CN116876111B - High-temperature-resistant ceramic aerogel fiber and preparation method thereof - Google Patents
High-temperature-resistant ceramic aerogel fiber and preparation method thereof Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 87
- 239000004964 aerogel Substances 0.000 title claims abstract description 86
- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 115
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- -1 polysiloxane Polymers 0.000 claims description 23
- 229920001296 polysiloxane Polymers 0.000 claims description 22
- 239000011240 wet gel Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000007710 freezing Methods 0.000 claims description 17
- 230000008014 freezing Effects 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000000499 gel Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical group CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000004965 Silica aerogel Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 229960000583 acetic acid Drugs 0.000 description 9
- 239000012362 glacial acetic acid Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006740 morphological transformation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a high-temperature-resistant ceramic aerogel fiber and a preparation method thereof, and belongs to the technical field of aerogel fibers.
Description
Technical Field
The invention belongs to the technical field of aerogel fibers, and particularly relates to a high-temperature-resistant ceramic aerogel fiber and a preparation method thereof.
Background
The silica aerogel is a novel super heat insulation material formed by a three-dimensional nano network with silica bonds as a main body, and has wide application prospects in the fields of heat insulation, sound insulation, noise reduction, environmental protection, medicine, catalysis, building energy conservation, petrochemical industry, aerospace and the like.
Aerogel fibers have been developed primarily in recent twenty years and show a strong application background in the fields of intelligent thermal management, adsorption, catalysis, etc. The silica aerogel material in the form of fibers has higher length-diameter ratio and better mechanical property, is hopeful to help solve the brittleness problem of the silica aerogel, and in the application aspect, the fibrous silica aerogel can be mutually overlapped to form an independent application whole, so that the silica aerogel has stronger expansion flexibility. Currently, silica aerogel fibers are mainly prepared by wet spinning technology, such as the patents CN202111181330.1, CN201511029850.5, CN201911347836.8, CN201911346524.5, and the like. The silica aerogel fibers prepared by the method generally need to undergo organic solvent replacement and supercritical drying processes to ensure structural performance advantages compared with other aerogel materials, have higher production cost and are not beneficial to large-scale preparation.
The silica aerogel prepared by the sol-gel method mainly comprises a three-dimensional porous structure formed by an amorphous silica network, the amorphous silica skeleton network can be broken and reconstructed in chemical bond at about 600 ℃ and is converted into glass-state or crystalline silica with higher thermal stability, the skeleton structure collapses in the conversion process, and the porous structure is basically disappeared in a high-temperature state to finally form compact crystalline silica, so that the silica aerogel is difficult to apply in a high-temperature environment.
Nonpolar groups in the organic-inorganic hybrid polysiloxane aerogel can be quickly carbonized in the high-temperature treatment or direct flame burning process, so that the porous framework structure is collapsed, the volume of the aerogel material is severely contracted and gradually densified, and the pore structure characteristics are lost. Therefore, the organic-inorganic hybrid siloxane network is converted into a silicon dioxide network with better high temperature resistance through the high temperature treatment process under the condition of retaining the characteristics of the aerogel, and the silicon dioxide network still has certain challenges.
Disclosure of Invention
In order to solve the technical problems, the invention provides the high-temperature-resistant ceramic aerogel fiber and the preparation method thereof, and the preparation method is simple in process, short in preparation period and wide in application range.
In order to achieve the above purpose, the invention provides a high temperature resistant ceramic aerogel fiber, which has the density of 10-300 mg/cm 3, the thermal conductivity of 0.010-0.060W/(m.K), the diameter of 10-300 mu m, the length-diameter ratio of more than 10, the initial decomposition temperature of more than 900 ℃ and the specific surface area of 100-1500 m 2/g.
The invention also provides a preparation method of the high-temperature-resistant ceramic aerogel fiber, which comprises the following steps:
mixing an acid catalyst, deionized water, a surfactant and an organic-inorganic hybrid silicon source, controlling the pH value of the mixed solution to be between 2 and 6, and stirring to prepare silica sol;
Adding an alkali catalyst into the silica sol, controlling the pH value of the mixed solution to be 7-11, and obtaining polysiloxane wet gel after gel;
Placing the polysiloxane wet gel in a directional freezing device for directional freezing, and drying the frozen product to obtain aerogel fibers;
Calcining the aerogel fiber in an oxygen atmosphere to obtain the high-temperature-resistant ceramic aerogel fiber.
According to the invention, organic-inorganic hybrid siloxane containing different nonpolar groups is used as a silicon source, water is used as a solvent to reduce raw material cost, a surfactant is used to realize microstructure regulation and control of the polysiloxane aerogel, and a rapid directional freezing technology is combined to obtain various polysiloxane aerogel fibers with different carbon contents.
According to the invention, a stable polysiloxane network is slowly heated and calcined in an oxygen atmosphere, a part of nonpolar groups are blocked and converted into carbon elements, under the influence of certain residual carbon, an amorphous silicon oxide network is converted into a more stable glassy or crystalline silicon dioxide network, the fiber morphology of the aerogel is reserved, and finally the high-temperature-resistant silicon dioxide ceramic aerogel fiber is obtained.
The preparation method does not need to involve any organic solvent in the preparation process, and effectively reduces the raw material cost and the production safety cost in the aerogel fiber production process.
Further, the mass ratio of the surfactant to the organic-inorganic hybrid silicon source is 1:10-400.
Further, the acid catalyst is a weak acid, for example, acetic acid or oxalic acid; the surfactant is an ionic surfactant or a nonionic surfactant, and can be, for example, a cationic surfactant, such as cetyltrimethylammonium chloride, an anionic surfactant, such as sodium dodecyl sulfate, and a nonionic surfactant, such as F127.
Further, the organic-inorganic hybrid silicon source is organic-inorganic hybrid siloxane, one or more nonpolar groups which do not participate in hydrolytic condensation reaction exist on the molecule of the organic-inorganic hybrid silicon source, and the mass fraction of carbon atoms in the organic-inorganic hybrid silicon source is 10-50wt% and comprises methyltriethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane.
Further, during directional freezing, the temperature range of the cold source in the directional freezing is as follows: the temperature gradient of the polysiloxane wet gel is distributed between 1 ℃ and 300 ℃ below zero and between-20 ℃ and-300 ℃.
Further, the oxygen atmosphere is a gas environment with different oxygen contents, the polysiloxane aerogel fiber is placed in a closed space in a nitrogen atmosphere before calcination, the oxygen content in the calcination process is controlled by adjusting the oxygen flow rate, the oxygen flow rate control range is 0 mL/min-20 mL/min, and the oxygen flow rate is not 0mL/min.
Further, the calcination is temperature rising calcination, the temperature rising rate is 0.001-5 ℃/min, the calcination temperature is 700-1400 ℃, and the temperature is kept for at least 1h.
Further, the calcination is gradient heating calcination, and gradient heating is sequentially performed in a heating-heat preservation-heating-heat preservation mode, and the final temperature is raised to 700-1400 ℃ and the heat preservation time is at least 1h.
Compared with the prior art, the invention has the following advantages and technical effects:
1. The invention combines the sol-gel technology and the directional freezing technology to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with uniform mesoporous distribution and non-polar group end capping, utilizes the solubilization of the surfactant to obtain a porous structure with uniform pore diameter, and utilizes different silicon sources to prepare aerogel fibers with different carbon contents.
2. According to the invention, the high-temperature-resistant ceramic aerogel fiber is prepared by taking water as a solvent, any organic solvent is not required in the preparation process, and deionized water is used for preparation, so that the preparation safety is greatly improved.
3. According to the invention, the carbonization rate of nonpolar groups in the aerogel fiber is regulated by controlling the oxygen content in the gas atmosphere, the stable aerogel structure is not damaged all the time in the high-temperature calcination process, the nonpolar groups are partially converted into carbon dioxide or carbon monoxide, the carbon is partially converted into carbon to remain in the aerogel, the amorphous silicon oxide network is converted into a glassy or crystalline silicon dioxide network under the influence of the residual carbon, and the fiber morphology of the aerogel is maintained.
4. The silica ceramic aerogel fiber prepared by the method has the excellent performances of good microstructure, low density, low heat conductivity coefficient and high heat stability, and can be well applied to the fields of sound absorption, noise reduction, heat insulation, heat preservation, adsorption filtration and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a scanning electron microscope microscopic morphology of the high temperature resistant silica ceramic aerogel fiber prepared in example 1.
FIG. 2 is an infrared spectrum of the high temperature resistant silica ceramic aerogel fiber prepared in example 1.
FIG. 3 is a thermogravimetric curve of the high temperature resistant silica ceramic aerogel fiber prepared in example 1.
FIG. 4 is an XRD pattern of the high temperature resistant silica ceramic aerogel fiber prepared in example 1 during morphological transformation;
FIG. 5 is an apparent morphology of the high temperature resistant silica ceramic aerogel fiber prepared in example 1.
FIG. 6 is an apparent morphology of the high temperature resistant silica ceramic aerogel fiber prepared in example 2.
FIG. 7 is a graph of the micro morphology of the high temperature resistant silica ceramic aerogel fibers prepared in example 2.
FIG. 8 is a nitrogen adsorption/desorption isotherm of the high temperature resistant silica ceramic aerogel fiber prepared in example 2.
FIG. 9 is a thermogravimetric analysis of the high temperature resistant silica ceramic aerogel fiber prepared in example 2.
FIG. 10 is an infrared spectrum of the high temperature resistant silica ceramic aerogel fiber prepared in example 2.
FIG. 11 is a graph of the micro morphology of the high temperature resistant silica ceramic aerogel fibers prepared in example 3.
FIG. 12 is an apparent morphology of the high temperature resistant silica ceramic aerogel fiber prepared in example 3.
FIG. 13 is a graph of the micro morphology of the high temperature resistant silica ceramic aerogel fibers prepared in example 4.
FIG. 14 is an apparent morphology of the refractory silica ceramic aerogel fibers prepared in example 4.
FIG. 15 is a graph of the micro morphology of the high temperature resistant silica ceramic aerogel fibers prepared in example 5.
FIG. 16 is an apparent morphology of the refractory silica ceramic aerogel fibers prepared in example 5.
FIG. 17 is a graph of the micro morphology of the refractory silica ceramic fiber prepared in example 8.
FIG. 18 is an apparent morphology of the refractory silica ceramic fiber prepared in example 8.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials in the embodiment of the invention are all obtained through purchase.
Example 1
Mixing deionized water, glacial acetic acid, cetyl trimethyl ammonium bromide and methyltrimethoxysilane in a beaker, wherein the mass ratio is 50:0.1:1:10, the pH is 5, obtaining silica-containing sol after hydrolysis for 30min, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, obtaining polysiloxane wet gel after gel, placing the polysiloxane wet gel on a copper block semi-immersed in liquid nitrogen, and performing freeze drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 15%. Placing the aerogel fiber in a heating furnace under the nitrogen atmosphere, introducing oxygen at the speed of 1mL/min, heating to 800 ℃ at the speed of 1 ℃/min, and preserving heat for 3 hours to obtain the high-temperature-resistant silica ceramic aerogel fiber. The scanning electron microscope microscopic morphology diagram of the high-temperature-resistant silica ceramic aerogel fiber prepared in the embodiment 1 is shown in fig. 1, the infrared spectrogram is shown in fig. 2, the thermogravimetric curve is shown in fig. 3, the XRD diagram in the morphology transformation process is shown in fig. 4, and the apparent morphology diagram is shown in fig. 5.
Example 2
Mixing deionized water, glacial acetic acid, cetyl trimethyl ammonium bromide and methyltrimethoxysilane in a beaker, wherein the mass ratio is 60:0.2:3:20, the pH is 5, obtaining silica-containing sol after hydrolysis for 1h, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, obtaining wet gel after gel, placing the wet gel on a copper block with the temperature of-80 ℃, and carrying out freeze drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 15%. Placing the aerogel fiber in a heating furnace under the nitrogen atmosphere, introducing oxygen at the speed of 1mL/min, heating to 1200 ℃ at the speed of 3 ℃/min, and preserving heat for 3 hours to obtain the high-temperature-resistant silica ceramic aerogel fiber. The scanning electron microscope appearance morphology diagram of the high-temperature-resistant silica ceramic aerogel fiber prepared in the embodiment 2 is shown in fig. 6, the microstructure diagram is shown in 7, the nitrogen adsorption and desorption isotherms are shown in fig. 8, the thermogravimetric analysis curve is shown in fig. 9, and the infrared spectrogram is shown in fig. 10.
Example 3
Mixing deionized water, glacial acetic acid, hexadecyl trimethyl ammonium bromide and methyltriethoxysilane in a beaker, wherein the mass ratio is 50:0.1:2:15, the pH is 5, obtaining silica-containing sol after hydrolysis for 3 hours, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, obtaining wet gel after gel, placing the wet gel on a copper block semi-immersed in liquid nitrogen, and freeze-drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 15%. Placing the aerogel fiber in a heating furnace under the nitrogen atmosphere, introducing oxygen at the speed of 0mL/min, heating to 900 ℃ at the speed of 3 ℃/min, and preserving heat for 3 hours to obtain the high-temperature-resistant silica ceramic aerogel fiber. The scanning electron microscope microscopic morphology diagram of the high-temperature-resistant silica ceramic aerogel fiber prepared in the embodiment 3 is shown in fig. 11, and the apparent morphology diagram is shown in fig. 12.
Example 4
Mixing deionized water, glacial acetic acid, cetyltrimethylammonium bromide and vinyltrimethoxysilane in a beaker, wherein the mass ratio is 60:0.2:3:20, the pH is 5, obtaining silica-containing sol after hydrolysis for 3 hours, adding urea with the mass fraction of 2%, heating to 80 ℃, adjusting the pH to 9, obtaining wet gel after gel, placing the wet gel on a copper block with the temperature gradient of-80 ℃ to be 10 ℃/cm, and freeze-drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 30%. Placing the aerogel fiber in a heating furnace under nitrogen atmosphere, introducing oxygen at a speed of 1mL/min, and setting a gradient heating program at a heating rate of 5 ℃/min to be: heating to 300 ℃ for 4 hours, heating to 500 ℃ for 2 hours, and heating to 900 ℃ for 3 hours to obtain the high-temperature-resistant silica ceramic aerogel fiber. The scanning electron microscope microscopic morphology diagram of the high-temperature-resistant silica ceramic aerogel fiber prepared in the embodiment 4 is shown in fig. 13, and the apparent morphology diagram is shown in fig. 14.
Example 5
Mixing deionized water, glacial acetic acid, F127 and methyltrimethoxysilane in a beaker, wherein the mass ratio is 50:0.1:1:15, the pH is 5, obtaining silica-containing sol after hydrolysis for 30min, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, obtaining wet gel after gel, placing the wet gel on a copper block semi-immersed in liquid nitrogen, and performing freeze drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 15%. Placing the aerogel fiber in a heating furnace under nitrogen atmosphere, heating to 300 ℃ and preserving heat for 4 hours, introducing oxygen at a speed of 4mL/min after the first-stage heat preservation, heating to 500 ℃ and preserving heat for 2 hours, and heating to 900 ℃ and preserving heat for 3 hours to obtain the high-temperature-resistant silica ceramic aerogel fiber. The scanning electron microscope microscopic morphology diagram of the high-temperature-resistant silica ceramic aerogel fiber prepared in the embodiment 5 is shown in fig. 15, and the apparent morphology diagram is shown in fig. 16.
Example 6
Mixing deionized water, glacial acetic acid, cetyl trimethyl ammonium chloride and phenyl trimethoxy silane in a beaker, wherein the mass ratio is 50:0.1:5:15, the pH is 5, obtaining silica-containing sol after hydrolysis for 6 hours, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, obtaining wet gel after gel, placing the wet gel on a copper block semi-immersed in liquid nitrogen, and freeze-drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 50%. Placing the aerogel fiber in a heating furnace under nitrogen atmosphere, heating to 300 ℃ and preserving heat for 4 hours, introducing oxygen at a speed of 2mL/min after the first-stage heat preservation, heating to 500 ℃ and preserving heat for 2 hours, and heating to 900 ℃ and preserving heat for 3 hours to obtain the high-temperature-resistant silica ceramic aerogel fiber.
Example 7
Mixing deionized water, glacial acetic acid and methyltrimethoxysilane in a beaker, wherein the mass ratio is 50:0.1:10, the pH is 5, obtaining silica-containing sol after hydrolysis for 30min, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, standing for 12h, layering the sol, and forming white powdery precipitate at the bottom of the solution, so that a stable wet gel structure cannot be obtained. This example does not allow for the subsequent preparation of aerogels since no surfactant is added to obtain a stable wet gel.
Example 8
Mixing deionized water, glacial acetic acid, cetyl trimethyl ammonium bromide and methyltrimethoxysilane in a beaker, wherein the mass ratio is 50:0.1:1:10, the pH is 5, obtaining silica-containing sol after hydrolysis for 30min, then adding ammonia water with the mass fraction of 1%, adjusting the pH to 9, obtaining wet gel after gel, placing the wet gel on a copper block semi-immersed in liquid nitrogen, and freeze-drying after freezing to obtain the organic-inorganic hybrid polysiloxane aerogel fiber with the carbon content of 15%. Placing the aerogel fiber in a heating furnace under the nitrogen atmosphere, introducing oxygen at the speed of 1mL/min, heating to 1500 ℃ at the speed of 10 ℃/min, and preserving heat for 3 hours to obtain the compact silica fiber. The scanning electron microscope microscopic morphology of the dense silica ceramic fiber prepared in example 8 is shown in fig. 17, and the apparent morphology is shown in fig. 18.
The structure and performance parameters of the aerogel fibers obtained in examples 1 to 8 are shown in table 1, and as can be seen from table 1, the high-temperature-resistant silica aerogel fibers obtained by the preparation method of the invention have a continuous and stable three-dimensional porous network structure and have good high-temperature resistance; the process can utilize the key parameters of surfactant, carbon content, oxygen content, calcination temperature and the like to realize the controllable preparation of the aerogel fiber forming and microstructure; and the preparation process is simple, low in energy consumption, safe, low in cost and suitable for mass production. Through the embodiments 1 to 5, the silica aerogel fiber obtained by the method has great application prospect in the fields of high-temperature heat insulation, sound absorption, noise reduction and the like. From examples 6 to 8, it was found that it was difficult to prepare high temperature resistant silica aerogel fibers having good structural properties at a high silicon source content without using a surfactant and at a calcination temperature exceeding the above-described process specification.
TABLE 1 Structure and Performance parameters of aerogel fibers obtained in examples 1-8
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (3)
1. The preparation method of the high-temperature-resistant silica ceramic aerogel fiber is characterized by comprising the following steps of:
mixing an acid catalyst, deionized water, a surfactant and an organic-inorganic hybrid silicon source, controlling the pH value of the mixed solution to be between 2 and 6, and stirring to prepare silica sol;
Adding an alkali catalyst into the silica sol, controlling the pH value of the mixed solution to be 7-11, and obtaining polysiloxane wet gel after gel;
Placing the polysiloxane wet gel in a directional freezing device for directional freezing, and drying the frozen product to obtain aerogel fibers;
Calcining the aerogel fiber in an oxygen atmosphere to obtain a high-temperature-resistant ceramic aerogel fiber;
The oxygen atmosphere is a gas environment with different oxygen contents, the polysiloxane aerogel fiber is placed in a closed space of nitrogen atmosphere before calcination, the oxygen content in the calcination process is controlled by adjusting the oxygen flow, the oxygen flow control range is 0-20 mL/min, and the oxygen flow is not 0mL/min;
the mass ratio of the surfactant to the organic-inorganic hybrid silicon source is 1:10-15;
the organic-inorganic hybrid silicon source is methyltriethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane;
During directional freezing, the temperature range of the cold source in the directional freezing is as follows: the temperature gradient of the polysiloxane aerogel fiber is distributed between 1 and 300 ℃ below zero and between-20 ℃ and-300 ℃;
The calcination is temperature rising calcination, the temperature rising rate is 1-5 ℃/min, the calcination temperature is 700-1400 ℃, and the temperature is kept for at least 1h.
2. The method for preparing high temperature resistant silica ceramic aerogel fibers according to claim 1, wherein the acid catalyst is a weak acid; the surfactant is an ionic surfactant or a nonionic surfactant.
3. The high-temperature-resistant silica ceramic aerogel fiber prepared by the preparation method of the high-temperature-resistant silica ceramic aerogel fiber according to claim 1 or 2, wherein the density of the high-temperature-resistant silica ceramic aerogel fiber is 10-300 mg/cm 3, the thermal conductivity is 0.010-0.060W/(m.k), the diameter is 10-300 μm, the length-diameter ratio is more than 10, the initial decomposition temperature exceeds 900 ℃, and the specific surface area is 100-1500 m 2/g.
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