CN115259845A - Preparation method of flexible continuous mullite filament - Google Patents
Preparation method of flexible continuous mullite filament Download PDFInfo
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- CN115259845A CN115259845A CN202210735437.4A CN202210735437A CN115259845A CN 115259845 A CN115259845 A CN 115259845A CN 202210735437 A CN202210735437 A CN 202210735437A CN 115259845 A CN115259845 A CN 115259845A
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- mullite
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- aluminum
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 73
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 238000009987 spinning Methods 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000000578 dry spinning Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- -1 aluminum alkoxide Chemical class 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 159000000013 aluminium salts Chemical class 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 6
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 6
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 5
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 3
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6224—Fibres based on silica
- C04B35/62245—Fibres based on silica rich in aluminium oxide
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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Abstract
The invention relates to a preparation method of a flexible continuous mullite filament, which comprises the steps of preparing mullite precursor sol and alumina precursor sol, mixing the mullite precursor sol and the alumina precursor sol, fully stirring, adding an additive and a high-molecular spinning auxiliary agent, heating, stirring, condensing and refluxing to obtain clear and transparent composite sol; then carrying out reduced pressure distillation to obtain spinnable mullite precursor sol; preparing the hybridized mullite continuous filament by dry spinning molding; and finally, drying and sintering at high temperature to obtain the continuous mullite filament. Compared with the prior art, the continuous mullite filament prepared by the dry spinning method has the advantages of 10-50 um diameter, smooth surface, good flexibility and high strength.
Description
Technical Field
The invention relates to the technical field of inorganic fiber preparation, in particular to a preparation method of a flexible continuous mullite filament.
Background
Mullite fiber is used as the present novel ultra-light high-temperature heat-resistant fiber without fixed composition and chemical groupTo between 3Al 2 O 3 ·2SiO 2 ～2Al 2 O 3 ·SiO 2 The structure is a polycrystalline structure, and the main crystal phase is mullite microcrystal. The mullite fiber has the excellent performances of high melting point, low density, low thermal conductivity and thermal expansion coefficient, excellent high-temperature creep resistance and thermal shock resistance, oxidation resistance and the like, so that the mullite fiber is widely used as a high-temperature structural material and is more and more valued by people.
Because the mullite fiber has many excellent characteristics, the mullite fiber has good environmental stability and high-temperature mechanical property under a high-temperature oxidation atmosphere, and is widely applied to thermal protection systems of various industries, such as metallurgy, mechanical industry, high-temperature kilns and the like.
At present, the sol-gel method is one of the most common methods for preparing mullite fiber, and has the advantages of mild reaction process, high uniformity of each component of the fiber, low requirement on equipment and the like; however, the control variables are more in the reaction process, which easily causes the sol to flocculate or gel. CN104086200 discloses a preparation method of mullite fiber, which uses anhydrous aluminum chloride and aluminum powder as aluminum sources, ethyl orthosilicate as silicon sources, glacial acetic acid as a colloid stabilizer and a spinning auxiliary agent, and adopts a sol-gel method and a centrifugal spinning method to prepare the mullite fiber; the spinnable mullite precursor sol is successfully prepared in the patent, but the preparation method has high danger of using concentrated nitric acid, is not suitable for large-scale industrial production of mullite fiber, and the prepared mullite short fiber cannot be used for spinning and three-dimensional weaving. At present, the preparation method of the mullite short fiber is mature, and the large-scale production can be realized. However, the method for preparing continuous mullite filaments has many problems, such as the prepared mullite precursor sol has no spinnability or poor spinnability, and fibers are easy to break during dry spinning.
Therefore, the preparation process of the mullite sol with simple preparation process, good spinning property, good stability and long storage time needs to be developed urgently, and the continuous mullite filament is produced on a large scale based on the method spinning forming technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of the flexible continuous mullite filament, the diameter of the prepared continuous mullite filament is 10-50 um by dry spinning, and the prepared continuous mullite filament has smooth surface, good flexibility and high strength.
The purpose of the invention can be realized by the following technical scheme:
the invention aims to provide a preparation method of a flexible continuous mullite filament, which comprises the following steps:
s1: preparation of spinnable mullite precursor sol
a. Adding ionizable aluminum salt, aluminum alkoxide and silicon alkoxide into deionized water, and stirring at constant temperature to obtain clear and transparent mullite precursor sol A;
b. adding ionizable aluminum salt and aluminum alkoxide into deionized water, and stirring at constant temperature to obtain translucent alumina precursor sol B;
c. mixing the mullite precursor sol A and the alumina precursor sol B, stirring at room temperature, adding an additive and a high-molecular spinning auxiliary agent, heating, stirring, condensing and refluxing to obtain a clear and transparent composite sol C; and carrying out reduced pressure distillation on the clear and transparent composite sol C to obtain a spinnable mullite precursor sol D.
S2: preparation of continuous mullite filaments
And (3) performing vacuum deaeration on the spinnable mullite precursor sol D, preparing the hybridized mullite continuous filament by using dry spinning forming, and drying and sintering the hybridized mullite continuous filament at high temperature to obtain the continuous mullite filament.
In S1, the ionizable aluminum salt is one or a combination of more than two of aluminum nitrate nonahydrate, aluminum chloride hexahydrate and aluminum sulfate octadecahydrate; the aluminum alkoxide is selected from one or a combination of more than two of aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum triethoxide and aluminum tri-n-propoxide, and the silicon alkoxide is selected from one or a combination of more than two of tetra-n-propoxysilane, trimethylsilyl acetate, tetra-n-butoxysilane and tetraethyl orthosilicate.
Furthermore, in the step a of S1, the feeding proportion meets the requirement of M (Aluminium salts + aluminium alkoxides) /M Deionized water =1: (10 to 40) and satisfies M Ionizable aluminium salt /M Alkoxide of aluminium ＝1：(2～6)，M Alkoxide of silicon /M Alkoxides of aluminium ＝1：(1.5～3.5)。
Further, in b of S1, in the charging proportion, M is satisfied (Aluminium salts + aluminium alkoxides) /M Deionized water =1: (5 to 20) and M is satisfied Ionizable aluminium salt /M Alkoxide of aluminium ＝1：(2～6)；
Further, in the step c of S1, m is satisfied in the feeding proportion (mullite precursor sol A) /m (alumina precursor Sol B) = (5 to 40): 1, and the mass of the alumina accounts for 1 to 10 percent of the mass of the mullite.
Further, in c of S1, the additive refers to one or a combination of magnesium chloride, copper chloride, ferric chloride, magnesium nitrate and ferric nitrate.
The addition amount of the additive is 0.01-2% of the total mass of the continuous mullite filament.
Further, in the step c of S1, the polymer spinning aid is one or a combination of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol and carboxymethyl cellulose.
The addition amount of the high molecular spinning auxiliary agent is 2-8% of the total mass of the continuous mullite filament.
Further, in a and b of S1, the conditions of constant-temperature stirring are as follows: stirring at 25-60 deg.c for 4-12 hr.
In the step c of S1, the constant-temperature stirring conditions are as follows: the temperature is 25-60 ℃, and the constant-temperature stirring time is 0.5-2 h;
the conditions of heating, stirring and condensing reflux are as follows: the temperature is 50-90 ℃, and the time is 1-4 h;
the conditions of reduced pressure distillation were: the temperature is 30-80 ℃, and the vacuum degree is-0.1 to-0.04 MPa.
Further, in the step c of S1, the spinnable mullite precursor sol has a viscosity of 20 to 150 pas after distillation under reduced pressure.
Further, in S2, the vacuum defoaming conditions are: the vacuum degree is-0.1 to-0.04 MPa, and the defoaming time is 1 to 3 hours;
the dry spinning forming conditions are as follows: the temperature condition of the spinning assembly is 20-50 ℃, the relative humidity is 10-70%, the pump supply is 30-100 ml/min, the number of spinneret holes is 500-2000, the diameter of the spinneret hole is 0.05-0.2 mm, the temperature of the spinning channel is 80-150 ℃, and the winding speed is 50-400 m/min.
Further, in S2, the drying conditions are: the environment humidity is 30-80%, the drying temperature is 50-100 ℃, and the drying time is 3-8 h;
the high-temperature calcination treatment comprises the following steps: the temperature is raised to a first target temperature at the rate of 0.5-2 ℃/min, and the temperature is kept for 10-60 min, wherein the first target temperature is 150-400 ℃; then heating to a second target temperature at the heating rate of 2-8 ℃/min, and preserving the heat for 10-60 min, wherein the second target temperature is 400-800 ℃; finally, the temperature is increased to a third target temperature at the heating rate of 10 ℃/min, and the third target temperature is 1000-1600 ℃.
The mechanism of the invention is as follows:
the ionizable aluminum salt in the present invention ionizes into aluminum ions and anions, and the aluminum ions attract surrounding water molecules to form solvent units [ Al (H) 2 O) n ] 3+ At the same time, H is strongly released to maintain coordination number + The tendency of (1) is that the system contains a large amount of H + ，H + The existence of the metal alkoxide is beneficial to protonation of alkoxy groups with negative charges, and the hydrolysis and polycondensation reaction of the metal alkoxide are promoted, so that Al-O-Al, si-O-Si and Al-O-Si structures are formed, a series of chain molecules are formed in a system, the chain molecules are also the basis for spinning of the sol after concentration, and the purpose of adding the high-molecular spinning auxiliary agent is to form hydrogen bond action between the colloidal particles and the high-molecular spinning auxiliary agent and improve the spinning performance of the sol.
The system of the invention utilizes alumina precursor sol, mullite precursor sol, additives and macromolecule spinning aidThe agent is used for preparing spinnable mullite precursor sol, after decompression concentration and vacuum deaeration, the hybrid continuous mullite filament is prepared by dry spinning forming, and after drying and high-temperature sintering treatment, the mullite-containing hybrid continuous mullite filament with a main crystal phase and a small amount of alpha-Al is obtained 2 O 3 Flexible continuous mullite filaments of the phase. By introducing alpha-Al into the mullite phase 2 O 3 The phase functions as mullite and alpha-Al 2 O 3 The free enthalpy of the dual-phase grain boundary is high, which is not beneficial to the fusion growth among grains. The two-phase wrappage appears at the crystal boundary, can produce the nail-pricking function to the movement of the crystal boundary, and inhibit the rapid growth of crystal grains during high-temperature sintering. The function of the additive is that metal ions of the additive occupy the position of aluminum or silicon in the original mullite crystal lattice, so that the mullite crystal lattice generates distortion, the crystallization temperature of the mullite crystal structure is reduced, and the adverse effect on the surface appearance of the filament is generated if the additive is not excessive; in addition, metal ions of the additive are taken as solid solution and tend to gather at the grain boundary, so that the movement of the grain boundary is hindered, the migration rate of the grain boundary is reduced, and the rapid growth of the grain is inhibited.
Compared with the prior art, the invention has the following technical advantages:
(1) The spinnable mullite precursor sol prepared by the invention has the advantages of simple preparation process, no need of high temperature and high pressure, green and environment-friendly raw materials, and extremely stable prepared clear and transparent mullite precursor sol, and is suitable for large-scale production.
(2) The invention introduces a small amount of alpha-Al into mullite phase 2 O 3 The phase inhibits the fusion growth among crystal grains, and the two-phase wrappage appears at the crystal boundary, which can generate the nail-binding effect on the movement of the crystal boundary and inhibit the rapid growth of the crystal grains during high-temperature sintering; and the addition of the additive reduces the crystallization temperature of the mullite crystal completely converted, and avoids the rapid growth of the mullite grains at high temperature, so that the continuous mullite filament with small mullite grains and good flexibility can be obtained.
(3) The continuous mullite filament prepared by the dry spinning method has the filament diameter of 10-50 mu m, smooth surface, good flexibility, high strength and the like, can be spun, three-dimensionally woven and the like, and is widely applied to the fields of structural reinforcement materials, high-temperature heat insulation materials and the like.
Drawings
FIG. 1: SEM image of continuous mullite filaments prepared in example 1.
FIG. 2: XRD pattern of continuous mullite filaments prepared in example 1.
FIG. 3: the continuous mullite filament force-elongation plot prepared in example 1.
Detailed Description
The preparation method of the flexible continuous mullite filament provided by the invention specifically comprises the following steps:
the first step is as follows: preparation of spinnable mullite precursor sol
a. Adding ionizable aluminum salt, aluminum alkoxide and silicon alkoxide into deionized water, and stirring at constant temperature to obtain clear and transparent mullite precursor sol A;
b. adding ionizable aluminum salt and aluminum alkoxide into deionized water, and stirring at constant temperature to obtain a translucent alumina precursor sol B;
c. mixing the mullite precursor sol A and the alumina precursor sol B, stirring at a constant temperature, adding an additive and a high-molecular spinning auxiliary agent, heating, stirring and condensing for reflux to obtain a clear and transparent composite sol C; and carrying out reduced pressure distillation on the clear and transparent composite sol C to obtain a spinnable mullite precursor sol D.
The second step is that: preparation of continuous mullite filaments
Carrying out vacuum defoaming on the spinnable mullite precursor sol D, and preparing the hybrid mullite continuous filament by using dry spinning forming; and finally, drying and sintering the hybrid mullite continuous filament at high temperature to obtain the continuous mullite filament.
In one embodiment of the present invention, in the first step, the ionizable aluminum salt refers to one or a combination of two or more of aluminum nitrate nonahydrate, aluminum chloride hexahydrate, and aluminum sulfate octadecahydrate; the aluminum alkoxide is selected from one or a combination of more than two of aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum triethoxide and aluminum tri-n-propoxide, and the silicon alkoxide is selected from one or a combination of more than two of tetra-n-propoxysilane, trimethylsilyl acetate, tetra-n-butoxysilane and tetraethyl orthosilicate.
In one embodiment of the invention, in step a of the first step, the molar ratio of (ionizable aluminum salt + aluminum alkoxide) to deionized water in the mullite precursor sol a is 1 (10-40), the molar ratio of ionizable aluminum salt to aluminum alkoxide is 1 (2-6), and the molar ratio of silicon alkoxide to aluminum alkoxide is 1 (1.5-3.5).
In one embodiment of the invention, in the step a, the constant temperature stirring is performed under the temperature condition of 25-50 ℃ and the stirring time of 5-12 h.
In one embodiment of the present invention, in step B of the first step, the molar ratio of (ionizable aluminum salt + aluminum alkoxide) to deionized water in the alumina precursor sol B is 1 (5-20), and the molar ratio of ionizable aluminum salt to aluminum alkoxide is 1 (2-6).
In one embodiment of the present invention, in the step b, the constant temperature stirring is performed at a temperature of 25 to 50 ℃ for 5 to 12 hours.
In one embodiment of the present invention, in the first step C, the mass ratio of the mullite precursor sol a to the alumina precursor sol B in the composite sol C is (5-40): 1, and the mass of alumina is 1-10% of the mass of mullite.
In an embodiment of the present invention, in step c of the first step, the additive refers to one or a combination of magnesium chloride, copper chloride, ferric chloride, magnesium nitrate and ferric nitrate.
In one embodiment of the present invention, in the first step c, the additive is added in an amount of 0.01 to 2% of the total mass of the continuous mullite filaments.
In an embodiment of the present invention, in step c, the polymeric spinning aid is one or a combination of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol and carboxymethyl cellulose.
In one embodiment of the invention, in the step c, the addition amount of the polymeric spinning aid is 2-8% of the total mass of the continuous mullite filament.
In one embodiment of the invention, in the step c, the constant-temperature stirring is performed at a temperature of 25-60 ℃ for 0.5-2 hours; the conditions of heating, stirring and condensing reflux are as follows: the temperature is 50-90 ℃, and the time is 1-4 h; the reduced pressure distillation refers to the temperature condition of 30-80 ℃ and the vacuum degree of-0.1-0.04 MPa.
In one embodiment of the present invention, in the first step c, the spinnable mullite precursor sol D has a viscosity of 20 to 150Pa · s. The method for measuring the viscosity referred to in the present invention is "4-rotation method" in the standard "GB/T10247-2008 viscosity test method".
In one embodiment of the invention, in the second step, the vacuum defoaming refers to that the vacuum degree condition is-0.1 to-0.04 MPa, and the defoaming time is 1 to 3 hours;
in one embodiment of the present invention, in the second step, the dry spinning forming conditions are as follows: the temperature condition of the spinning assembly is 20-50 ℃, the relative humidity is 10-70%, the pump supply is 30-100 ml/min, the number of spinneret holes is 500-2000, the diameter of the spinneret hole is 0.05-0.2 mm, the temperature of the spinning channel is 80-150 ℃, and the winding speed is 50-400 m/min.
In one embodiment of the present invention, in the second step, the drying is performed under conditions of an ambient humidity of 30 to 80%, a drying temperature of 50 to 100 ℃, and a drying time of 3 to 8 hours.
In one embodiment of the present invention, in the second step, the high-temperature calcination treatment is: the temperature is raised to a first target temperature at the rate of 0.5-2 ℃/min, and the temperature is kept for 10-60 min, wherein the first target temperature is 150-400 ℃; then heating to a second target temperature at the heating rate of 2-8 ℃/min, and preserving the heat for 10-60 min, wherein the second target temperature is 400-800 ℃; finally, the temperature is increased to a third target temperature at the heating rate of 10 ℃/min, and the third target temperature is 1000-1600 ℃.
The invention is described in detail below with reference to the figures and the specific embodiments. In the technical scheme, characteristics such as preparation means, materials, structures or composition ratios and the like which are not explicitly described are all regarded as common technical characteristics disclosed in the prior art.
Example 1
The first step is as follows: preparation of spinnable mullite precursor sol
a. Adding aluminum nitrate nonahydrate, ethyl orthosilicate and aluminum isopropoxide into deionized water, and stirring for 6 hours at the temperature of 30 ℃ to obtain clear and transparent mullite precursor sol A;
b. adding aluminum nitrate nonahydrate and aluminum isopropoxide into deionized water, and stirring for 6 hours at the temperature of 30 ℃ to obtain translucent alumina precursor sol B;
c. mixing the mullite precursor sol A and the alumina precursor sol B, stirring for 0.5h at the temperature of 30 ℃, adding magnesium nitrate and polyvinyl alcohol, condensing, refluxing and stirring for 1.5h at the temperature of 60 ℃, and obtaining clear and transparent composite sol C; concentrating under the conditions of vacuum degree of-0.07 MPa and temperature of 50 ℃ to obtain spinnable mullite precursor sol D with the viscosity of 35Pa s. Wherein, in the step a, the molar ratio of aluminum nitrate nonahydrate, aluminum isopropoxide, ethyl orthosilicate and deionized water is 1.5; in the step b, the molar ratio of aluminum nitrate nonahydrate to aluminum isopropoxide to deionized water is 1; in the step c, the mass ratio of the mullite precursor sol A to the alumina precursor sol B is 18.72; the addition amount of the magnesium nitrate is 0.1 percent of the total mass of the continuous mullite filament, and the addition amount of the polyvinyl alcohol is 4 percent of the total mass of the continuous mullite filament.
The second step: preparation of continuous mullite filaments
Adding the spinnable precursor sol into a liquid storage tank of a dry spinning machine, defoaming for 3 hours under the condition that the vacuum degree is-0.098 MPa, and preparing hybrid continuous filaments through dry spinning forming; drying the hybrid continuous filament for 4 hours under the conditions that the ambient humidity is 50% and the temperature is 70 ℃, then enabling the temperature rise rate of a muffle furnace to reach 200 ℃ at the speed of 0.5 ℃/min, and preserving the temperature for 20min; then the temperature rises to 700 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 20min; finally, the temperature is raised to 1200 ℃ at a heating rate of 10 ℃/min, and the continuous mullite filament with the diameter of 10-50 um, high strength and good flexibility is obtained. Wherein, the parameters of the dry spinning are as follows: the temperature of the assembly is 35 ℃, the relative humidity is 40%, the number of spinneret holes is 600, the diameter of the spinneret hole is 0.12, the pump supply is 25ml/min, the temperature of the spinning shaft is 90 ℃, and the winding speed is 100m/min.
Fig. 1 is an SEM image of continuous mullite filaments prepared in this example 1; FIG. 2 is an XRD pattern of continuous mullite filaments made in example 1; FIG. 3 is a force-elongation plot of continuous mullite filaments made in this example 1; as can be seen from the figure, the continuous mullite filament prepared in this example has a smooth surface, 37nm mullite grains, an average elongation of 4.5%, and an average strength of 1.71GPa.
Example 2
The first step is as follows: preparation of spinnable mullite precursor sol
a. Adding aluminum chloride hexahydrate, tetra-n-propoxysilane and aluminum sec-butoxide into deionized water, and stirring at 40 deg.C for 8h to obtain clear and transparent mullite precursor sol A;
b. adding aluminum nitrate and aluminum isopropoxide into deionized water, and stirring for 8 hours at 40 ℃ to obtain a translucent alumina precursor sol B;
c. mixing the mullite precursor sol A and the alumina precursor sol B, stirring for 0.5h at 40 ℃, adding magnesium nitrate and polyvinylpyrrolidone powder, condensing, refluxing and stirring for 2h at 50 ℃ to obtain clear and transparent composite sol C; concentrating under the conditions of vacuum degree of minus 0.08MPa and temperature of 60 ℃ to obtain spinnable mullite precursor sol D with viscosity of 50Pa s. Wherein, in the step a, the molar ratio of aluminum chloride hexahydrate, aluminum sec-butoxide, tetra-n-propoxysilane and deionized water is 1; in the step b, the molar ratio of aluminum chloride hexahydrate, aluminum sec-butoxide and deionized water is 1; in the step c, the mass ratio of the mullite precursor sol A to the alumina precursor sol B is 32.07; the adding amount of the magnesium nitrate is 1 percent of the total mass of the continuous mullite filaments, and the adding amount of the polyvinyl alcohol is 7 percent of the total mass of the continuous mullite filaments.
The second step is that: preparation of continuous mullite filaments
Adding the spinnable precursor sol into a liquid storage tank of a dry spinning machine, defoaming for 2.5 hours under the condition that the vacuum degree is-0.098 MPa, and preparing hybrid continuous filaments through dry spinning forming; drying the hybrid continuous filament for 5h under the conditions that the ambient humidity is 40% and the temperature is 60 ℃, then enabling the temperature of the muffle furnace to reach 200 ℃ at the heating rate of 1 ℃/min, and preserving the heat for 30min; then, the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 30min; finally, the temperature is raised to 1400 ℃ at the heating rate of 10 ℃/min, and the continuous mullite filament with the diameter of 10-50 um, high strength and good flexibility is obtained. Wherein, the parameters of the dry spinning are as follows: the temperature of the assembly is 40 ℃, the relative humidity is 50%, the number of spinneret holes is 800, the diameter of the spinneret hole is 0.15, the pump supply is 35ml/min, the temperature of the spinning shaft is 95 ℃, and the winding speed is 150m/min.
The continuous mullite filament prepared by the embodiment has smooth surface, 45nm mullite grains, average elongation rate of 3.8 percent and average strength of 1.83GPa.
Example 3
The first step is as follows: preparation of spinnable mullite precursor sol
a. Adding aluminum nitrate nonahydrate, trimethylsilyl acetate and n-butyl aluminum alkoxide into deionized water, and stirring for 7 hours at the temperature of 55 ℃ to obtain clear and transparent mullite precursor sol A;
b. adding aluminum nitrate nonahydrate and aluminum n-butoxide into deionized water, and stirring for 7h at 55 ℃ to obtain translucent alumina precursor sol B;
c. mixing the mullite precursor sol A and the alumina precursor sol B, stirring for 0.5h at the temperature of 55 ℃, adding copper chloride and polyethylene oxide, condensing, refluxing and stirring for 3h at the temperature of 55 ℃, and obtaining clear and transparent composite sol C; concentrating under the conditions of vacuum degree of-0.065 MPa and temperature of 75 ℃ to obtain spinnable mullite precursor sol D with viscosity of 70Pa s. Wherein the molar ratio of the aluminum nitrate nonahydrate to the aluminum n-butoxide to the trimethylsilyl acetate to the deionized water in the step a is 1.8; in the step b, the molar ratio of aluminum nitrate nonahydrate to aluminum n-butoxide to deionized water is 1; in the step c, the mass ratio of the mullite precursor sol A to the alumina precursor sol B is 11.61; the addition amount of the magnesium nitrate is 0.05 percent of the total mass of the continuous mullite filaments, and the addition amount of the polyvinyl alcohol is 8 percent of the total mass of the continuous mullite filaments.
The second step: preparation of continuous mullite filaments
Adding the spinnable precursor sol into a liquid storage tank of a dry spinning machine, defoaming for 1.5 hours under the condition that the vacuum degree is-0.98 MPa, and preparing continuous precursor filaments through dry spinning forming; drying the hybrid continuous filament for 6 hours under the conditions that the environmental humidity is 60 percent and the temperature is 80 ℃, then enabling the temperature rise rate of a muffle furnace to reach 300 ℃ at the speed of 0.5 ℃/min, and preserving the temperature for 40min; then the temperature rises to 900 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 30min; finally, the temperature is increased to 1300 ℃ at the heating rate of 10 ℃/min, and the continuous mullite filament with the diameter of 10-60 um, high strength and good flexibility is obtained. Wherein, the parameters of the dry spinning are as follows: the temperature of the assembly was 45 ℃, the relative humidity was 60%, the number of spinneret holes was 500, the diameter of the spinneret hole was 0.15, the pump supply was 30ml/min, the temperature of the spinning shaft was 100 ℃, and the winding speed was 120m/min.
The continuous mullite filament prepared by the embodiment has smooth surface, 40nm mullite grains, average elongation of 4.12 percent and average strength of 1.76GPa.
Comparative example 1
CN104086200 discloses a preparation method of mullite fiber, which takes anhydrous aluminum chloride and aluminum powder as aluminum sources, ethyl orthosilicate as silicon sources, glacial acetic acid as a colloid stabilizer and a spinning auxiliary agent, and adopts a sol-gel method and a centrifugal spinning method process to prepare the mullite fiber; the spinnable mullite precursor sol is successfully prepared in the patent, but the preparation method has high danger of using concentrated nitric acid, is not suitable for large-scale industrial production of mullite fiber, and the prepared mullite short fiber cannot be used for spinning and three-dimensional weaving.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of flexible continuous mullite filaments is characterized by comprising the following steps:
s1: preparation of spinnable mullite precursor sol
a. Adding ionizable aluminum salt, aluminum alkoxide and silicon alkoxide into deionized water, and stirring at constant temperature to obtain clear and transparent mullite precursor sol A;
b. adding ionizable aluminum salt and aluminum alkoxide into deionized water, and stirring at constant temperature to obtain translucent alumina precursor sol B;
c. mixing the mullite precursor sol A and the alumina precursor sol B, stirring at a constant temperature, adding an additive and a high-molecular spinning auxiliary agent, heating, stirring and condensing for reflux to obtain a clear and transparent composite sol C; carrying out reduced pressure distillation on the clear and transparent composite sol C to obtain a spinnable mullite precursor sol D;
s2: preparation of continuous mullite filaments
And (3) performing vacuum deaeration on the spinnable mullite precursor sol D, preparing the hybridized mullite continuous filament by using dry spinning forming, and drying and sintering the hybridized mullite continuous filament at high temperature to obtain the continuous mullite filament.
2. The method of claim 1, wherein in a and b of S1, the ionizable aluminum salt is one or more of aluminum nitrate nonahydrate, aluminum chloride hexahydrate and aluminum sulfate octadecahydrate;
the alkoxide of the aluminum is one or a combination of more of aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, aluminum triethoxide and aluminum tri-n-propoxide;
the silicon alkoxide is one or a combination of more of tetra-n-propoxysilane, trimethylsilyl acetate, tetra-n-butoxysilane, and tetraethyl orthosilicate.
3. The method for preparing the flexible continuous mullite filament of claim 1, wherein the feeding proportion in the step a of S1 meets the requirement of M (Aluminium salts + aluminium alkoxides) /M Deionized water (10-40) and satisfies M Ionizable aluminium salts /M Alkoxides of aluminium ＝1:(2～6)，M Alkoxides of silicon /M Alkoxides of aluminium ＝1:(1.5～3.5)。
4. The method for preparing a flexible continuous mullite filament in accordance with claim 1, wherein in b of S1, the feeding ratio satisfies M (Alkylated aluminium salt + aluminium alkoxide) /M Deionized water (5-20) and satisfies M Ionizable aluminium salts /M Alkoxides of aluminium ＝1:(2～6)。
5. The method for preparing a flexible continuous mullite filament in accordance with claim 1, wherein in c of S1, the feeding ratio satisfies m (mullite precursor sol A) /m (alumina precursor Sol B) And (5-40) 1, wherein the mass of the alumina accounts for 1-10% of that of the mullite.
6. The method for preparing the flexible continuous mullite filament according to claim 1, wherein in the step c of S1, the additive is one or more of magnesium chloride, copper chloride, ferric chloride, magnesium nitrate and ferric nitrate;
the addition amount of the additive is 0.01-2% of the total mass of the continuous mullite filament.
7. The method for preparing a flexible continuous mullite filament according to claim 1, wherein in c of S1, the polymeric spinning assistant is one or more of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol and carboxymethyl cellulose;
the addition amount of the high molecular spinning auxiliary agent is 2-8% of the total mass of the continuous mullite filament.
8. The method for preparing the flexible continuous mullite filament according to claim 1, wherein in the a and b of S1, the constant temperature stirring conditions are as follows: the temperature is 25-60 ℃, and the constant-temperature stirring time is 4-12 h;
in the step c of S1, the constant-temperature stirring conditions are as follows: the temperature is 25-60 ℃, and the constant-temperature stirring time is 0.5-2 h;
the conditions of heating, stirring and condensing reflux are as follows: the temperature is 50-90 ℃ and the time is 1-4 h;
the conditions of reduced pressure distillation were: the temperature is 30-80 ℃, the vacuum degree is-0.1 to-0.04 MPa;
after reduced pressure distillation, the viscosity of the spinnable mullite precursor sol is 20-150 Pa.s.
9. The method for preparing a flexible continuous mullite filament according to claim 1 wherein in S2, the vacuum deaeration condition is as follows: the vacuum degree is-0.1 to-0.04 MPa, and the defoaming time is 1 to 4 hours;
the dry spinning forming conditions are as follows: the temperature condition of the spinning assembly is 20-50 ℃, the relative humidity is 10-70%, the pump supply is 30-100 ml/min, the number of spinneret holes is 500-2000, the diameter of the spinneret hole is 0.05-0.2 mm, the temperature of the spinning channel is 80-150 ℃, and the winding speed is 50-400 m/min.
10. The method for preparing a flexible continuous mullite filament according to claim 1 wherein in S2 the drying conditions are: the environment humidity is 30-80%, the drying temperature is 50-100 ℃, and the drying time is 3-8 h;
the high-temperature calcination treatment comprises the following steps: the temperature is raised to a first target temperature at the rate of 0.5-2 ℃/min, and the temperature is kept for 10-60 min, wherein the first target temperature is 150-400 ℃; then heating to a second target temperature at the heating rate of 2-8 ℃/min, and preserving the heat for 10-60 min, wherein the second target temperature is 400-800 ℃; finally, the temperature is increased to a third target temperature at the heating rate of 10 ℃/min, and the third target temperature is 1000-1600 ℃.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0416506A (en) * | 1990-05-07 | 1992-01-21 | Natl Inst For Res In Inorg Mater | Production of mullite fiber or membranous material |
| WO2008138554A1 (en) * | 2007-05-15 | 2008-11-20 | Clariant Finance (Bvi) Limited | Spinning mass for producing aluminum oxide and mullite fibers |
| CN101717257A (en) * | 2009-12-01 | 2010-06-02 | 西安交通大学 | Technology of preparing aluminium oxide based continuous fibers by sol-gel process |
| CN102786305A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Method for preparing continuous zirconium boride ceramic precursor fiber |
| CN104073918A (en) * | 2014-07-01 | 2014-10-01 | 华东理工大学 | Method for synthesizing polycrystalline mullite fibers under low temperature condition |
| CN104086200A (en) * | 2014-07-22 | 2014-10-08 | 南京理工大学 | Preparation method of mullite fiber |
| CN104357944A (en) * | 2014-11-06 | 2015-02-18 | 东华大学 | Method for preparing polyimide fiber through dry spinning |
| JP2017179619A (en) * | 2016-03-28 | 2017-10-05 | 株式会社ニチビ | Alumina-based oxide continuous fiber and manufacturing method therefor |
| CN107473749A (en) * | 2017-08-30 | 2017-12-15 | 成都理工大学 | A kind of mullite complex phase fiber and preparation method thereof |
| CN109851336A (en) * | 2019-01-23 | 2019-06-07 | 中南大学 | A kind of fine and close continuously mullite nano ceramic fibre and preparation method thereof of high-modulus |
| CN110078482A (en) * | 2019-05-21 | 2019-08-02 | 山东大学 | A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre |
| CN110282963A (en) * | 2019-04-17 | 2019-09-27 | 山东东珩胶体材料有限公司 | A kind of high tenacity iron content mullite flexible fiber and preparation method thereof |
| CN110846741A (en) * | 2019-10-09 | 2020-02-28 | 清华大学 | Flexible mullite fiber aerogel material and preparation method thereof |
| CN113716575A (en) * | 2020-11-26 | 2021-11-30 | 山东工业陶瓷研究设计院有限公司 | Preparation method of spinnable mullite sol |
| CN114162844A (en) * | 2021-12-07 | 2022-03-11 | 中南大学 | Precursor composite sol for alumina/mullite dual-phase fiber and preparation method thereof |
| CN114230341A (en) * | 2021-11-19 | 2022-03-25 | 东华大学 | Flexible high-entropy ceramic nanofiber and polymer-free template preparation method thereof |
| CN114232136A (en) * | 2021-11-19 | 2022-03-25 | 东华大学 | Preparation method of flexible ceramic nanofiber without adding polymer template |
-
2022
- 2022-06-27 CN CN202210735437.4A patent/CN115259845A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0416506A (en) * | 1990-05-07 | 1992-01-21 | Natl Inst For Res In Inorg Mater | Production of mullite fiber or membranous material |
| WO2008138554A1 (en) * | 2007-05-15 | 2008-11-20 | Clariant Finance (Bvi) Limited | Spinning mass for producing aluminum oxide and mullite fibers |
| CN101717257A (en) * | 2009-12-01 | 2010-06-02 | 西安交通大学 | Technology of preparing aluminium oxide based continuous fibers by sol-gel process |
| CN102786305A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Method for preparing continuous zirconium boride ceramic precursor fiber |
| CN104073918A (en) * | 2014-07-01 | 2014-10-01 | 华东理工大学 | Method for synthesizing polycrystalline mullite fibers under low temperature condition |
| CN104086200A (en) * | 2014-07-22 | 2014-10-08 | 南京理工大学 | Preparation method of mullite fiber |
| CN104357944A (en) * | 2014-11-06 | 2015-02-18 | 东华大学 | Method for preparing polyimide fiber through dry spinning |
| JP2017179619A (en) * | 2016-03-28 | 2017-10-05 | 株式会社ニチビ | Alumina-based oxide continuous fiber and manufacturing method therefor |
| CN107473749A (en) * | 2017-08-30 | 2017-12-15 | 成都理工大学 | A kind of mullite complex phase fiber and preparation method thereof |
| CN109851336A (en) * | 2019-01-23 | 2019-06-07 | 中南大学 | A kind of fine and close continuously mullite nano ceramic fibre and preparation method thereof of high-modulus |
| CN110282963A (en) * | 2019-04-17 | 2019-09-27 | 山东东珩胶体材料有限公司 | A kind of high tenacity iron content mullite flexible fiber and preparation method thereof |
| CN110078482A (en) * | 2019-05-21 | 2019-08-02 | 山东大学 | A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre |
| CN110846741A (en) * | 2019-10-09 | 2020-02-28 | 清华大学 | Flexible mullite fiber aerogel material and preparation method thereof |
| CN113716575A (en) * | 2020-11-26 | 2021-11-30 | 山东工业陶瓷研究设计院有限公司 | Preparation method of spinnable mullite sol |
| CN114230341A (en) * | 2021-11-19 | 2022-03-25 | 东华大学 | Flexible high-entropy ceramic nanofiber and polymer-free template preparation method thereof |
| CN114232136A (en) * | 2021-11-19 | 2022-03-25 | 东华大学 | Preparation method of flexible ceramic nanofiber without adding polymer template |
| CN114162844A (en) * | 2021-12-07 | 2022-03-11 | 中南大学 | Precursor composite sol for alumina/mullite dual-phase fiber and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| XIAOTA CHENG 等: "Direct synthesis of highly stretchable ceramic nanofibrous aerogels via 3D reaction electrospinning", 《NATURE COMMUNICATION》 * |
| 王德刚等: "水分散体系溶胶――凝胶法制备莫来石凝胶纤维的研究", 《东华大学学报(自然科学版)》 * |
| 马小玲等: "PVA作纺丝助剂制备莫来石-氧化铝长纤维", 《无机盐工业》 * |
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