CN117430911A - Light ablation-resistant closed-cell composite material and preparation method and application thereof - Google Patents
Light ablation-resistant closed-cell composite material and preparation method and application thereof Download PDFInfo
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- CN117430911A CN117430911A CN202311759431.1A CN202311759431A CN117430911A CN 117430911 A CN117430911 A CN 117430911A CN 202311759431 A CN202311759431 A CN 202311759431A CN 117430911 A CN117430911 A CN 117430911A
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002679 ablation Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000004005 microsphere Substances 0.000 claims abstract description 51
- 239000000835 fiber Substances 0.000 claims abstract description 33
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 17
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 16
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 16
- 239000005011 phenolic resin Substances 0.000 claims abstract description 16
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 42
- 239000000945 filler Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 10
- 229920000126 latex Polymers 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011240 wet gel Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 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
- 238000005266 casting Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000243 solution Substances 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
- 229920000103 Expandable microsphere Polymers 0.000 claims description 4
- 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
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000002791 soaking Methods 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
- 229920002748 Basalt fiber Polymers 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
- 239000007864 aqueous solution Substances 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
- 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
- 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
- 239000000843 powder 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
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract 1
- 239000004964 aerogel Substances 0.000 description 14
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004965 Silica aerogel Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 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
- C08J9/0085—Use of fibrous 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
- 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 a light ablation-resistant closed-cell composite material, and a preparation method and application thereof, wherein the preparation raw materials of the light ablation-resistant closed-cell composite material comprise: phenolic resins, hexamethylenetetramine, ethylene glycol, ceramifiable expanded microspheres, 3-aminopropyl triethoxysilane, and chopped fibers; the mass ratio of the phenolic resin to the hexamethylenetetramine to the glycol to the ceramifiable expanded microspheres to the 3-aminopropyl triethoxysilane to the chopped fibers is 1 (0.01-0.10), 3-6, 0.02-0.10, 0.25-1 and 0.01-0.11. The low density and closed pore structure of the composite material obviously improve the heat insulation performance of the material, have good heat stability and ablation resistance, and good processability, and are convenient for industrialization and large-scale production.
Description
Technical Field
The invention belongs to the field of ablation-resistant composite material preparation, and relates to a light ablation-resistant closed-cell composite material, and a preparation method and application thereof.
Background
The ultra-high temperature ablation heat protection technology and materials are of great importance to the development of ultra-high speed spacecrafts, space reentry spacecrafts, rocket propulsion devices and missile launchers. Specifically, ablative materials are used to reduce heat transfer from an ionized bow-wave layer and resist strong external thermal loads through self-sacrifice mechanisms such as phase change, chemical reactions, and physical changes. Polymer-based materials have been widely used in the aerospace industry as ablative materials, wherein phenolic resin-based composites play an important role due to their high thermal stability, chemical stability, dimensional stability and excellent ablative properties, and have received extensive attention from researchers.
The fiber reinforced phenolic aerogel ablation-resistant composite material in recent years has the characteristics of low density, high temperature resistance and high thermal blockage, is uniform in ablation and small in retreating amount in a high-temperature environment, can well maintain the ablation shape in the service process, and well solves the heat protection problems of high heat flow, high standing point pressure and short-time extreme severe environments of spacecrafts such as return satellites and airships. However, the fiber reinforced phenolic aerogel ablation-resistant composite material is of a through hole structure, so that heat on the surface of the material can be transferred into the material through a large number of communicated air holes and irreversibly damages the structure and the function of the material, and therefore, a novel light ablation-resistant closed-hole composite material is urgently required to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a light ablation-resistant closed-cell composite material, and a preparation method and application thereof. The invention solves the technical problem that the heat insulation performance of the traditional fiber reinforced phenolic aerogel ablation-resistant composite material is poor due to a through hole structure.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in one aspect, the invention provides a lightweight ablation-resistant closed cell composite material, the preparation raw materials of which comprise:
phenolic resins, hexamethylenetetramine, ethylene glycol, ceramifiable expanded microspheres, 3-aminopropyl triethoxysilane, and chopped fibers;
the mass ratio of the phenolic resin to the hexamethylenetetramine to the glycol to the ceramifiable expanded microspheres to the 3-aminopropyl triethoxysilane to the chopped fibers is 1 (0.01-0.10), 3-6, 0.02-0.10, 0.25-1 and 0.01-0.11.
In the invention, the composite material has low density and a closed cell structure, and the heat insulation performance of the material is obviously improved, so that the composite material has good heat stability and ablation resistance, and has good processability, thereby being convenient for industrialization and large-scale production.
In the invention, the phenolic resin, the hexamethylenetetramine and the 3-aminopropyl triethoxysilane are used as raw materials for preparing the silica/phenolic double-system aerogel, the ethylene glycol is used as a solvent, the chopped fiber 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 invention, the mass ratio of the phenolic resin to the hexamethylenetetramine to the ethylene glycol to the ceramifiable expansion microsphere to the 3-aminopropyl triethoxysilane to the chopped fiber is 1 (0.01-0.10) to (3-6) to (0.02-0.10) to (0.25-1) to (0.01-0.11), namely the use amount of the hexamethylenetetramine can be 0.01, 0.02, 0.03, 0.05, 0.07, 0.08 or 0.10, the use amount of the ethylene glycol can be 3, 3.5, 4, 4.5, 5.5 or 6, the use amount of the ceramifiable expansion microsphere can be 0.02, 0.03, 0.05, 0.07, 0.08 or 0.10, and the use amount of the 3-aminopropyl triethoxysilane can be 0.25, 0.30, 0.35, 0.4, 0.5, 0.8 or 0.9.1; the chopped fibers may be used in an amount of 0.01, 0.02, 0.03, 0.05, 0.07, 0.08, 0.10, or 0.11.
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 chopped fiber 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: 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;
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 160 ℃ to 220 ℃, such as 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃.
Preferably, the drying temperature is 60-100 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, and the drying time is 4-24 hours, such as 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours.
Preferably, the chopped fibers are any one or a combination of at least two of chopped carbon fibers, chopped quartz fibers, chopped mullite fibers or chopped basalt fibers.
Preferably, the chopped fibers have a diameter of 5 to 20 μm (e.g., 5 μm, 7 μm, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm) and a length of 0.5 to 3mm (e.g., 0.5mm, 0.8mm, 1mm, 1.5mm, 1.8mm, 2mm, 2.5mm, 2.8mm, or 3 mm).
In another aspect, the invention provides a method of making a lightweight ablation resistant closed cell composite as described above, the method comprising the steps of:
(1) Dispersing phenolic resin, hexamethylenetetramine, ethylene glycol, ceramic expanded microspheres and 3-aminopropyl triethoxysilane into the ethylene glycol, and then adding chopped fibers and uniformly dispersing to obtain slurry;
(2) Transferring the slurry obtained in the step (1) into a casting mold, vacuumizing until bubbles are completely eliminated, sealing the casting mold, and heating to obtain a wet gel composite material;
(3) And (3) demolding the wet gel composite material obtained in the step (2), removing ethylene glycol, and drying to obtain the light ablation-resistant closed cell composite material.
According to the invention, the lightweight ablation-resistant closed-cell composite material is prepared by the preparation method, in the preparation method, the ceramic expanded microspheres are adopted to carry out closed-cell modification, the silica/phenolic double-system aerogel is adopted as a matrix, the thermal barrier effect of the inorganic silica aerogel is utilized to inhibit the thermal decomposition rate of the phenolic organic framework, and the strength and the thermal stability of the phenolic aerogel framework structure are effectively improved.
The light ablation-resistant closed-cell composite material disclosed by the invention has the advantages of low density, excellent heat insulation performance, excellent ablation resistance, good processability, simple preparation process, stable performance and convenience in industrialization and large-scale production.
Compared with the traditional fiber reinforced phenolic aerogel ablation-resistant composite material, the light ablation-resistant closed-cell composite material has lower density, more excellent heat insulation performance and ablation resistance, and can expand the application of the light fiber reinforced phenolic aerogel composite material in medium-high heat flow, low residence pressure and long-time thermal environment.
Preferably, the dispersing of the phenolic resin, the hexamethylenetetramine, the ethylene glycol, the ceramic expandable microspheres and the 3-aminopropyl triethoxysilane into the ethylene glycol in the step (1) is realized through mechanical stirring and ultrasonic dispersing.
Preferably, the heating in the step (2) is performed by heating at 90-140 ℃ (e.g. 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃) for 1-3 hours (e.g. 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours), then raising the temperature to 160-200 ℃ (e.g. 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃) and continuing to heat for 1-3 hours (e.g. 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours).
Preferably, the glycol is removed in step (3) by soaking in absolute ethanol.
Preferably, the drying in the step (3) is directly performed in normal pressure air at room temperature (less than or equal to 30 ℃), until no weight loss occurs.
In another aspect, the invention provides the use of a lightweight ablation resistant closed cell composite as described above as a thermal protective material.
Compared with the prior art, the invention has the following beneficial effects:
the light ablation-resistant closed-cell composite material disclosed by the invention has low density, a closed-cell structure, good thermal stability and ablation resistance, good processability and convenience in industrialization and large-scale production, and the heat insulation performance of the material is obviously improved. Compared with the traditional fiber reinforced phenolic aerogel ablation-resistant composite material, the fiber reinforced phenolic aerogel ablation-resistant composite material has lower density, more excellent heat insulation performance and ablation resistance, and can expand the application of the light fiber reinforced phenolic aerogel composite material in medium-high heat flow, low residence pressure and long-time heat environment.
Drawings
FIG. 1 is a schematic illustration of the process flow 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.
Example 1
In this embodiment, a light ablation-resistant closed-cell composite material is provided, and the preparation process flow is shown in fig. 1, and the preparation method specifically includes the following steps:
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 175M of Guangzhou Utility materials 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 80 ℃ 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, hexamethylenetetramine, ethylene glycol, ceramifiable expansion microspheres, 3-aminopropyl triethoxysilane and chopped carbon fibers of 1:0.05:4:0.05:0.5:0.05, wherein the diameter of the chopped carbon fibers is 7 mu m, and the length of the chopped carbon fibers is 2mm. Phenolic resin, hexamethylenetetramine, ethylene glycol, ceramic expanded microspheres and 3-aminopropyl triethoxysilane are firstly dispersed into the ethylene glycol by mechanical stirring and ultrasonic dispersing. Then adding chopped carbon fibers and uniformly dispersing to obtain slurry;
transferring the slurry obtained in the step two into a casting mold, vacuumizing until bubbles are completely eliminated, sealing the casting mold, adding 3 hours at 120 ℃, and then increasing the temperature to 180 ℃ and continuing adding 3 hours to obtain a wet gel composite material;
and step four, demolding the wet gel composite material obtained in the step three, soaking the wet gel composite material in absolute ethyl alcohol to remove ethylene glycol, and finally directly drying the wet gel composite material in normal pressure air at room temperature (less than or equal to 30 ℃) until no weight loss exists, so that the light ablation-resistant closed cell composite material is obtained.
The volume density of the light ablation-resistant closed-cell composite material prepared by the embodiment is 0.2g/cm 3 The thermal conductivity at room temperature was 0.029W/(mK), the distance between the nozzle tip of the oxyacetylene gun and the sample was 40mm, the inner diameter of the tip was 2mm, and the flow rates of oxygen and acetylene were 0.4 and 0.5m, respectively 3 The line ablation rate was 0.077mm/s under the oxyacetylene flame ablation conditions of/h, 33 s.
The density test method in the examples is (the same as in the following examples): 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 2
This embodiment differs from embodiment 1 in that: the chopped fiber used for preparing the light ablation-resistant closed-cell composite material is chopped mullite fiber with the diameter of 1 mu m and the length of 0.5mm, wherein the particle size of the expanded microsphere is 15 mu m. The other steps are the same as in example 1.
The volume density of the light ablation-resistant closed-cell composite material prepared by the embodiment is 0.18g/cm 3 The thermal conductivity at room temperature was 0.023W/(mK), the distance between the nozzle tip of the oxyacetylene gun and the sample was 40mm, the inner diameter of the tip was 2mm, and the flow rates of oxygen and acetylene were 0.4 and 0.5m, respectively 3 The linear ablation rate is 0.068mm/s under the condition of oxyacetylene flame ablation of/h and 33 s.
Example 3
This embodiment differs from embodiment 1 in that: the chopped fibers used for preparing the light ablation-resistant closed-cell composite material are chopped quartz fibers, the diameter is 9 mu m, the length is 1mm, and the particle size of the expanded microspheres is 15 mu m. The other steps are the same as in example 1.
The volume density of the light ablation-resistant closed-cell composite material prepared by the embodiment is 0.17g/cm 3 The thermal conductivity at room temperature was 0.022W/(mK), the distance between the tip of the nozzle of the oxyacetylene gun and the sample was 40mm, the inner diameter of the tip was 2mm, and the flow rates of oxygen and acetylene were 0.4 and 0.5m, respectively 3 The linear ablation rate is 0.069mm/s under the condition of oxyacetylene flame ablation of/h and 33 s.
Example 4
This embodiment differs from embodiment 1 in that: the mass ratio of phenolic resin, hexamethylenetetramine, ethylene glycol, ceramifiable expanded microspheres, 3-aminopropyl triethoxysilane and chopped carbon fibers was 1:0.05:4:0.05:0.5:0.07, except that the method was the same as in example 1.
The volume density of the light ablation-resistant closed-cell composite material prepared by the embodiment is 0.21g/cm 3 The thermal conductivity at room temperature is 0.03W/(m.K), and the temperature is measured at the nozzle tip and sample of the oxyacetylene gunThe distance between the products is 40mm, the inner diameter of the tip is 2mm, the flow rates of oxygen and acetylene are 0.4 and 0.5m respectively 3 The line ablation rate was 0.078mm/s under the oxyacetylene flame ablation conditions of/h, 33 s.
Comparative example 1
This comparative example differs from example 1 only in that the ceramifiable expanded microspheres were replaced with expanded microspheres (WP 175M, 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 light ablation-resistant closed-cell composite material obtained in this comparative example was 0.18g/cm 3 The thermal conductivity at room temperature was 0.026W/(mK), the distance between the nozzle tip of the oxyacetylene gun and the sample was 40mm, the inner diameter of the tip was 2mm, and the flow rates of oxygen and acetylene were 0.4 and 0.5m, respectively 3 The linear ablation rate was 0.082mm/s under the condition of oxyacetylene flame ablation per hour and 33 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 light ablation-resistant closed-cell composite material obtained in this comparative example was 0.24g/cm 3 The thermal conductivity at room temperature was 0.033W/(mK), the distance between the nozzle tip of the oxyacetylene gun and the sample was 40mm, the inner diameter of the tip was 2mm, and the flow rates of oxygen and acetylene were 0.4 and 0.5m, respectively 3 The linear ablation rate was 0.083mm/s under the condition of oxyacetylene flame ablation per hour, 33 s.
As is apparent from the above examples 1 to 4 and comparative examples 1 to 2, in the examples, compared with the comparative examples, the ceramic expandable microspheres with the core-shell structure prepared in the first step and the microspheres are fully expanded in the heat treatment in the third and fourth steps, and the density and the thermal conductivity of the composite material are remarkably reduced and the heat resistance is further improved because the ceramic expandable microspheres are used as key modified materials in the composite material. The ceramic expanded microsphere has the advantages that the ceramic expanded microsphere forms a three-dimensional closed-cell aerogel structure in the composite material, the ceramic filler on the surface of the microsphere can play a role in supporting and strengthening the shell of the expanded microsphere to a certain extent, the strength is higher, the ceramic expanded microsphere is not easy to crack in the service process, and the defects that the conventional through-hole aerogel composite material is easy to pulverize, the structure is easy to collapse, the heat insulation performance is invalid and the like are overcome.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. 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 light ablation-resistant closed-cell composite material is characterized by comprising the following preparation raw materials:
phenolic resins, hexamethylenetetramine, ethylene glycol, ceramifiable expanded microspheres, 3-aminopropyl triethoxysilane, and chopped fibers;
the mass ratio of the phenolic resin to the hexamethylenetetramine to the glycol to the ceramifiable expanded microspheres to the 3-aminopropyl triethoxysilane to the chopped fibers is 1 (0.01-0.10), 3-6, 0.02-0.10, 0.25-1 and 0.01-0.11;
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 lightweight ablation resistant closed cell 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 the combination of at least two of the following inorganic powders: montmorillonite, kaolin, wollastonite, halloysite, mica, clay, silica, titania, alumina, magnesia, zinc oxide, zirconium boride, boron carbide or strontium hexaboride;
the preparation method of the functionalized ceramic filler comprises the following steps: 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.
3. The light ablation resistant closed cell composite of claim 1, wherein the concentration of latex in the aqueous latex solution is 1-6 wt%;
the mass ratio of the functionalized ceramic filler to the latex to the expanded microspheres is 1 (0.5-2): 0.3-1;
the ultrasonic treatment time is 10-60 min;
the particle size range of the expanded microspheres is 10-50 mu m;
the drying temperature is 60-100 ℃, and the drying time is 4-24 hours.
4. The lightweight ablation-resistant closed cell composite of claim 1 wherein the chopped fibers are any one or a combination of at least two of chopped carbon fibers, chopped quartz fibers, chopped mullite fibers, or chopped basalt fibers;
the diameter of the chopped fiber is 5-20 mu m, and the length of the chopped fiber is 0.5-3 mm.
5. A method of making a lightweight ablation resistant closed cell composite material as in any one of claims 1-4 wherein the method of making comprises the steps of:
(1) Dispersing phenolic resin, hexamethylenetetramine, ethylene glycol, ceramic expanded microspheres and 3-aminopropyl triethoxysilane into the ethylene glycol, and then adding chopped fibers and uniformly dispersing to obtain slurry;
(2) Transferring the slurry obtained in the step (1) into a casting mold, vacuumizing until bubbles are completely eliminated, sealing the casting mold, and heating to obtain a wet gel composite material;
(3) And (3) demolding the wet gel composite material obtained in the step (2), removing ethylene glycol, and drying to obtain the light ablation-resistant closed cell composite material.
6. The method of claim 5, wherein the dispersing of the phenolic resin, hexamethylenetetramine, ethylene glycol, the ceramifiable expanded microspheres and 3-aminopropyl triethoxysilane into the ethylene glycol in step (1) is accomplished by mechanical stirring and ultrasonic dispersion.
7. The method according to claim 5, wherein the heating in the step (2) is performed by heating at 90-140 ℃ for 1-3 hours, then heating to 160-200 ℃ for 1-3 hours.
8. The method of claim 5, wherein the step (3) of removing ethylene glycol is by soaking with absolute ethanol;
and (3) drying the material in the step (3) is directly dried in the air at room temperature and normal pressure until no weight loss exists.
9. Use of the lightweight ablation resistant closed cell composite material according to any one of claims 1 to 4 as a thermal protection material.
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