CN117430912A - Expanded microsphere modified fiber reinforced phenolic aerogel composite material and preparation method and application thereof - Google Patents
Expanded microsphere modified fiber reinforced phenolic aerogel composite material and preparation method and application thereof Download PDFInfo
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- CN117430912A CN117430912A CN202311759433.0A CN202311759433A CN117430912A CN 117430912 A CN117430912 A CN 117430912A CN 202311759433 A CN202311759433 A CN 202311759433A CN 117430912 A CN117430912 A CN 117430912A
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- aerogel composite
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- 239000004005 microsphere Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000000835 fiber Substances 0.000 title claims abstract description 58
- 239000004964 aerogel Substances 0.000 title claims abstract description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims abstract description 20
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 20
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 39
- 239000000945 filler Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 10
- 229920000126 latex Polymers 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002748 Basalt fiber Polymers 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229920000103 Expandable microsphere Polymers 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000002679 ablation Methods 0.000 abstract description 34
- 238000009413 insulation Methods 0.000 abstract description 13
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Abstract
The invention provides an expanded microsphere modified fiber reinforced phenolic aerogel composite material, a preparation method and application thereof, wherein the preparation raw materials of the composite material comprise: phenolic resin, hexamethylenetetramine, ethanol, ceramifiable expanded microspheres and fiber preforms. The expanded microsphere modified fiber reinforced phenolic aerogel composite material has low density, a closed cell structure, remarkably improved heat insulation performance, good heat stability and ablation resistance, good processability and convenient industrialization and large-scale production. Compared with the traditional fiber reinforced phenolic aerogel ablation-resistant composite material, the composite material has lower density, more excellent heat insulation performance and ablation resistance, and provides stronger guarantee for the flight stability of hypersonic aircrafts.
Description
Technical Field
The invention belongs to the field of ablation-resistant composite material preparation, and particularly relates to an expanded microsphere modified fiber reinforced phenolic aerogel composite material as well as a preparation method and application thereof.
Background
The fiber reinforced aerogel composite material is an important ablation heat protection material in the aerospace industry and has the characteristics of light weight, heat insulation and the like. The matrix is usually resin with high thermal stability and high pyrolysis residual weight, such as phenolic resin. The mass injection and pyrolysis gas thermal resistance in the ablation process enable the fiber reinforced phenolic aerogel composite material to bear extremely high temperature. Accordingly, fiber reinforced phenolic aerogel composites are used for high temperature thermal protection of reentry vehicles and are increasingly being applied to hypersonic vehicles.
However, the fiber reinforced phenolic aerogel composite material has a through hole structure inside, heat on the surface of the material is more easily transferred to the inside of the material through communicated air holes, and the pyrolysis of a phenolic matrix and the loss of a fiber reinforcement lead to linear backing and mass reduction of the surface of the material, and the serious backing can influence the flight stability of an aircraft and cause potential safety hazards, especially in hypersonic flight. In addition, the higher degree of aggregation of the fibers in the fiber reinforcement results in a higher density of the fiber reinforced composite, and a larger weight reduction space is also present in the composite. Therefore, development of a novel fiber reinforced phenolic aerogel composite is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an expanded microsphere modified fiber reinforced phenolic aerogel composite material, and a preparation method and application thereof. The invention solves the technical problem of heat-proof performance decline of the material in the service process caused by the through hole structure of the traditional fiber reinforced phenolic aerogel ablation-resistant composite material, and the composite material has low density, excellent heat-proof performance and simple preparation process.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in one aspect, the invention provides an expanded microsphere modified fiber reinforced phenolic aerogel composite, the composite comprises the following raw materials:
phenolic resin, hexamethylenetetramine, ethanol, ceramifiable expanded microspheres and fiber preforms.
Preferably, the mass ratio of phenolic resin, hexamethylenetetramine, ethanol and ceramifiable expanded microspheres is 1 (0.1-0.2): (0.5-9): (0.02-0.10), such as 1:0.1:0.5:0.02, 1:0.1:0.8:0.02, 1:0.1:0.02, 1:0.1:1.5:0.05, 1:0.2:0.02, 1:0.2:4:0.02, 1:0.1:5:0.02, 1:0.1:3:0.05, 1:0.2:3:0.10, 1:0.2:7:0.10, 1:0.2:9:0.08, 1:0.1:9:0.02, 1:0.1:9:0.03, 1:0.2:0.2:0.9:0.10, or 1:0.8:0.10, etc.).
In the invention, the composite material has low density, excellent heat insulation performance and ablation resistance, and provides stronger guarantee for the flight stability of the hypersonic aircraft.
In the invention, the phenolic resin and the hexamethylenetetramine are used as raw materials for preparing the phenolic aerogel, the ethanol is used as a solvent, the fiber preform is used as a reinforcement, and the ceramic expanded microsphere has the function of further improving the heat insulation performance of the material by forming a ceramic closed cell structure in the composite material.
In the present invention, the size of the fiber preform is cut according to the size of the cavity of the mold.
Preferably, the ceramifiable expanded microsphere is prepared by the following method:
and (3) grafting the ceramic filler by using a silane coupling agent to obtain a functionalized ceramic filler, adding the functionalized ceramic filler into a latex aqueous solution, performing ultrasonic treatment, then adding the expanded microspheres, uniformly dispersing, and drying to obtain the ceramifiable expanded microspheres.
According to the invention, the ceramic expanded microsphere prepared by the method can be used for obtaining the light closed-cell hollow microsphere which is expandable by heating and can be ceramic at high temperature, and the diameter and the volume of the hollow microsphere can be changed in the high-temperature curing process, and the volume of the hollow microsphere can be increased by tens of times, so that the density of the aerogel heat-insulating composite material can be further reduced.
The ceramic expanded microsphere provided by the invention has the advantages that under the ultra-high temperature service state, the ceramic filler on the surface can form hard ceramic to strengthen the shell of the microsphere, and meanwhile, the introduction of the fiber preform can compensate the brittleness of a closed cell structure, so that the ablation-resistant heat-insulation composite material can be endowed with a high-strength closed cell structure, and the heat-insulation performance of the material is obviously improved.
Preferably, the silane coupling agent is selected from any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane or vinyltris (beta-methoxyethoxy) silane.
Preferably, the ceramic filler is any one or a combination of at least two of montmorillonite, kaolin, wollastonite, halloysite, mica, clay, silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, zirconium boride, boron carbide or strontium hexaboride and other inorganic powders.
Preferably, the functionalized ceramic filler is prepared as follows: the silane coupling agent is dissolved in a solvent to prepare a dilute solution with the concentration of 0.5 to 1 percent (for example, 0.5 percent, 0.6 percent, 0.7 percent, 0.8 percent, 0.9 percent or 1 percent), and the ceramic filler is added and uniformly dispersed, and the functionalized ceramic filler can be obtained after drying.
Preferably, the solvent is selected from water, an alcoholic solvent, or a mixture of water and an alcoholic solvent;
preferably, the alcoholic solvent is selected from methanol or ethanol.
Preferably, the concentration of the latex in the aqueous latex solution is 1 to 6wt%, for example 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt%.
Preferably, the mass ratio of the functionalized ceramic filler, latex and expanded microspheres is 1 (0.5-2): (0.3-1), such as 1:0.5:0.3, 1:0.5:0.5, 1:0.5:0.7, 1:0.5:0.9, 1:0.5:1, 1:0.8:0.3, 1:0.8:0.5, 1:0.8:0.7, 1:0.8:0.9, 1:0.8:1, 1:1:0.3, 1:1:0.5, 1:1:0.8, 1:1:1, 1:1.5:0.3, 1:1.5:0.8, 1:1.8:1, 1:2:0.3, 1:2:0.5, 1:2:1, etc.
Preferably, the power of the ultrasonic treatment is 800W, and the treatment time is 10-60 min, for example, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min.
Preferably, the expanded microspheres have a particle size in the range of 10 to 50 μm, for example 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm.
Preferably, the foaming temperature of the expanded microspheres ranges from 70 ℃ to 130 ℃, such as 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃.
Preferably, the drying temperature is 40-60 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, or 60 ℃, and the drying time is 24-48 hours, such as 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours, or 48 hours.
Preferably, the fiber preform is selected from at least one of carbon fiber, quartz fiber, mullite fiber or basalt fiber preform.
In another aspect, the invention provides a method for preparing the expanded microsphere modified fiber reinforced phenolic aerogel composite material, which comprises the following steps:
(1) Dispersing phenolic resin and hexamethylenetetramine into ethanol, then adding the ceramic expanded microspheres, stirring, and vacuumizing to completely defoam to obtain an expanded microsphere/phenolic resin solution;
(2) Placing the fiber preform in a vacuum device, vacuumizing, adding the expanded microsphere/phenolic resin solution obtained in the step (1) into the vacuum device, enabling the expanded microsphere/phenolic resin solution to permeate the surface of the fiber preform, maintaining pressure and immersing, and then performing gel curing reaction to obtain the expanded microsphere modified fiber reinforced phenolic aerogel composite material.
According to the invention, the composite material prepared by the preparation method is light in weight and ablation-resistant, has the characteristics of low density and excellent heat-proof and heat-insulating properties, has high heat-insulating properties in an ultra-high temperature service state, and provides stronger guarantee for the flight stability of the hypersonic aircraft.
In the invention, the ceramic filler coated on the surface of the ceramic expanded microsphere can form hard ceramic under the service state of ultra-high temperature, strengthen the shell of the microsphere, and can form a high-strength micron-sized closed cavity in the ablation-resistant heat insulation composite material, thereby remarkably improving the heat insulation performance of the material.
The composite material uses the expanded microsphere modified fiber reinforced phenolic aerogel composite material, adopts the ceramifiable expanded microsphere to carry out closed-cell modification, and is organically combined with the phenolic aerogel and the fiber preform reinforced material, so that the weight is further reduced, the heat transfer in the material is greatly weakened, and the composite material still has good dimensional capacity.
Preferably, the stirring time of step (1) is 0.5 to 2 hours, for example 0.5 hours, 0.8 hours, 1 hour, 1.3 hours, 1.5 hours, 1.8 hours or 2 hours.
Preferably, the vacuum in step (2) is applied to a pressure of-0.06 to-0.09 MPa, for example-0.06 MPa, -0.07MPa, -0.08MPa or-0.09 MPa.
Preferably, the time of the pressure maintaining impregnation in the step (2) is 10 to 40min, for example 10min, 15min, 18min, 20min, 25min, 28min, 30min, 35min, 38min or 40min.
Preferably, the temperature of the gel curing reaction in step (2) is 70 to 130 ℃, such as 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃, and the reaction time is 24 to 48 hours, such as 24 hours, 28 hours, 30 hours, 33 hours, 36 hours, 40 hours, 42 hours, 44 hours, 46 hours or 48 hours.
Preferably, after the gel curing reaction, the product is dried in air at normal temperature and normal pressure until no weight loss occurs.
In another aspect, the invention provides the use of an expanded microsphere modified fiber reinforced phenolic aerogel composite as described above as a thermal protective material.
Compared with the prior art, the invention has the following beneficial effects:
the expanded microsphere modified fiber reinforced phenolic aerogel composite material has low density, a closed cell structure, remarkably improved heat insulation performance, good heat stability and ablation resistance, good processability and convenient industrialization and large-scale production. Compared with the traditional fiber reinforced phenolic aerogel ablation-resistant composite material, the composite material has lower density, more excellent heat insulation performance and ablation resistance, and provides stronger guarantee for the flight stability of hypersonic aircrafts.
Drawings
FIG. 1 is a schematic illustration of a process flow for preparing an expanded microsphere modified fiber reinforced phenolic aerogel composite of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The following examples and comparative examples were tested for density: the composite material was cut into a cube, its dimensions were measured and the volume calculated, and its mass was obtained by weighing, and the density was obtained by dividing the mass by the volume.
Thermal conductivity test method (same in the following examples): the thermal conductivity of the composite material at room temperature was measured using a Netzsch brand thermal conductivity meter (model HFM 436) with test standard GB/T10295-2008.
Example 1
In this example, an expanded microsphere modified fiber reinforced phenolic aerogel composite was prepared by the following preparation method:
step one, raw materials are weighed according to the mass ratio of commercial grade latex (Shenzhen Jitian chemical Co., ltd., H0103), functionalized ceramic filler and expanded microspheres (WP 140M of Uvulgare New Material Co., ltd.) of 1:1:1, wherein the particle size of the expanded microspheres is 10 mu M. Uniformly diluting commercial latex in deionized water to a concentration of 3wt%, adding a functionalized ceramic filler, performing ultrasonic treatment with a power of 800W for 20min, adding the expanded microspheres, uniformly dispersing, and then drying at 60 ℃ for 24 hours to obtain the ceramifiable expanded microspheres;
wherein the functionalized ceramic filler is prepared by the following steps: dissolving vinyl triethoxysilane in ethanol to prepare a dilute solution with the concentration of 1%, adding ceramic filler, uniformly dispersing, and drying to obtain functionalized ceramic filler;
step two, weighing raw materials according to the mass ratio of phenolic resin to hexamethylenetetramine to ceramifiable expansion microspheres to ethanol of 1:0.14:0.05:6, dissolving the phenolic resin to hexamethylenetetramine in ethanol, adding the ceramifiable expansion microspheres to mechanically stir for 1h, and vacuumizing to completely defoam to obtain an expansion microsphere/phenolic resin solution;
placing the carbon fiber preform (manufactured by high-tech Co., ltd.) in a vacuum tank, and vacuumizing to-0.09 MPa, wherein the density of the carbon fiber preform is 0.18g/cm 3 And (3) pouring the expanded microsphere/phenolic resin solution obtained in the second step into a vacuum tank until the solution is beyond the surface of the carbon fiber preform, maintaining the pressure and immersing for 30min, then placing a sample into an environment at 95 ℃ for 48 hours for sol-gel and gel curing reaction, and finally drying in air at normal temperature and normal pressure until no weight loss exists, thereby obtaining the expanded microsphere modified fiber reinforced phenolic aerogel composite material.
The volume density of the expanded microsphere modified fiber reinforced phenolic aerogel composite material prepared by the embodiment is 0.21g/cm 3 The thermal conductivity at room temperature is 0.026W/(mK), at 3.62MW/m 2 Under the condition of 30s oxyacetylene flame ablation, the mass ablation rate is 0.0075g/s, and the linear ablation rate is 0.031mm/s.
Example 2
This embodiment differs from embodiment 1 in that: the fiber preform used for preparing the expanded microsphere modified fiber reinforced phenolic aerogel composite material is basalt fiber preform (BCS 3-50, haining Anjie composite material Co., ltd.) with density of 0.24g/cm 3 Wherein the expanded microspheres have a particle size of 15 μm. The other steps are the same as in example 1.
The volume density of the expanded microsphere modified fiber reinforced phenolic aerogel composite material prepared by the embodiment is 0.28g/cm 3 The thermal conductivity at room temperature is 0.034W/(mK), 3.62MW/m 2 Under the ablation condition of 30s oxyacetylene flame, the mass ablation rate is 0.0068g/s, and the linear ablation rate isAt 0.027mm/s.
Example 3
This embodiment differs from embodiment 1 in that: the fiber preform used for preparing the expanded microsphere modified fiber reinforced phenolic aerogel composite material is a quartz fiber preform (Shanxi Huate New Material Co., ltd.) with the density of 0.20g/cm 3 Wherein the expanded microspheres have a particle size of 15 μm. The other steps are the same as in example 1.
The volume density of the expanded microsphere modified fiber reinforced phenolic aerogel composite material prepared by the embodiment is 0.25g/cm 3 The thermal conductivity at room temperature is 0.031W/(m.K), 3.62MW/m 2 Under the ablation condition of 30s oxyacetylene flame, the mass ablation rate is 0.0071g/s, and the linear ablation rate is 0.029mm/s.
Example 4
This embodiment differs from embodiment 1 in that: the mass ratio of phenolic resin, hexamethylenetetramine, ceramifiable expanded microspheres and ethanol was 1:0.14:0.05:4, otherwise identical to example 1.
The volume density of the expanded microsphere modified fiber reinforced phenolic aerogel composite material prepared by the embodiment is 0.23g/cm 3 The thermal conductivity at room temperature is 0.028W/(mK), at 3.62MW/m 2 Under the ablation condition of 30s oxyacetylene flame, the mass ablation rate is 0.0079g/s, and the linear ablation rate is 0.033mm/s.
Comparative example 1
This comparative example differs from example 1 only in that the ceramifiable expanded microspheres were replaced with expanded microspheres (WP 140M, new materials, wu, guangzhou) by adding the commercially available expanded microspheres directly to the composite system without the treatment of the coated ceramic filler.
The volume density of the expanded microsphere modified fiber reinforced phenolic aerogel composite material prepared in the comparative example is 0.19g/cm 3 The thermal conductivity at room temperature is 0.025W/(m.K), at 3.62MW/m 2 Under the ablation condition of 30s oxyacetylene flame, the mass ablation rate is 0.0078g/s, and the linear ablation rate is 0.034mm/s.
Comparative example 2
The difference between this comparative example and example 4 is that the ceramifiable expanded microspheres were replaced with ceramifiable hollow glass microspheres, i.e., hollow glass microspheres (3010, guangdong Megaku glass-plastic technology Co., ltd.) having the same particle size as the expanded microspheres were purchased and then added to the composite system after the same coated ceramic filler was treated.
The volume density of the expanded microsphere modified fiber reinforced phenolic aerogel composite material prepared in the comparative example is 0.25g/cm 3 The thermal conductivity at room temperature is 0.032W/(m.K), 3.62MW/m 2 Under the ablation condition of 30s oxyacetylene flame, the mass ablation rate is 0.0083g/s, and the linear ablation rate is 0.037mm/s.
As can be seen from the above examples 1-4 and comparative examples 1-2, the sample of the examples was at 3.62MW/m 2 Under the ablation condition of 30s oxyacetylene flame, the sample still has a complete structure, the heat insulation effect is excellent, the decay is less, the expanded microspheres in comparative example 1 are not coated with the ceramic filler, and the sample cannot form a closed complete ceramic structure in high-temperature ablation; in comparative example 2, since the ceramic-capable expanded microspheres were replaced with ceramic-capable hollow glass microspheres, the hollow glass microspheres were not capable of being expanded by heat during the heating stage of the composite preparation process, and thus, a larger volume of closed cavity could not be formed in the composite, and the composite could not be further lightened, and thus, the heat insulation performance of the samples prepared in comparative example was inferior to that of the samples in examples.
The applicant states that the invention is illustrated by the above examples of the expanded microsphere modified fiber reinforced phenolic aerogel composite of the invention and the method of making and using it, but the invention is not limited to, i.e. it is not meant that the invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (9)
1. The expanded microsphere modified fiber reinforced phenolic aerogel composite material is characterized in that the preparation raw materials of the composite material comprise:
phenolic resin, hexamethylenetetramine, ethanol, ceramifiable expanded microspheres and fiber preform;
the ceramic expandable microspheres are prepared by the following method:
and (3) grafting the ceramic filler by using a silane coupling agent to obtain a functionalized ceramic filler, adding the functionalized ceramic filler into a latex aqueous solution, performing ultrasonic treatment, then adding the expanded microspheres, uniformly dispersing, and drying to obtain the ceramifiable expanded microspheres.
2. The expanded microsphere modified fiber reinforced phenolic aerogel composite material according to claim 1, wherein the mass ratio of phenolic resin, hexamethylenetetramine, ethanol and ceramic expanded microspheres is 1 (0.1-0.2): (0.5-9): (0.02-0.10).
3. The expanded microsphere modified fiber-reinforced phenolic aerogel composite of claim 1, wherein the silane coupling agent is selected from any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, or vinyltris (β -methoxyethoxy) silane;
the ceramic filler is any one or a combination of at least two of montmorillonite, kaolin, wollastonite, halloysite, mica, clay, silicon dioxide, titanium dioxide, aluminum oxide, magnesium oxide, zinc oxide, zirconium boride, boron carbide or strontium hexaboride and other inorganic powder.
4. The expanded microsphere modified fiber-reinforced phenolic aerogel composite of claim 1, wherein the functionalized ceramic filler is prepared by the following method:
dissolving a silane coupling agent in a solvent to prepare a dilute solution with the concentration of 0.5-1%, adding ceramic filler, uniformly dispersing, and drying to obtain functionalized ceramic filler;
the solvent is selected from water, an alcohol solvent, or a mixture of water and an alcohol solvent;
the alcohol solvent is selected from methanol or ethanol;
the concentration of the latex in the latex aqueous solution is 1-6wt%;
the mass ratio of the functionalized ceramic filler to the latex to the expanded microspheres is 1 (0.5-2): 0.3-1;
the power of the ultrasonic treatment is 800W, and the treatment time is 10-60 min.
5. The expanded microsphere modified fiber-reinforced phenolic aerogel composite material of claim 1, wherein the expanded microsphere has a particle size in the range of 10-50 μm;
the drying temperature is 40-60 ℃, and the drying time is 24-48 hours.
6. The expanded microsphere-modified fiber-reinforced phenolic aerogel composite of claim 1, wherein the fiber preform is selected from at least one of carbon fiber, quartz fiber, mullite fiber, or basalt fiber preform.
7. A method of preparing an expanded microsphere modified fiber-reinforced phenolic aerogel composite according to any one of claims 1 to 6, comprising the steps of:
(1) Dispersing phenolic resin and hexamethylenetetramine into ethanol, then adding the ceramic expanded microspheres, stirring, and vacuumizing to completely defoam to obtain an expanded microsphere/phenolic resin solution;
(2) Placing the fiber preform in a vacuum device, vacuumizing, adding the expanded microsphere/phenolic resin solution obtained in the step (1) into the vacuum device, enabling the expanded microsphere/phenolic resin solution to permeate the surface of the fiber preform, maintaining pressure and immersing, and then performing gel curing reaction to obtain the expanded microsphere modified fiber reinforced phenolic aerogel composite material.
8. The method according to claim 7, wherein the stirring time in the step (1) is 0.5 to 2 hours;
the vacuumizing in the step (2) is carried out until the vacuumizing is-0.06 to-0.09 MPa;
the pressure maintaining and soaking time in the step (2) is 10-40 min;
the temperature of the gel curing reaction in the step (2) is 70-130 ℃, and the reaction time is 24-48 hours;
and after the gel curing reaction, drying the product in the air at normal temperature and normal pressure until no weight loss exists.
9. Use of the expanded microsphere modified fiber-reinforced phenolic aerogel composite according to any one of claims 1-6 as a thermal protection material.
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