CN115253938A - High-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and preparation method thereof - Google Patents
High-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and preparation method thereof Download PDFInfo
- Publication number
- CN115253938A CN115253938A CN202210954810.5A CN202210954810A CN115253938A CN 115253938 A CN115253938 A CN 115253938A CN 202210954810 A CN202210954810 A CN 202210954810A CN 115253938 A CN115253938 A CN 115253938A
- Authority
- CN
- China
- Prior art keywords
- temperature
- silicon carbide
- nanofiber
- resistant
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 188
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 151
- 239000004964 aerogel Substances 0.000 title claims abstract description 115
- 239000000463 material Substances 0.000 title claims abstract description 67
- 230000003471 anti-radiation Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 63
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 53
- 239000011259 mixed solution Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- -1 ferrocene compound Chemical class 0.000 claims abstract description 26
- 239000004088 foaming agent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003605 opacifier Substances 0.000 claims abstract description 26
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
- 238000004108 freeze drying Methods 0.000 claims abstract description 20
- 239000002562 thickening agent Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000007710 freezing Methods 0.000 claims abstract description 12
- 230000008014 freezing Effects 0.000 claims abstract description 12
- 230000006835 compression Effects 0.000 claims abstract description 7
- 238000007906 compression Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 41
- 230000005855 radiation Effects 0.000 claims description 31
- 239000011859 microparticle Substances 0.000 claims description 30
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000008096 xylene Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 14
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims 1
- 239000002657 fibrous material Substances 0.000 abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229930182470 glycoside Natural products 0.000 description 3
- 150000002338 glycosides Chemical class 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- VGBAECKRTWHKHC-UHFFFAOYSA-N cyclopenta-1,3-diene;1-ethenylcyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[CH2-]C=C1C=CC=C1 VGBAECKRTWHKHC-UHFFFAOYSA-N 0.000 description 2
- JHYFIGYFHLCBRI-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(2+);5-pentylcyclopenta-1,3-diene Chemical compound [Fe+2].C=1C=C[CH-]C=1.CCCCCC1=CC=C[CH-]1 JHYFIGYFHLCBRI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000718 radiation-protective agent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention relates to a high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing polycarbosilane, a high-molecular thickening agent, a ferrocene compound and an organic solvent to obtain a nanofiber precursor mixed solution, carrying out electrostatic spinning on the nanofiber precursor mixed solution, and carrying out pre-oxidation treatment and high-temperature pyrolysis on a fiber material obtained by electrostatic spinning to obtain silicon carbide nanofibers; uniformly mixing silicon carbide nano fibers, water, an infrared opacifier, a binder, a foaming agent and graphene oxide to obtain an aerogel precursor mixed solution, and then sequentially carrying out pre-freezing, freeze drying and thermal annealing treatment to obtain the high-temperature-resistant anti-radiation elastic silicon carbide nano fiber aerogel material. The material obtained by the invention can be prepared in large batch, the temperature resistance limit reaches 1100-1200 ℃, the thermal conductivity at the high temperature of 900 ℃ is lower than 0.059W/m.K, and the resilience rate is 96-100% when the maximum compression deformation is not lower than 80%.
Description
Technical Field
The invention belongs to the technical field of silicon carbide nanofiber aerogels, and particularly relates to a high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and a preparation method thereof.
Background
The silicon carbide nanofiber aerogel is a nano porous material formed by mutually lapping one-dimensional silicon carbide nanowires serving as construction elements in a three-dimensional space, and the type of aerogel has a plurality of excellent performances such as high temperature resistance, low thermal expansion, thermal shock resistance, oxidation resistance, corrosion resistance and the like endowed by the intrinsic property of a silicon carbide material, and has excellent mechanical behaviors such as unique flexibility, elasticity, high bending strength, young modulus and the like of the one-dimensional nanowires. Therefore, the prepared silicon carbide nanofiber aerogel has wide application prospects in various fields of elastic heat insulation, high-temperature heat insulation, electromagnetic wave absorption, filtration, adsorption and the like in extreme thermal environments and high-corrosivity environments.
The preparation method of the basic construction element silicon carbide nano-fiber of the silicon carbide nano-fiber aerogel mainly comprises a chemical vapor deposition method and an electrostatic spinning method at present. The chemical vapor deposition method is based on the chemical vapor deposition reaction of a carbon source providing carbon monoxide gas and a silicon source providing silicon monoxide gas under an inert atmosphere to generate silicon carbide nanofibers, for example, see chinese patent application CN113968582a, etc. The silicon carbide nano-fiber prepared by the chemical vapor deposition method has a relatively perfect crystal form, and the prepared silicon carbide nano-fiber has good long-term temperature resistance in an aerobic environment. However, this method requires a high temperature resistant atmosphere furnace, is complicated to operate, and is difficult to realize mass production of silicon carbide nanofibers with stable properties, which severely limits its practical engineering application. In recent years, by utilizing a strategy such as an electrostatic spinning method which can prepare nanofibers on a large scale, and by using a silicon carbide ceramic precursor solution such as polycarbosilane as a spinning solution, research on a preparation technology of silicon carbide nanofibers is carried out. The electrostatic spinning method for preparing the silicon carbide nano-fiber has the obvious advantages of low cost, simple operation, capability of designing the structural composition of materials and the like. However, the silicon carbide nano-fiber prepared by electrostatic spinning has imperfect crystal form and more defects, and is very easy to oxidize, melt and sinter in a high-temperature aerobic environment, so that the temperature resistance of the prepared silicon carbide nano-fiber is not more than 800 ℃.
In addition, in addition to the above-mentioned lack of strategy for preparing high-temperature resistant silicon carbide nanofibers on a large scale, the current high-temperature resistant high-performance silicon carbide nanofiber aerogel has acceptable room temperature thermal conductivity due to the fact that the aerogel is directly assembled from silicon carbide nanofibers, but the thermal insulation performance at high temperature is difficult to meet the practical application requirements due to the fact that the infrared radiation resistance is still weak.
Therefore, it is urgently needed to break through the batch preparation, high temperature resistance improvement and anti-radiation modification technology of the silicon carbide nanofiber raw material to finally prepare the high temperature resistant and anti-radiation silicon carbide nanofiber aerogel material.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and a preparation method thereof. The high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material prepared by the invention has the advantages of high temperature resistance, high-temperature heat insulation, elasticity, ultralow density, capability of being prepared in a macroscopic scale and the like.
The invention provides a preparation method of a high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material in a first aspect, which comprises the following steps:
(1) Uniformly mixing polycarbosilane, a high-molecular thickener, a ferrocene compound and an organic solvent to obtain a nanofiber precursor mixed solution;
(2) Performing electrostatic spinning by taking the nanofiber precursor mixed solution as an electrostatic spinning solution to obtain polycarbosilane nanofiber;
(3) Carrying out pre-oxidation treatment on the polycarbosilane nanofiber to obtain pre-oxidized polycarbosilane nanofiber;
(4) Carrying out high-temperature pyrolysis on the pre-oxidized polycarbosilane nano fiber to obtain silicon carbide nano fiber;
(5) Uniformly mixing the silicon carbide nano-fibers, water, an infrared opacifier, a binder, a foaming agent and graphene oxide to obtain an aerogel precursor mixed solution;
(6) Sequentially pre-freezing and freeze-drying the aerogel precursor mixed solution to obtain the silicon carbide nanofiber aerogel composite material;
(7) And carrying out thermal annealing treatment on the silicon carbide nanofiber aerogel composite material to obtain the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material.
Preferably, the number average molecular weight of the polycarbosilane is 800-3200 g/mol, preferably 1600g/mol; the macromolecular thickening agent is polyvinylpyrrolidone, and the number average molecular weight of the macromolecular thickening agent is 10000-1300000 g/mol, preferably 1300000g/mol; the organic solvent is one or more of DMF, THF and xylene, preferably the organic solvent is formed by mixing DMF, THF and xylene, and more preferably the organic solvent is formed by mixing DMF, THF and xylene according to the mass ratio of (2-5): (4-7): 1, and more preferably, the organic solvent is prepared by mixing DMF, THF and xylene according to a mass ratio of 2.5; and/or the ferrocene compound is one or more of alkenyl substituted ferrocene with the carbon number of 2-8, ferrocene, alkyl substituted ferrocene with the carbon number of 1-8 and benzoyl ferrocene, and vinyl ferrocene is preferred.
Preferably, the mass fraction of polycarbosilane contained in the nanofiber precursor mixed solution is 2-10%, preferably 6%; the mass fraction of the macromolecular thickening agent contained in the nanofiber precursor mixed solution is 3-12%, and preferably 5%; and/or the mass fraction of the ferrocene compound contained in the nanofiber precursor mixed solution is 0.1-3.5%, preferably 1.5%.
Preferably, the electrostatic spinning is carried out at a voltage of 6 to 30kV, an injection speed of 0.2 to 4mL/h, a reception distance of 8 to 28cm and an ambient temperature of 15 to 35 ℃.
Preferably, the temperature of the pre-oxidation treatment is 80-280 ℃, and preferably 160 ℃; the time of the pre-oxidation treatment is 2 to 48 hours, and is preferably 12 hours; and/or the temperature rise rate of raising the temperature to the temperature of the pre-oxidation treatment is 1 to 4 ℃/min, preferably 2 ℃/min.
Preferably, the pyrolysis temperature is 1300-1700 ℃, preferably 1400 ℃; the pyrolysis time is 1-8 h, preferably 3h; and/or the heating rate of heating to the pyrolysis temperature is 0.5-6 ℃/min, preferably 2 ℃/min.
Preferably, the infrared opacifier is one or more of silicon carbide microparticles, titanium oxide microparticles, carbon black, iron oxide microparticles, titanium oxide microparticles, potassium hexatitanate whiskers, boron carbide microparticles and iron oxide microparticles; the particle size of the infrared opacifier is 1-15 microns, preferably 2-4 microns; the binder is one or more of aluminum dihydrogen phosphate, methyl orthosilicate, ethyl orthosilicate, silica sol and aluminum sol; the foaming agent is one or more of APG0810, APG1214, TX-10, AEO-3, AEG300, AEO-7, isomeric tridecanol polyoxyethylene ether 1309, SOE surfactant and SKYIN EP2445 surfactant; and/or the graphene oxide is graphene oxide with 1-8 layers, preferably single-layer graphene oxide.
Preferably, the mass fraction of the silicon carbide nanofibers contained in the aerogel precursor mixed solution is 0.5-10%, preferably 5%; the mass ratio of the infrared opacifier to the silicon carbide nano fiber is (0.1-0.6): 1 is preferably 0.25; the mass ratio of the binder to the silicon carbide nano-fibers is (0.02-0.2): 1 is preferably 0.08; the mass fraction of the foaming agent contained in the aerogel precursor mixed solution is 0.5-8%, preferably 3%; and/or the mass fraction of the graphene oxide contained in the aerogel precursor mixed solution is 0.3-2%, preferably 1%.
Preferably, the pre-freezing is freezing under liquid nitrogen for 5-60 min, preferably 20min; the freeze drying is carried out in a freeze dryer, in the freeze drying process, the temperature of a chamber of the freeze dryer is controlled to be 10-35 ℃, the temperature of a cold trap of the freeze dryer is controlled to be-80-40 ℃, the pressure of the freeze drying is 0.1-20 Pa, and the freeze drying time is 24-72 hours; and/or the temperature of the thermal annealing treatment is 800-1200 ℃, preferably 1100 ℃, and the time of the thermal annealing treatment is 0.5-4 h, preferably 1h.
In a second aspect, the invention provides a high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material prepared by the preparation method in the first aspect; preferably, the high temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material has one or more of the following properties: the temperature resistance limit of the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material in an aerobic environment is 1100-1200 ℃; the room temperature thermal conductivity of the high temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material is not higher than 0.032W/(m.K), and the 900 ℃ thermal conductivity is lower than 0.059W/(m.K); the maximum compression deformation of the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material is not less than 80%, and the rebound rate is 96-100%; the lowest density of the high-temperature-resistant and anti-radiation elastic silicon carbide nanofiber aerogel material is 7mg/cm 3 (ii) a The diameter of the nanofiber contained in the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material is 80-800 nm; the high-temperature-resistant and anti-radiation elastic silicon carbide nanofiber aerogel material can be prepared in large scale.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) Compared with the existing silicon carbide nano fiber prepared by a chemical vapor deposition method, the diameter of the silicon carbide nano fiber can be controlled and conveniently adjusted in a larger range through electrostatic spinning, in addition, the mass preparation of the nano fiber can be realized through an electrostatic spinning strategy, the performance among the silicon carbide nano fibers in different batches can be kept stable, the process for preparing the silicon carbide nano fiber by the chemical vapor deposition method is complex, the mass stable preparation is difficult to realize, and the size adjustability of the silicon carbide nano wire prepared by the chemical vapor deposition method is relatively poor.
(2) According to the invention, the ferrocene compound is innovatively introduced into the electrostatic spinning solution, the ferrocene compound is embedded in the polycarbosilane nanofiber obtained by spinning, and in the process of converting the polycarbosilane nanofiber into the silicon carbide nanofiber by high-temperature cracking, a very small amount of the ferrocene compound can regulate and control the micro-area purity, the grain size, the micro-arrangement and the micro-cracks of the silicon carbide crystal in the nanofiber, so that the temperature resistance of the silicon carbide nanofiber in an aerobic environment is improved; the invention is based on the high-temperature resistant silicon carbide nano-fiber, the high-temperature resistant infrared opacifier and the binder, so that the temperature resistance of the prepared silicon carbide nano-fiber aerogel material is greatly improved.
(3) The method solves the problem of uniform and stable distribution of the high-content infrared opacifier in the silicon carbide nanofiber aerogel, on one hand, the fluid and viscosity characteristics of the aerogel precursor mixed solution are changed through the bubbles of the foaming agent, so that the high-concentration micron-sized and high-density infrared opacifier can be initially and stably dispersed at room temperature, on the other hand, partial physical or chemical crosslinking of graphene oxide in the solution is utilized, so that the effect of stabilizing bubbles is achieved, the viscosity and rheological characteristics of the aerogel precursor mixed solution can be further increased, and the infrared opacifier can be stably dispersed for a long time without agglomeration and precipitation; due to the technical breakthrough, the prepared silicon carbide nanofiber aerogel can effectively prevent infrared radiation from transmitting and reduce the radiation heat conductivity of the aerogel material at high temperature, so that the silicon carbide nanofiber aerogel has good radiation resistance and excellent heat insulation performance at high temperature.
(4) The high-temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material prepared by the invention has the temperature resistance limit of 1100-1200 ℃, the thermal conductivity of less than 0.059W/m.K at the high temperature of 900 ℃, the resilience rate of not less than 80% of the maximum compression deformation of 96-100%, and the advantages of high temperature resistance, high temperature heat insulation, elasticity, ultralow density, macroscopic preparation and the like.
Drawings
FIG. 1 is a schematic diagram and a physical photograph of an electrostatic spinning process for obtaining polycarbosilane nanofiber by electrostatic spinning in example 1 of the present invention; in the figure, (a) is an electrostatic spinning schematic diagram, and (b) is a real photograph.
FIG. 2 is a physical photograph and a scanning electron microscope image of the pre-oxidized polycarbosilane nanofiber obtained by pre-oxidation fixing in example 1 of the present invention; in the figure, (a) is a real image and (b) is a scanning electron micrograph.
FIG. 3 is a physical representation and a scanning electron microscope image of silicon carbide nanofibers obtained by thermal cracking at high temperature in example 1 of the present invention; in the figure, (a) is a real image and (b) is a scanning electron micrograph.
FIG. 4 is a high-resolution transmission electron microscope image of the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material in a first aspect, which comprises the following steps:
(1) Uniformly mixing polycarbosilane, a high-molecular thickening agent, a ferrocene compound and an organic solvent to obtain a nanofiber precursor mixed solution; in the step (1), the uniform mixing is carried out, for example, ultrasonic dispersion is carried out for 8-16 h, and then stirring is carried out for 8-12 h at the rotating speed of 1200-2000 rpm, so as to obtain homogeneous nanofiber precursor mixed liquor; the invention has no special requirements on ultrasonic dispersion, and can be carried out by adopting conventional operation; in the invention, the macromolecular thickener is polyvinylpyrrolidone, for example, and the ferrocene compound is vinylferrocene, for example, the invention has no special requirement on the sources of polycarbosilane, polyvinylpyrrolidone, vinylferrocene and the like, and can adopt products which can be directly purchased from the market or be synthesized by the existing method;
(2) Performing electrostatic spinning by using the nanofiber precursor mixed solution as an electrostatic spinning solution to obtain polycarbosilane nanofiber (also called polycarbosilane nanofiber membrane);
(3) Pre-oxidizing the polycarbosilane nano fiber to obtain pre-oxidized polycarbosilane nano fiber (also called as a pre-oxidized polycarbosilane nano fiber film); in the present invention, the pre-oxidation treatment (pre-oxidation fixing treatment) is performed to obtain a polycarbosilane nanofiber membrane having a definite shape;
(4) Carrying out high-temperature pyrolysis on the pre-oxidized polycarbosilane nano fiber to obtain silicon carbide nano fiber (also called as a silicon carbide nano fiber film); in the present invention, the pyrolysis is carried out, for example, under an inert atmosphere;
(5) Uniformly mixing the silicon carbide nano-fibers, water, an infrared opacifier, a binder, a foaming agent and graphene oxide to obtain an aerogel precursor mixed solution; in the invention, when the aerogel precursor mixed solution is formed, the mixture is uniformly mixed, for example, by stirring, wherein the stirring speed is, for example, 2000 to 4000rpm, and the stirring time is, for example, 2 to 4 hours, so as to obtain a stably dispersed aerogel precursor mixed solution;
(6) Sequentially pre-freezing and freeze-drying the aerogel precursor mixed solution to obtain the silicon carbide nanofiber aerogel composite material; in the present invention, the pre-freezing is carried out, for example, in liquid nitrogen for rapid pre-freezing;
(7) Carrying out thermal annealing treatment on the silicon carbide nanofiber aerogel composite material to obtain a high-temperature-resistant and anti-radiation elastic silicon carbide nanofiber aerogel material; in the invention, after thermal annealing treatment, graphene oxide is burnt off; in the present invention, the thermal annealing treatment is performed, for example, under an air atmosphere.
The invention provides a preparation method of a high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material; on one hand, the invention adopts Polycarbosilane (PCS) doped with ferrocene compounds as electrostatic spinning solution, can realize simple, rapid and macro preparation of silicon carbide nano-fiber by electrostatic spinning strategy, and can realize the improvement of the temperature resistance of the silicon carbide nano-fiber by the special regulation and control effect of the ferrocene compounds on the crystal grain and the appearance of the silicon carbide after the polycarbosilane is pyrolyzed and converted into the silicon carbide, thereby breaking through the macroscopic batch preparation of the high temperature resistant silicon carbide nano-fiber as the aerogel raw material; on the other hand, the high-temperature radiation performance of the silicon carbide nanofiber aerogel is well inhibited by introducing an infrared opacifier such as silicon carbide microparticles as an anti-radiation agent of the silicon carbide nanofiber aerogel and realizing stable and uniform dispersion of the silicon carbide microparticles in the aerogel through a bubble-assisted dispersion strategy.
The method solves the problem of uniform and stable distribution of high-content infrared opacifier in silicon carbide nanofiber aerogel, on one hand, the fluid and viscosity characteristics of aerogel precursor mixed liquor are changed through bubbles of a foaming agent, so that the high-concentration micron-sized and high-density infrared opacifier can be initially dispersed stably at room temperature, on the other hand, partial physical or chemical crosslinking of graphene oxide in the solution is utilized, so that the effect of stabilizing bubbles is achieved, the viscosity and rheological characteristics of the aerogel precursor mixed liquor can be further increased, and the infrared opacifier can be stably dispersed for a long time without agglomeration and precipitation; due to the technical breakthrough, the prepared silicon carbide nanofiber aerogel can effectively prevent infrared radiation from transmitting and reduce the radiation heat conductivity of the aerogel material at high temperature, so that the silicon carbide nanofiber aerogel has good radiation resistance and excellent heat insulation performance at high temperature.
According to some preferred embodiments, the polycarbosilane has a number average molecular weight of 800 to 3200g/mol, preferably 1600g/mol, i.e. a molar mass of 800 to 3200g/mol, preferably 1600g/mol; the macromolecular thickener is polyvinylpyrrolidone, the number average molecular weight of the macromolecular thickener is 10000-1300000 g/mol, preferably 1300000g/mol, namely the molar mass of the macromolecular thickener is 10000-1300000 g/mol, preferably 1300000g/mol; in the present invention, the polymeric thickener is, for example, one or more of 1300000g/mol, 63000g/mol, 58000g/mol, 24000g/mol, 10000g/mol, etc., in number average molecular weight.
According to some preferred embodiments, the organic solvent is one or more of DMF (N, N-dimethylformamide), THF (tetrahydrofuran) and xylene, preferably, the organic solvent is a mixture of DMF, THF and xylene, more preferably, the organic solvent is a mixture of DMF, THF and xylene in a mass ratio of (2 to 5): (4-7): 1.5; the present invention does not require a particular para-xylene, which may be composed of, for example, one or more of meta-xylene, para-xylene, and ortho-xylene.
According to some preferred embodiments, the ferrocene-based compound is one or more of alkenyl substituted ferrocene having a carbon number of 2 to 8, ferrocene, alkyl substituted ferrocene having a carbon number of 1 to 8 (e.g., pentylferrocene), benzoyl ferrocene, preferably vinyl ferrocene.
According to some preferred embodiments, the mass fraction of polycarbosilane contained in the nanofiber precursor mixture is 2 to 10% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%) and preferably 6%; the mass fraction of the macromolecular thickening agent contained in the nanofiber precursor mixed solution is 3-12 percent (for example, 3 percent 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12%) preferably 5%; and/or the mass fraction of the ferrocene compound contained in the nanofiber precursor mixed solution is 0.1-3.5% (e.g. 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% or 3.5%), preferably 1.5%, so that the high-temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material with good comprehensive performance can be obtained more favorably; in the present invention, it is preferable that the mass fraction of polycarbosilane contained in the nanofiber precursor mixture is 2 to 10%, the mass fraction of the polymeric thickener contained in the nanofiber precursor mixture is 3 to 12%, if the content of polycarbosilane and polymeric thickener is too low, polycarbosilane nanofibers with a target diameter cannot be effectively formed by spinning, and if the content of polycarbosilane and polymeric thickener is too high, spinning is unstable, and the diameters of nanofibers are not uniform, which may even result in failure to form nanofibers; in the invention, the mass fraction of the ferrocene compound contained in the nanofiber precursor mixed solution is preferably 0.1-3.5%, and if the content of the ferrocene compound is too low or too high, the ferrocene compound is not favorable for regulating and controlling the purity, the grain size, the microscopic arrangement and the microscopic cracks of the silicon carbide crystal in the nanofiber, so that the temperature resistance of the silicon carbide nanofiber in an aerobic environment is not favorable for improving; in addition, if the content of the ferrocene compound is too high, the thermal conductivity and the density of the nanofiber aerogel can be improved due to the fact that the content of the residual iron oxide is too high.
According to some preferred embodiments, the electrospinning is carried out at a voltage of 6 to 30kV (e.g., 6, 10, 15, 20, 25, or 30 kV), an injection rate of 0.2 to 4mL/h (e.g., 0.2, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 4 mL/h), a receiving distance of 8 to 28cm (e.g., 8, 10, 12, 15, 18, 20, 22, 25, or 28 ℃), and an ambient temperature of 15 to 35 ℃ (e.g., 15 ℃, 20 ℃, 25 ℃, 30 ℃, or 35 ℃).
According to some preferred embodiments, the temperature of the pre-oxidation treatment is 80 to 280 ℃ (e.g. 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 220 ℃, 250 ℃ or 280 ℃), preferably 160 ℃; the time of the pre-oxidation treatment is 2 to 48h (for example, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46 or 48 h), and preferably 12h; and/or the rate of temperature rise to the temperature of the pre-oxidation treatment is 1 to 4 ℃/min (e.g., 1, 2, 3, or 4 ℃/min), preferably 2 ℃/min.
According to some preferred embodiments, the temperature of the pyrolysis is 1300 to 1700 ℃ (e.g. 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃ or 1700 ℃), preferably 1400 ℃; the pyrolysis time is 1 to 8h (e.g. 1, 2, 3, 4, 5, 6, 7 or 8 h), preferably 3h; and/or the rate of temperature rise to the pyrolysis temperature is 0.5 to 6 deg.C/min (e.g., 0.5, 1, 2, 3, 4, 5, or 6 deg.C/min), preferably 2 deg.C/min.
According to some preferred embodiments, the infrared opacifier is one or more of silicon carbide microparticles, titanium oxide microparticles, carbon black, iron oxide microparticles, titanium oxide microparticles, potassium hexatitanate whiskers, boron carbide microparticles, iron oxide microparticles, preferably silicon carbide microparticles; the particle size of the infrared opacifier is 1-15 microns, preferably 2-4 microns; the binder is one or more of aluminum dihydrogen phosphate, methyl orthosilicate, ethyl orthosilicate, silica sol and aluminum sol, and is preferably aluminum dihydrogen phosphate; the foaming agent is one or more of APG0810 (alkyl glycoside APG 0810), APG1214 (alkyl glycoside APG 1214), TX-10 (alkylphenol polyoxyethylene ether TX-10), AEO-3 (fatty alcohol polyoxyethylene ether AEO-3), AEG300 (alcohol ether glycoside AEG 300), AEO-7 (fatty alcohol polyoxyethylene ether AEO-7), isomeric tridecanol polyoxyethylene ether 1309, SOE surfactant and SKYIN EP2445 surfactant, preferably APG0810; in the present invention, these products are all available directly from the market; the foaming agent carefully selected in the invention has a stable foaming effect, on one hand, bubbles generated in the stirring process can be frequently deformed or rotated under the shearing of a flow field, on the other hand, the generation of the bubbles can greatly change the fluid and viscosity characteristics of an aerogel precursor mixed solution, the gas-liquid viscosity can play a role in buoyancy on high-concentration, micron-grade and high-density infrared opacifiers, and the comprehensive effect is that the high-content infrared opacifiers can be preliminarily dispersed stably at room temperature; and/or the graphene oxide is graphene oxide with 1-8 layers, preferably single-layer (1-layer) graphene oxide.
According to some preferred embodiments, the mass fraction of the silicon carbide nanofibers contained in the aerogel precursor mixture is 0.5 to 10% (e.g., 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%) preferably 5%; the mass ratio of the infrared opacifier to the silicon carbide nano fiber is (0.1-0.6): 1 (e.g. 0.1; the mass ratio of the binder to the silicon carbide nano-fibers is (0.02-0.2): 1 (e.g. 0.02; in the present invention, it is preferable that the mass ratio of the binder to the silicon carbide nanofibers is (0.02 to 0.2): if the content of the binder is too low, the purpose of effectively bonding the silicon carbide nanofibers and the infrared opacifier cannot be achieved, the elastic mechanical property of the finally prepared aerogel material is poor, but if the content of the binder is too high, the overlapping degree between the silicon carbide nanofibers and the infrared opacifier is too high, and the material is converted from elastic mechanics to brittle mechanics; in the invention, the silicon carbide nanofibers and the infrared opacifier are preferably overlapped to a proper degree, so that the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material has better elasticity mechanics; the mass fraction of the foaming agent contained in the aerogel precursor mixture is preferably 0.5 to 8% (e.g., 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, or 8%) and is preferably 3%; and/or the mass fraction of graphene oxide contained in the aerogel precursor mixed solution is 0.3-2% (e.g., 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8% or 2%) and is preferably 1%, so that the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material with good comprehensive performance can be obtained more favorably; in the present invention, it is preferable that the mass fraction of the foaming agent contained in the aerogel precursor mixture is 0.5 to 8%, and if the content of the foaming agent is too small, stable foaming cannot be effectively performed, which may result in that the infrared light screening agent cannot be stably dispersed well, and if the content of the foaming agent reaches a certain ratio, the increase of the content of the foaming agent does not work well; in the present invention, it is preferable that the mass fraction of the graphene oxide contained in the aerogel precursor mixture is 0.3 to 2%, and in the present invention, the graphene oxide has an effect of stabilizing bubbles and further increasing the solution viscosity, and the effect cannot be well achieved if the concentration of the graphene oxide is too low, whereas the graphene oxide itself may agglomerate and settle if the concentration of the graphene oxide is too high.
According to some preferred embodiments, the pre-freezing is freezing under liquid nitrogen for 5-60 min (e.g. 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60 min), preferably 20min; the freeze drying is carried out in a freeze dryer, in the freeze drying process, the temperature of a chamber of the freeze dryer is controlled to be 10-35 ℃, the temperature of a cold trap of the freeze dryer is controlled to be-80-40 ℃, the pressure of the freeze drying is 0.1-20 Pa, and the freeze drying time is 24-72 hours; and/or the temperature of the thermal annealing treatment is 800 to 1200 ℃ (e.g. 800 ℃, 850 ℃,900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃) and preferably 1100 ℃, and the time of the thermal annealing treatment is 0.5 to 4h (e.g. 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 4 h) and preferably 1h.
In a second aspect, the invention provides a high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material prepared by the preparation method in the first aspect; preferably, the high temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material has one or more of the following properties: the high-temperature resistant and anti-radiation elastic silicon carbide nanofiber aerogel material has the temperature resistance limit of 1100-1200 ℃ in an aerobic environment (air atmosphere muffle examination), and shows the high-temperature resistant characteristic; the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material has the advantages that the room-temperature thermal conductivity is not higher than 0.032W/(m.K), the 900-DEG C thermal conductivity is lower than 0.059W/(m.K), the heat-insulating property at room temperature, particularly at high temperature, is excellent, and the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material has good radiation resistance; the maximum compression deformation of the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material is not less than 80%, the rebound rate is 96-100%, and the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material has good elastic characteristics; the density of the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material can be as low as 7mg/cm 3 Exhibits ultra-light characteristics; the average diameter of the nanofibers contained in the high-temperature-resistant and anti-radiation elastic silicon carbide nanofiber aerogel material is 80-800 nm; the average diameter of the nanofibers contained in the high-temperature-resistant and anti-radiation elastic silicon carbide nanofiber aerogel material can be in the range of 80-800 nm according to needsRegulation and control are required; the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material can be prepared in large scale.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
(1) Adding 6g of polycarbosilane (with the number average molecular weight of 1600 g/mol), 5g of polyvinylpyrrolidone (with the number average molecular weight of 1300000 g/mol) and 1.5g of vinyl ferrocene into 87.5g of a mixed solvent consisting of DMF, THF and xylene (wherein the mass ratio of DMF, THF and xylene is 2.5.
(2) And (2) extracting the nanofiber precursor mixed solution as an electrostatic spinning solution by using an injector with a stainless steel needle, spinning by using an electrostatic spinning machine, and collecting by using an aluminum foil to obtain the polycarbosilane nanofiber, wherein the electrostatic spinning process parameters comprise the voltage of 12kV, the injection speed of 2.5mL/h, the receiving distance of 20cm and the ambient temperature of 20 ℃. And drying the aluminum foil with the collected polycarbosilane nano fibers in a 60 ℃ oven for 2h to remove volatile solvent in the polycarbosilane nano fibers, carefully scraping the polycarbosilane nano fiber film from the aluminum foil into a crucible, and keeping the polycarbosilane nano fiber film for later use.
(3) And (3) putting the crucible filled with the polycarbosilane nano fiber into an oven, raising the temperature from room temperature to 160 ℃ at the heating rate of 2 ℃/min, keeping the temperature at 160 ℃ for 2h for pre-oxidation treatment, and cooling to room temperature to obtain the pre-oxidized polycarbosilane nano fiber.
(4) And (3) placing the crucible filled with the pre-oxidized polycarbosilane nano fiber in an atmosphere furnace, repeatedly pumping and discharging for three times to enable the atmosphere furnace to be in an argon environment, raising the temperature from room temperature to 1400 ℃ at the heating rate of 2 ℃/min, keeping the temperature at 1400 ℃ for 3h for pyrolysis, and cooling to room temperature to obtain the silicon carbide nano fiber.
(5) 5g of silicon carbide nano-fiber, 1.25g of silicon carbide micro-particles (average particle size is 3 μm), 0.4g of aluminum dihydrogen phosphate, 3g of foaming agent APG0810, 1g of single-layer graphene oxide and 89.35g of water are stirred at the speed of 3000rpm for 3 hours to obtain the stably dispersed aerogel precursor mixed solution.
(6) And (3) putting the beaker filled with the aerogel precursor mixed solution into liquid nitrogen for quick freezing for 20min, then putting the beaker into a freeze dryer for freeze drying, controlling the pressure in a freeze drying box to be below 20Pa, controlling the chamber temperature of the freeze dryer to be 25 ℃, controlling the temperature of a freeze drying cold trap to be-70 ℃, and freeze drying for 48h to obtain the silicon carbide nanofiber aerogel composite material.
(7) And (3) putting the silicon carbide nanofiber aerogel composite material into an air atmosphere muffle furnace at the temperature of 1100 ℃ for annealing treatment for 1h, taking out and cooling to room temperature to obtain the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material.
Example 2
Example 2 is essentially the same as example 1, except that:
in the step (1), 6g of polycarbosilane (number average molecular weight 1600 g/mol), 5g of polyvinylpyrrolidone (number average molecular weight 1300000 g/mol) and 1.5g of benzoyl ferrocene are added into 87.5g of a mixed solvent consisting of DMF, THF and xylene (wherein the mass ratio of DMF, THF and xylene is 2.5.
Example 3
Example 3 is essentially the same as example 1, except that:
in the step (1), 6g of polycarbosilane (number average molecular weight 1600 g/mol), 5g of polyvinylpyrrolidone (number average molecular weight 1300000 g/mol) and 1.5g of ferrocene are added into 87.5g of a mixed solvent consisting of DMF, THF and xylene (wherein the mass ratio of DMF, THF and xylene is 2.5.
Example 4
Example 4 is essentially the same as example 1, except that:
in the step (1), 6g of polycarbosilane (number average molecular weight 1600 g/mol), 5g of polyvinylpyrrolidone (number average molecular weight 1300000 g/mol) and 1.5g of pentylferrocene are added into 87.5g of a mixed solvent consisting of DMF, THF and xylene (wherein the mass ratio of DMF, THF and xylene is 2.5.
Example 5
Example 5 is essentially the same as example 1, except that:
in the step (5), 0.5g of silicon carbide nanofibers, 0.05g of silicon carbide microparticles (average particle size of 3 μm), 0.01g of aluminum dihydrogen phosphate, 0.5g of foaming agent APG0810, 0.3g of single-layer graphene oxide, and 98.64g of water were stirred at 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixture.
Example 6
Example 6 is essentially the same as example 1, except that:
in the step (5), 10g of silicon carbide nano-fiber, 6g of silicon carbide micro-particle (average particle size 3 μm), 2g of aluminum dihydrogen phosphate, 8g of foaming agent APG0810, 2g of single-layer graphene oxide and 72g of water are stirred at a speed of 3000rpm for 3h to obtain a stably dispersed aerogel precursor mixed solution.
Example 7
Example 7 is essentially the same as example 1, except that:
in the step (5), 5g of the silicon carbide nanofiber membrane, 1.25g of silicon carbide micro-particles (average particle size of 3 μm), 0.05g of aluminum dihydrogen phosphate, 3g of a foaming agent APG0810, 1g of single-layer graphene oxide and 89.7g of water are stirred at a speed of 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixed solution.
Example 8
Example 8 is essentially the same as example 1, except that:
in the step (5), 5g of the silicon carbide nanofiber membrane, 1.25g of silicon carbide microparticles (with an average particle size of 3 μm), 1.25g of aluminum dihydrogen phosphate, 3g of a foaming agent APG0810, 1g of single-layer graphene oxide and 88.5g of water are stirred at a speed of 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixed solution.
Example 9
Example 9 is essentially the same as example 1, except that:
in the step (5), 5g of the silicon carbide nanofiber membrane, 1.25g of silicon carbide microparticles (average particle size of 3 μm), 0.4g of aluminum dihydrogen phosphate, 0.4g of a foaming agent APG0810, 0.2g of single-layer graphene oxide, and 92.75g of water were stirred at 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixture.
Example 10
Example 10 is essentially the same as example 1, except that:
in step (5), 5g of silicon carbide nanofiber membrane, 1.25g of silicon carbide microparticles (average particle size of 3 μm), 0.4g of aluminum dihydrogen phosphate, 9g of foaming agent APG0810, 2.5g of single-layer graphene oxide and 81.85g of water are stirred at 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixed solution.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that:
in the step (1), 6g of polycarbosilane (number average molecular weight 1600 g/mol) and 5g of polyvinylpyrrolidone (number average molecular weight 1300000 g/mol) are added into 89g of a mixed solvent composed of DMF, THF and xylene (wherein the mass ratio of DMF, THF and xylene is 2.5.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that:
in the step (5), 5g of silicon carbide nanofibers, 0.4g of aluminum dihydrogen phosphate, 3g of a foaming agent APG0810, 1g of single-layer graphene oxide and 90.6g of water are stirred at a speed of 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixed solution.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that:
in the step (5), 5g of silicon carbide nanofibers, 1.25g of silicon carbide microparticles (average particle size of 3 μm), 0.4g of aluminum dihydrogen phosphate, 1g of single-layer graphene oxide and 92.35g of water are stirred at 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixed solution.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that:
in the step (5), 5g of silicon carbide nanofibers, 1.25g of silicon carbide microparticles (average particle size of 3 μm), 0.4g of aluminum dihydrogen phosphate, 3g of foaming agent APG0810, and 90.35g of water were stirred at 3000rpm for 3 hours to obtain a stably dispersed aerogel precursor mixture.
Comparative example 5
(1) 500g of polycarbosilane (number average molecular weight 1600 g/mol) is dissolved in 500mL of xylene, added into a reactor, then 100g of ferrocene is added into the reactor, reacted for 2 hours at 350 ℃, naturally cooled to normal temperature to become solid, dissolved by 950mL of xylene, filtered to remove insoluble substances, the filtrate is placed in a three-neck flask, and distilled for 1 hour at 320 ℃ under reduced pressure to obtain 539g of precursor polymer containing iron.
(2) The precursor polymer containing iron is placed in a melting cylinder of a melt spinning device, heated to 348 ℃ under the protection of inert atmosphere, and drawn and spun at the speed of 410 m/min at the pressure of 0.7MPa and the temperature of 270 ℃ after the precursor polymer is completely melted into uniform melt, so that fibrils with the average diameter of 15um and the continuous length of 800m are obtained.
(3) The fibril is placed in an air non-melting treatment device for non-melting treatment, then is heated to 200 ℃ at a heating rate of 40 ℃/h, is kept at 200 ℃ for 1h, and is then cooled to room temperature. And then placing the fiber in another non-melting furnace, replacing the fiber with nitrogen for three times, introducing mixed gas of boron tribromide and nitrogen, wherein the volume of the boron tribromide accounts for 95% of the volume of the mixed gas, heating to 360 ℃ at the heating speed of 50 ℃/h, and keeping the temperature for 5 hours to obtain the non-melting fiber. And (3) putting the unmelted fiber in a graphite furnace, introducing nitrogen for protection, heating to 1200 ℃ at the heating rate of 100 ℃/hour, preserving the temperature for 0.5 hour, and cooling to obtain the Si-C-O-Fe fiber. Then the fiber is continuously sintered at high temperature of 2000 ℃ by a tube furnace under the protection of argon gas at the speed of 10 m/h to obtain the SiC fiber material.
The SiC fiber material obtained in this comparative example could not be made into an aerogel material.
Comparative example 6
Comparative example 6 is substantially the same as example 1 except that:
in the step (1), 60g of polycarbosilane (with the number average molecular weight of 1600 g/mol) is dissolved in 60mL of xylene, added into a reactor, then 15g of vinyl ferrocene is added into the reactor, reacted for 2 hours at 350 ℃, naturally cooled to normal temperature to become solid, dissolved by 200mL of xylene, filtered to remove insoluble substances, the filtrate is placed into a three-neck flask, and distilled for 1 hour at 320 ℃ under reduced pressure to obtain a precursor polymer containing iron; adding 7.5g of precursor polymer containing iron and 5g of polyvinylpyrrolidone (with the number average molecular weight of 1300000 g/mol) into 87.5g of mixed solvent consisting of DMF, THF and xylene (wherein the mass ratio of DMF, THF and xylene is 2.5.
The invention tests the performance indexes of the finally prepared materials of examples 1-10 and comparative examples 1-6, and the test results are shown in Table 1; in the present invention, the 80% compression set is a compression amount of the material in the thickness direction which accounts for 80% of the initial thickness of the material; in the present invention, the temperature resistance limit test is: examining the material finally prepared in each embodiment and comparative example in a muffle furnace at a certain high temperature in an air atmosphere for 12h, wherein the average linear shrinkage rate of the material in the x, y and z directions is less than 2%, and then the material is considered to be capable of resisting the high temperature, taking embodiment 1 as an example, after the material prepared in embodiment 1 is examined in the muffle furnace at the high temperature of 1200 ℃ in the air atmosphere for 12h, the average linear shrinkage rate of the material in the x, y and z directions is 0.5%, namely the temperature resistance limit of the material is 1200 ℃; the "-" symbol in Table 1 indicates that the performance index was not tested.
Table 1: the performance indexes of the materials obtained in examples 1 to 10 and comparative examples 1 to 6.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material is characterized by comprising the following steps:
(1) Uniformly mixing polycarbosilane, a high-molecular thickening agent, a ferrocene compound and an organic solvent to obtain a nanofiber precursor mixed solution;
(2) Performing electrostatic spinning by taking the nanofiber precursor mixed solution as an electrostatic spinning solution to obtain polycarbosilane nanofiber;
(3) Carrying out pre-oxidation treatment on the polycarbosilane nano fiber to obtain pre-oxidized polycarbosilane nano fiber;
(4) Carrying out high-temperature pyrolysis on the pre-oxidized polycarbosilane nano fiber to obtain silicon carbide nano fiber;
(5) Uniformly mixing the silicon carbide nano-fibers, water, an infrared opacifier, a binder, a foaming agent and graphene oxide to obtain an aerogel precursor mixed solution;
(6) Sequentially pre-freezing and freeze-drying the aerogel precursor mixed solution to obtain the silicon carbide nanofiber aerogel composite material;
(7) And carrying out thermal annealing treatment on the silicon carbide nanofiber aerogel composite material to obtain the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material.
2. The method of claim 1, wherein:
the number average molecular weight of the polycarbosilane is 800-3200 g/mol, preferably 1600g/mol;
the macromolecular thickening agent is polyvinylpyrrolidone, and the number average molecular weight of the macromolecular thickening agent is 10000-1300000 g/mol, preferably 1300000g/mol;
the organic solvent is one or more of DMF, THF and xylene, preferably the organic solvent is formed by mixing DMF, THF and xylene, and more preferably the organic solvent is formed by mixing DMF, THF and xylene according to the mass ratio of (2-5): (4-7): 1, and more preferably, the organic solvent is prepared by mixing DMF, THF and xylene according to a mass ratio of 2.5; and/or
The ferrocene compound is one or more of alkenyl substituted ferrocene with the carbon number of 2-8, ferrocene, alkyl substituted ferrocene with the carbon number of 1-8 and benzoyl ferrocene, and vinyl ferrocene is preferred.
3. The method of claim 1, wherein:
the mass fraction of polycarbosilane contained in the nanofiber precursor mixed solution is 2-10%, and preferably 6%;
the mass fraction of the macromolecular thickening agent contained in the nanofiber precursor mixed solution is 3-12%, and preferably 5%; and/or
The mass fraction of the ferrocene compound contained in the nanofiber precursor mixed solution is 0.1-3.5%, and the preferential mass fraction is 1.5%.
4. The production method according to claim 1, characterized in that:
the electrostatic spinning voltage is 6-30 kV, the injection speed is 0.2-4 mL/h, the receiving distance is 8-28 cm, and the environmental temperature is 15-35 ℃.
5. The method of claim 1, wherein:
the temperature of the pre-oxidation treatment is 80-280 ℃, and preferably 160 ℃;
the time of the pre-oxidation treatment is 2 to 48 hours, and is preferably 12 hours; and/or
The rate of temperature rise to the temperature of the pre-oxidation treatment is 1 to 4 ℃/min, preferably 2 ℃/min.
6. The method of claim 1, wherein:
the temperature of the high-temperature cracking is 1300-1700 ℃, and the preferable temperature is 1400 ℃;
the pyrolysis time is 1-8 h, preferably 3h; and/or
The heating rate of the temperature to the pyrolysis temperature is 0.5-6 ℃/min, preferably 2 ℃/min.
7. The method of claim 1, wherein:
the infrared opacifier is one or more of silicon carbide microparticles, titanium oxide microparticles, carbon black, iron oxide microparticles, titanium oxide microparticles, potassium hexatitanate whiskers, boron carbide microparticles and iron oxide microparticles;
the particle size of the infrared opacifier is 1-15 microns, preferably 2-4 microns;
the binder is one or more of aluminum dihydrogen phosphate, methyl orthosilicate, ethyl orthosilicate, silica sol and aluminum sol;
the foaming agent is one or more of APG0810, APG1214, TX-10, AEO-3, AEG300, AEO-7, isomeric tridecanol polyoxyethylene ether 1309, SOE surfactant and SKYIN EP2445 surfactant; and/or
The graphene oxide is graphene oxide with 1-8 layers, and is preferably single-layer graphene oxide.
8. The production method according to claim 1, characterized in that:
the mass fraction of the silicon carbide nano-fibers contained in the aerogel precursor mixed solution is 0.5-10%, preferably 5%;
the mass ratio of the infrared opacifier to the silicon carbide nano fibers is (0.1-0.6): 1 is preferably 0.25;
the mass ratio of the binder to the silicon carbide nano-fibers is (0.02-0.2): 1 is preferably 0.08;
the mass fraction of the foaming agent contained in the aerogel precursor mixed solution is 0.5-8%, and preferably 3%; and/or
The mass fraction of the graphene oxide contained in the aerogel precursor mixed solution is 0.3-2%, and preferably 1%.
9. The production method according to claim 1, characterized in that:
the pre-freezing is to freeze under liquid nitrogen for 5-60 min, preferably 20min;
the freeze drying is carried out in a freeze dryer, in the freeze drying process, the temperature of a chamber of the freeze dryer is controlled to be 10-35 ℃, the temperature of a cold trap of the freeze dryer is controlled to be-80-40 ℃, the pressure of the freeze drying is 0.1-20 Pa, and the freeze drying time is 24-72 hours; and/or
The temperature of the thermal annealing treatment is 800-1200 ℃, preferably 1100 ℃, and the time of the thermal annealing treatment is 0.5-4 h, preferably 1h.
10. The high temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material prepared by the preparation method of any one of claims 1 to 9; preferably, the high temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material has one or more of the following properties:
the temperature resistance limit of the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material in an aerobic environment is 1100-1200 ℃;
the room temperature thermal conductivity of the high temperature resistant and radiation resistant elastic silicon carbide nanofiber aerogel material is not higher than 0.032W/(m.K), and the 900 ℃ thermal conductivity is lower than 0.059W/(m.K);
the maximum compression deformation of the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material is not less than 80%, and the rebound rate is 96-100%;
the density of the high-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material is 7mg/cm at the lowest 3 ；
The diameter of the nanofiber contained in the high-temperature-resistant and anti-radiation elastic silicon carbide nanofiber aerogel material is 80-800 nm;
the high-temperature-resistant and radiation-resistant elastic silicon carbide nanofiber aerogel material can be prepared in large scale.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210954810.5A CN115253938B (en) | 2022-08-10 | 2022-08-10 | High-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210954810.5A CN115253938B (en) | 2022-08-10 | 2022-08-10 | High-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115253938A true CN115253938A (en) | 2022-11-01 |
| CN115253938B CN115253938B (en) | 2023-04-18 |
Family
ID=83750752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210954810.5A Active CN115253938B (en) | 2022-08-10 | 2022-08-10 | High-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115253938B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5855953A (en) * | 1994-03-31 | 1999-01-05 | The Regents, University Of California | Aerogel composites and method of manufacture |
| CN103254440A (en) * | 2013-06-15 | 2013-08-21 | 厦门大学 | Method of preparing liquid anaerobic polyferrocarbosilane |
| CN104528725A (en) * | 2015-01-08 | 2015-04-22 | 厦门大学 | Preparation method of magnetic silicon carbide ceramic nano particles |
| WO2017155455A1 (en) * | 2016-03-11 | 2017-09-14 | Innventia Ab | Nanocellulose aerogel particles having controlled electrical conductance, and uses thereof |
| CN108467253A (en) * | 2018-01-20 | 2018-08-31 | 南京航空航天大学 | A kind of silicon carbide nanometer line precast body enhancing alumina aerogels material and preparation method thereof |
| US20210079300A1 (en) * | 2006-05-25 | 2021-03-18 | Aspen Aerogels, Inc. | Aerogel compositions with enhanced performance |
| US20210114940A1 (en) * | 2019-10-16 | 2021-04-22 | Northwestern Polytechnical University | Process for the preparation of a ceramic nanowire preform |
| CN113603500A (en) * | 2021-08-04 | 2021-11-05 | 西北工业大学 | Non-oxide ceramic nanowire foam with layered structure and preparation method thereof |
| CN113663611A (en) * | 2021-09-23 | 2021-11-19 | 航天特种材料及工艺技术研究所 | High-temperature-resistant composite nanofiber aerogel material and preparation method thereof |
| CN114349526A (en) * | 2021-11-22 | 2022-04-15 | 东华大学 | Ceramic nanofiber aerogel with zigzag continuous phase structure and preparation method thereof |
| CN114573357A (en) * | 2022-02-28 | 2022-06-03 | 南京航空航天大学 | SiC nanowire reinforced SiC ceramic matrix composite and preparation method thereof |
-
2022
- 2022-08-10 CN CN202210954810.5A patent/CN115253938B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5855953A (en) * | 1994-03-31 | 1999-01-05 | The Regents, University Of California | Aerogel composites and method of manufacture |
| US20210079300A1 (en) * | 2006-05-25 | 2021-03-18 | Aspen Aerogels, Inc. | Aerogel compositions with enhanced performance |
| CN103254440A (en) * | 2013-06-15 | 2013-08-21 | 厦门大学 | Method of preparing liquid anaerobic polyferrocarbosilane |
| CN104528725A (en) * | 2015-01-08 | 2015-04-22 | 厦门大学 | Preparation method of magnetic silicon carbide ceramic nano particles |
| WO2017155455A1 (en) * | 2016-03-11 | 2017-09-14 | Innventia Ab | Nanocellulose aerogel particles having controlled electrical conductance, and uses thereof |
| CN108467253A (en) * | 2018-01-20 | 2018-08-31 | 南京航空航天大学 | A kind of silicon carbide nanometer line precast body enhancing alumina aerogels material and preparation method thereof |
| US20210114940A1 (en) * | 2019-10-16 | 2021-04-22 | Northwestern Polytechnical University | Process for the preparation of a ceramic nanowire preform |
| CN113603500A (en) * | 2021-08-04 | 2021-11-05 | 西北工业大学 | Non-oxide ceramic nanowire foam with layered structure and preparation method thereof |
| CN113663611A (en) * | 2021-09-23 | 2021-11-19 | 航天特种材料及工艺技术研究所 | High-temperature-resistant composite nanofiber aerogel material and preparation method thereof |
| CN114349526A (en) * | 2021-11-22 | 2022-04-15 | 东华大学 | Ceramic nanofiber aerogel with zigzag continuous phase structure and preparation method thereof |
| CN114573357A (en) * | 2022-02-28 | 2022-06-03 | 南京航空航天大学 | SiC nanowire reinforced SiC ceramic matrix composite and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| LI,J: "Facile fabrication of Fe-doped Si-C-N ceramic microspheres with flower-like morphology and the infrared extinction property" * |
| TEIMURI-MOFRAD,R: "Green synthesis of ferrocenyl-modified MnO2/carbon-based nanocomposite as an outstanding supercapacitor electrode material" * |
| WANG,YJ: "Preparation of SiC ceramic fiber from a photosensitve polycarbosilane" * |
| ZHANG,ES: "Insulatin and Robust Ceramic Nanorod Aerogels with High-Temperature Resistance over 1400 degrees C" * |
| 吴浩: "纳米四氧化三铁/碳气凝胶制备与吸波性能研究" * |
| 裴雨辰，张晚林，李文静: "空天领域气凝胶研究与应用进展" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115253938B (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Engineering cross-linking by coal-based graphene quantum dots toward tough, flexible, and hydrophobic electrospun carbon nanofiber fabrics | |
| Chung | Carbon fiber composites | |
| Banerjee et al. | Recent advancement in coal tar pitch-based carbon fiber precursor development and fiber manufacturing process | |
| CN102031593B (en) | Method for preparing pitch-based carbon fiber | |
| US20170241049A1 (en) | Method to Massively Manufacture Carbon Fibers through Graphene Composites and the Use Thereof | |
| KR101432541B1 (en) | Carbon fiber composition including graphene nano-powders and fabrication method for carbon fiber by using the same | |
| CN109023590B (en) | Silicon carbide hollow fiber and preparation method thereof | |
| CN110079896B (en) | Silicon carbide nanofiber bundle and preparation method thereof | |
| CN114849599B (en) | Nano-cellulose composite carbon aerogel ball and preparation method and application thereof | |
| CN112251914A (en) | High-temperature-resistant composite nanofiber membrane with good piezoelectric performance and preparation method thereof | |
| CN112761025B (en) | Carbon paper for gas diffusion layer, preparation method thereof and fuel cell | |
| CN113699684B (en) | Phenolic aldehyde matrix type micro/nano composite carbon fiber felt and preparation method thereof | |
| CN115253938B (en) | High-temperature-resistant anti-radiation elastic silicon carbide nanofiber aerogel material and preparation method thereof | |
| CN115557790B (en) | Elastic SiC ceramic sponge material and preparation method and application thereof | |
| CN115652479B (en) | Method for preparing silicon carbide hollow microspheres by electrostatic spinning method | |
| KR100864063B1 (en) | Manufacturing method of polycarbosilan mat by electrospinning process and manufacturing method of siliconcarbide through the process | |
| CN115611632B (en) | Preparation method of flexible high-temperature-resistant silicon carbide aerogel composite heat insulation material | |
| CN109750388B (en) | Preparation method of defect fluorite phase gadolinium zirconate fiber | |
| CN104212168A (en) | Preparation method of SiC nanowire modified CF/PI composite material | |
| CN112030544A (en) | Method for in-situ growth of silicon carbide nanowires on surface of silicon carbide fiber | |
| Kang et al. | SiC fibers with different diameters exhibiting excellent high-temperature resistance and oxidation resistance | |
| Yu et al. | Highly flexible and strong SiC fibre mats prepared by electrospinning and hot-drawing | |
| CN112962214A (en) | High-crystallization near-stoichiometric ratio SiC micro-nano fiber membrane and preparation method thereof | |
| KR20220128661A (en) | Insulation material suitable for use at high temperature and method for manufacturing the insulation material | |
| CN113278258A (en) | Bending-resistant mesophase pitch carbon fiber composite heat dissipation film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |