystalline mullite fibers, high-purity quartz fibers, basalt fibers or polycrystalline alumina fibers in any proportion when mixed;
step 1), step 2), step 3) said compound with fiber prefab after the procedure vacuum impregnation, after adding the prefab, the impregnation tank pressure is vacuumized to-0.1 MPa, the pressure is maintained for 60-120min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and maintain the pressure for 60-120min, then adjust the vacuum degree to-0.05- -0.01MPa and maintain the pressure for 60-120min, then adjust the vacuum degree to-0.1 MPa and maintain the pressure for 30-90min, finally boost the pressure to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure heating.
In the invention:
the ethanol in the step 1) is selected from 99.7 wt% ethanol.
The coupling agent in the step 2) and the step 3) is selected from silane coupling agent or glass fiber coupling agent, and the addition amount of the coupling agent is equivalent to that of SiO20.1-0.2% of the sol solution.
And 3) carrying out temperature programming in the water bath kettle, namely raising the temperature by 5 ℃ every 2-5 hours until the temperature reaches 55-60 ℃.
The organic solvent in the step 4) is an organic solvent with small surface tension, is selected from one or more of methanol, ethanol, tert-butyl alcohol and n-hexane, and is in any proportion when mixed.
The solvent replacement in the step 4) is carried out once every 2 to 5 hours for 2 to 3 days.
The drying process in the step 5) adopts a carbon dioxide supercritical drying method, the drying temperature is 45-80 ℃, and the pressure is 13-18 MPa.
The invention also relates to a thermal insulation and high temperature resistant aerogel gradient composite material obtained by the preparation method, which is a fiber preform reinforced SiO2The heat-insulating and high-temperature-resisting aerogel gradient composite material is formed from fibre prefabricated body and SiO2The aerogel is formed by the temperature resistance of 1000-1200 ℃ in the air atmosphere and the density of 0.3-0.6g/cm3The compression strength is 0.5-4MPa, the room temperature thermal conductivity is 0.025-0.035W/(m.K), and the 1000 ℃ thermal conductivity is0.151-0.159W/(mK), 0.261-0.268W/(mK) of heat conductivity at 1200 ℃, and 1.75-1.96MPa of room temperature compression strength and 10% deformation.
Compared with the prior art, the invention has the following advantages:
1. according to the preparation method of the heat-insulating and high-temperature-resistant aerogel gradient composite material, the silicon-based sol solution is synthesized by using the binary acid under the low-temperature condition, the crosslinking speed is inhibited under the low-temperature condition, and a three-dimensional network is more uniform and compact; the addition of dicyclopentenyloxyethyl acrylate is favorable to improving the coalescence performance of the system, promoting the flow and elastic deformation of the compound and increasing SiO2Tightness of bonding of the aerogel and the fiber preform material; meanwhile, the aerogel composite material is prepared by innovatively adopting a programmed vacuum impregnation method for vacuum impregnation, and the aerogel with better heat-insulating property can be obtained.
2. The heat-insulating and high-temperature-resistant aerogel gradient composite material prepared by the preparation method of the heat-insulating and high-temperature-resistant aerogel gradient composite material has lower heat conductivity and better mechanical strength.
Drawings
FIG. 1 is a schematic process flow diagram of the preparation method of the present invention.
Detailed Description
The present invention is described in further detail below by way of examples, which should not be construed as limiting the invention thereto.
Example 1:
a preparation method of a heat-insulating and high-temperature-resistant aerogel gradient composite material comprises the following steps:
1) preparing a silicon-based hydrolysis solution, mixing ethyl orthosilicate, ethanol (99.7 wt%) and deionized water according to a volume ratio of 1:0.2:0.8, stirring at normal temperature for 60min to obtain the silicon-based hydrolysis solution, slowly adding a binary acid solution (the equal volume of hydrochloric acid and acetic acid is mixed) which is equivalent to 5% of the volume of the silicon-based hydrolysis solution while stirring in an ice-water bath environment, adding dicyclopentenyloxyethyl acrylate which is equivalent to 0.02% of the mass of the silicon-based hydrolysis solution, and adjusting the pH value to 3 to obtain SiO2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain fiber composite SiO2Initial state gel;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber composite initial gel: SiO obtained in the previous step2-SiO2Uniformly adding a coupling agent between the surface of the gradient fiber composite initial gel and the surface of the new layer of fiber prefabricated member, and then adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Immediately adding the silicon-based hydrolysis solution obtained in the step 1) into the fiber composite initial gel for liquid sealing, placing the fiber composite initial gel into a constant-temperature water bath for programmed heating, heating the fiber composite initial gel for 5 ℃ every 2 hours until the temperature reaches 55 ℃, and keeping the temperature constant for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement, and performing replacement for 2d once every 2h to obtain gradient combination final-state gel;
5) drying the gradient combination final-state gel obtained in the previous step by adopting a carbon dioxide supercritical drying method, wherein the drying temperature is 45-80 ℃, and the pressure is 13-18MPa, so as to obtain the heat-insulation and high-temperature-resistant aerogel gradient composite material;
the fiber prefabricated member in the steps 1), 2) and 3) is selected from aluminum silicate fibers;
step 1), step 2), step 3) said compound with fiber prefab after the procedure vacuum impregnation, after adding the prefab, the impregnation tank pressure is vacuumized to-0.1 MPa, pressurize for 60min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and pressurize for 60min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 60min, then adjust the vacuum degree to-0.1 MPa and pressurize for 60min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 120min, then adjust the vacuum degree to-0.1 MPa and pressurize for 30min, finally boost to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure to heat up;
the coupling agent in the step 2) and the step 3) is selected from silane coupling agents;
the organic solvent in the step 4) is selected from methanol.
Example 2:
a preparation method of a heat-insulating and high-temperature-resistant aerogel gradient composite material comprises the following steps:
1) preparing a silicon-based hydrolysis solution, mixing methyl orthosilicate, ethanol (99.7 wt%) and deionized water according to a volume ratio of 1:0.4:0.4, stirring at normal temperature for 90min to obtain a silicon-based hydrolysis solution, and slowly adding a binary acid solution (acetic acid and nitric acid are mixed according to a ratio of 1: 2) is added, the dicyclopentenyloxyethyl acrylate which accounts for 0.03 percent of the mass of the silicon-based hydrolysis solution is added, the pH value is adjusted to be 6, and SiO is obtained2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain fiber composite SiO2Initial state gel;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber composite initial gel: SiO obtained in the previous step2-SiO2Uniformly adding a coupling agent between the surface of the gradient fiber composite initial gel and the surface of the new layer of fiber prefabricated member, and then adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Fiber composite initial gel, immediately adding stepCarrying out liquid sealing on the silicon-based hydrolysis solution in the step 1), putting the silicon-based hydrolysis solution into a constant-temperature water bath kettle, carrying out temperature programming, raising the temperature by 5 ℃ every 3 hours until the temperature reaches 60 ℃, and keeping the constant temperature for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement, and performing replacement for 3d once every 3h to obtain gradient combination final-state gel;
5) drying the gradient combination final-state gel obtained in the previous step by adopting a carbon dioxide supercritical drying method, wherein the drying temperature is 45-80 ℃, and the pressure is 13-18MPa, so as to obtain the heat-insulation and high-temperature-resistant aerogel gradient composite material;
the fiber preform in the steps 1), 2) and 3) is selected from graphite fibers;
step 1), step 2), step 3) said compound with fiber prefabricated member after the procedure vacuum impregnation, after adding the prefabricated member, the impregnation tank is vacuumized to-0.1 MPa, pressurize for 120min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and pressurize for 120min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 120min, then adjust the vacuum degree to-0.1 MPa and pressurize for 120min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 60min, then adjust the vacuum degree to-0.1 MPa and pressurize for 90min, finally boost to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure to heat up;
the coupling agent in the step 2) and the step 3) is selected from glass fiber coupling agents;
the organic solvent in the step 4) is selected from methanol and ethanol which are mixed in equal volume.
Example 3:
a preparation method of a heat-insulating and high-temperature-resistant aerogel gradient composite material comprises the following steps:
1) preparing a silicon-based hydrolysis solution, mixing polysiloxane, ethanol (99.7 wt%) and deionized water according to a volume ratio of 1:0.6:0.2, stirring at normal temperature for 70min to obtain the silicon-based hydrolysis solution, and slowly adding a binary acid solution (nitric acid and oxalic acid are in a ratio of 1: 1) is mixed, and then silicon-based water is addedHydrolyzing 0.025 percent of dicyclopentenyloxyethyl acrylate by mass of the solution, and adjusting the pH value to be 4 to obtain SiO2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain fiber composite SiO2Initial state gel;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber composite initial gel: SiO obtained in the previous step2-SiO2Uniformly adding a coupling agent between the surface of the gradient fiber composite initial gel and the surface of the new layer of fiber prefabricated member, and then adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Immediately adding the silicon-based hydrolysis solution obtained in the step 1) into the fiber composite initial gel for liquid sealing, placing the fiber composite initial gel into a constant-temperature water bath for programmed heating, heating the fiber composite initial gel for 5 ℃ every 4 hours until the temperature reaches 58 ℃, and keeping the temperature constant for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement, and performing replacement for 2d every 4h to obtain gradient combination final-state gel;
5) drying the gradient combination final-state gel obtained in the previous step by adopting a carbon dioxide supercritical drying method, wherein the drying temperature is 45-80 ℃, and the pressure is 13-18MPa, so as to obtain the heat-insulation and high-temperature-resistant aerogel gradient composite material;
the fiber prefabricated member in the steps 1), 2) and 3) is selected from superfine high silica fiber;
step 1), step 2), step 3) said compound with fiber prefab after the procedure vacuum impregnation, after adding the prefab, the impregnation tank pressure is vacuumized to-0.1 MPa, pressurize for 60min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and pressurize for 120min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 60min, then adjust the vacuum degree to-0.1 MPa and pressurize for 60min, finally boost to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure to heat up;
the coupling agent in the step 2) and the step 3) is selected from silane coupling agents;
the organic solvent in the step 4) is selected from methanol, ethanol and tert-butyl alcohol, and the weight ratio of the organic solvent to the solvent is 2: 2: 1 by volume.
Example 4:
a preparation method of a heat-insulating and high-temperature-resistant aerogel gradient composite material comprises the following steps:
1) preparing a silicon-based hydrolysis solution, mixing a silicon-based solution (methyl triethoxysilane and methyl trimethoxysilane are mixed in equal volume), ethanol (99.7 wt%) and deionized water according to the volume ratio of 1:0.8:0.5, stirring at normal temperature for 80min to obtain the silicon-based hydrolysis solution, and slowly adding a binary acid solution (oxalic acid and phosphoric acid are mixed according to the ratio of 1; 2) is added, the dicyclopentenyloxyethyl acrylate which accounts for 0.02 percent of the mass of the silicon-based hydrolysis solution is added, the pH value is adjusted to 5, and SiO is obtained2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain fiber composite SiO2Initial state gel;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber composite initial gel: SiO obtained in the previous step2-SiO2Gradient fiber composite initial stateUniformly adding a coupling agent between the gel surface and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Immediately adding the silicon-based hydrolysis solution obtained in the step 1) into the fiber composite initial gel for liquid sealing, placing the fiber composite initial gel into a constant-temperature water bath for programmed heating, heating the fiber composite initial gel for 5 hours until the temperature reaches 55 ℃, and keeping the temperature constant for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement, and performing replacement for 3d once every 5h to obtain gradient combination final-state gel;
5) drying the gradient combination final-state gel obtained in the previous step by adopting a carbon dioxide supercritical drying method, wherein the drying temperature is 45-80 ℃, and the pressure is 13-18MPa, so as to obtain the heat-insulation and high-temperature-resistant aerogel gradient composite material;
the fiber prefabricated member in the steps 1), 2) and 3) is selected from aluminum silicate ceramic fiber, stone charcoal fiber and glass fiber which are mixed in equal volume;
step 1), step 2), step 3) said compound with fiber prefabricated member after the procedure vacuum impregnation, after adding the prefabricated member, the impregnation tank is vacuumized to-0.1 MPa, pressurize for 120min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and pressurize for 60min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 120min, then adjust the vacuum degree to-0.1 MPa and pressurize for 75min, finally boost to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure to heat up;
the coupling agent in the step 2) and the step 3) is selected from glass fiber coupling agents;
the organic solvent in the step 4) is selected from methanol, ethanol and n-hexane according to a ratio of 2: 1: 1 by volume.
Example 5:
a preparation method of a heat-insulating and high-temperature-resistant aerogel gradient composite material comprises the following steps:
1) system for makingPreparing a silicon-based hydrolysis solution, mixing a silicon-based solution (silsesquioxane and gamma-glycidyl ether oxypropyl trimethoxy silane are mixed according to a volume ratio of 1: 2), ethanol (99.7wt percent) and deionized water according to a volume ratio of 1:0.5:0.6, stirring at normal temperature for 75min to obtain the silicon-based hydrolysis solution, slowly adding a dibasic acid solution (hydrochloric acid and oxalic acid are mixed according to a volume ratio of 2: 1) which is 20 percent of the volume of the silicon-based hydrolysis solution while stirring in an ice water bath environment, adding dicyclopentenyloxyethyl acrylate which is 0.03 percent of the mass of the silicon-based hydrolysis solution, and adjusting the pH value to 3 to obtain SiO2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain fiber composite SiO2Initial state gel;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber composite initial gel: SiO obtained in the previous step2-SiO2Uniformly adding a coupling agent between the surface of the gradient fiber composite initial gel and the surface of the new layer of fiber prefabricated member, and then adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Immediately adding the silicon-based hydrolysis solution obtained in the step 1) into the fiber composite initial gel for liquid sealing, placing the fiber composite initial gel into a constant-temperature water bath for programmed heating, heating the fiber composite initial gel for 5 hours until the temperature reaches 60 ℃, and keeping the temperature constant for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement, and performing replacement for 2d once every 2h to obtain gradient combination final-state gel;
5) drying the gradient combination final-state gel obtained in the previous step by adopting a carbon dioxide supercritical drying method, wherein the drying temperature is 45-80 ℃, and the pressure is 13-18MPa, so as to obtain the heat-insulation and high-temperature-resistant aerogel gradient composite material;
the fiber prefabricated member in the step 1), the step 2) and the step 3) is selected from polycrystalline mullite fiber, high-purity quartz fiber, basalt fiber and polycrystalline alumina fiber which are mixed in equal weight;
step 1), step 2), step 3) said compound with fiber prefabricated member after the procedure vacuum impregnation, after adding the prefabricated member, the impregnation tank is vacuumized to-0.1 MPa, pressurize for 90min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and pressurize for 90min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 90min, then adjust the vacuum degree to-0.1 MPa and pressurize for 90min, then adjust the vacuum degree to-0.05- -0.01MPa and pressurize for 100min, then adjust the vacuum degree to-0.1 MPa and pressurize for 80min, finally boost to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure to heat up;
the coupling agent in the step 2) and the step 3) is selected from silane coupling agents;
the organic solvent in the step 4) is selected from tert-butyl alcohol.
Comparative example 1:
in comparison with example 1, step 1) lacks the addition of dicyclopentenyloxyethyl acrylate, otherwise the same as in example 1.
Experimental example:
the products obtained in the above examples and comparative examples were tested for technical indices as follows:
and (4) analyzing results:
through comparison between the examples and the comparative examples, the thermal conductivity of the thermal insulation and high temperature resistant aerogel gradient composite material obtained in the examples is reduced by more than 18.5% at 1000 ℃, reduced by more than 10.1% at 1200 ℃, and improved by more than 14.0%, which shows that the addition of dicyclopentenyloxyethyl acrylate can better improve the SiO content2The mechanical properties of aerogel and reduce the thermal conductivity of low materials. Acrylic acid dicyclopentadienylThe alkenyl oxyethyl ester is a colorless transparent liquid with high boiling point, is easy to crosslink in the polymerization process, can improve the rigidity and heat resistance of chains after crosslinking, and is a better forming aid.
The comparison of the basic properties of the examples and comparative examples shows that the preparation process of the examples is significantly superior to the comparative examples.
Claims (8)
1. A preparation method of a heat-insulating and high-temperature-resistant aerogel gradient composite material is characterized by comprising the following steps of: the method comprises the following steps:
1) preparing a silicon-based hydrolysis solution, mixing a silicon-based solution, ethanol and deionized water according to a volume ratio of 1 (0.2-0.8) to (0.2-0.8), stirring at normal temperature for 60-90min to obtain the silicon-based hydrolysis solution, slowly adding a binary acid solution with the volume equivalent to 5-30% of the volume of the silicon-based hydrolysis solution while stirring in an ice-water bath environment, adding dicyclopentenyloxyethyl acrylate with the mass equivalent to 0.02-0.03% of the mass of the silicon-based hydrolysis solution, and adjusting the pH value to 3-6 to obtain SiO2Sol solution, then SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain fiber composite SiO2Initial state gel;
the silicon-based solution is selected from one or more of ethyl orthosilicate, methyl orthosilicate, polysiloxane, methyltriethoxysilane, methyltrimethoxysilane, silsesquioxane and gamma-glycidyl ether oxypropyltrimethoxysilane, and is mixed in any proportion;
the binary acid solution is selected from two of hydrochloric acid, acetic acid, nitric acid, oxalic acid and phosphoric acid in any proportion;
2) preparation of SiO2-SiO2Gradient fiber composite initial gel: the fiber composite SiO obtained in the previous step2Uniformly adding a coupling agent between the surface of the initial gel and the surface of the new layer of fiber prefabricated member, and adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain SiO2-SiO2Compounding the gradient fiber with initial gel;
3) preparation of gradient SiO2-SiO2-SiO2Fiber compositeSynthesizing initial gel: SiO obtained in the previous step2-SiO2Uniformly adding a coupling agent between the surface of the gradient fiber composite initial gel and the surface of the new layer of fiber prefabricated member, and then adding SiO2The sol solution is subjected to programmed vacuum impregnation and then is compounded with the fiber prefabricated part to obtain gradient SiO2-SiO2-SiO2Immediately adding the silicon-based hydrolysis solution obtained in the step 1) into the fiber composite initial gel for liquid sealing, placing the fiber composite initial gel into a constant-temperature water bath for programmed heating, and keeping the temperature constant for 2 days;
4) solvent replacement: adding an organic solvent into the gel obtained in the previous step for solvent replacement to obtain a gradient combination final-state gel;
5) drying the gradient combination final state gel obtained in the previous step to obtain a heat insulation and high temperature resistant aerogel gradient composite material;
the fiber prefabricated part in the steps 1), 2) and 3) is selected from one or more of aluminum silicate fibers, graphite fibers, superfine high silica fibers, aluminum silicate ceramic fibers, stone carbon fibers, glass fibers, polycrystalline mullite fibers, high-purity quartz fibers, basalt fibers or polycrystalline alumina fibers in any proportion when mixed;
step 1), step 2), step 3) said compound with fiber prefab after the procedure vacuum impregnation, after adding the prefab, the impregnation tank pressure is vacuumized to-0.1 MPa, the pressure is maintained for 60-120min, then change the vacuum degree to-0.05- -0.01MPa, then adjust the vacuum degree to-0.1 MPa and maintain the pressure for 60-120min, then adjust the vacuum degree to-0.05- -0.01MPa and maintain the pressure for 60-120min, then adjust the vacuum degree to-0.1 MPa and maintain the pressure for 30-90min, finally boost the pressure to the normal pressure, finish the procedure vacuum impregnation, transfer it to the water bath and carry on the procedure heating.
2. The method for preparing a thermal insulation and high temperature resistant aerogel gradient composite material according to claim 1, wherein the method comprises the following steps: the ethanol in the step 1) is selected from 99.7 wt% ethanol.
3. The method for preparing a thermal insulation and high temperature resistant aerogel gradient composite material according to claim 1, wherein the method comprises the following steps: the coupling agent in the step 2) and the step 3) is selected from a silane coupling agent or a glass fiber coupling agent.
4. The method for preparing a thermal insulation and high temperature resistant aerogel gradient composite material according to claim 1, wherein the method comprises the following steps: and 3) carrying out temperature programming in the water bath kettle, namely raising the temperature by 5 ℃ every 2-5 hours until the temperature reaches 55-60 ℃.
5. The method for preparing a thermal insulation and high temperature resistant aerogel gradient composite material according to claim 1, wherein the method comprises the following steps: the organic solvent in the step 4) is an organic solvent with small surface tension, is selected from one or more of methanol, ethanol, tert-butyl alcohol and n-hexane, and is in any proportion when mixed.
6. The method for preparing a thermal insulation and high temperature resistant aerogel gradient composite material according to claim 1, wherein the method comprises the following steps: the solvent replacement in the step 4) is carried out once every 2 to 5 hours for 2 to 3 days.
7. The method for preparing a thermal insulation and high temperature resistant aerogel gradient composite material according to claim 1, wherein the method comprises the following steps: the drying process in the step 5) adopts a carbon dioxide supercritical drying method, the drying temperature is 45-80 ℃, and the pressure is 13-18 MPa.
8. The utility model provides a thermal-insulated, high temperature resistant aerogel gradient composite which characterized in that: the thermal insulation and high temperature resistant aerogel gradient composite material prepared by the preparation method of any one of claims 1 to 7 has the temperature resistance of 1000-1200 ℃ in the air atmosphere and the density of 0.3-0.6g/cm3The compression strength is 0.5-4MPa, the room temperature thermal conductivity is 0.025-0.035W/(m.K), the 1000 ℃ thermal conductivity is 0.151-0.159W/(m.K), the 1200 ℃ thermal conductivity is 0.261-0.268W/(m.K), and the 10% deformation of the room temperature compression strength is 1.75-1.96 MPa.
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