CN108085786A - Mullite Ceramic Fibres cotton and preparation method thereof - Google Patents
Mullite Ceramic Fibres cotton and preparation method thereof Download PDFInfo
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- CN108085786A CN108085786A CN201711376816.4A CN201711376816A CN108085786A CN 108085786 A CN108085786 A CN 108085786A CN 201711376816 A CN201711376816 A CN 201711376816A CN 108085786 A CN108085786 A CN 108085786A
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- mullite
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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 135
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 135
- 229920000742 Cotton Polymers 0.000 title claims abstract description 61
- 239000000919 ceramic Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000009987 spinning Methods 0.000 claims abstract description 117
- 239000000835 fiber Substances 0.000 claims abstract description 116
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005336 cracking Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims description 58
- 239000002994 raw material Substances 0.000 claims description 55
- 238000007664 blowing Methods 0.000 claims description 24
- 239000003570 air Substances 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 210000002268 wool Anatomy 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 241000219146 Gossypium Species 0.000 abstract 4
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 208000012886 Vertigo Diseases 0.000 description 88
- 239000012752 auxiliary agent Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- 239000012700 ceramic precursor Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- MJWPFSQVORELDX-UHFFFAOYSA-K aluminium formate Chemical compound [Al+3].[O-]C=O.[O-]C=O.[O-]C=O MJWPFSQVORELDX-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
Abstract
The present invention relates to a kind of Mullite Ceramic Fibres cottons and preparation method thereof, the preparation method first passes through high temperature bunching and mullite precursor is prepared as mullite spinning material, then cellucotton precursor is prepared into fibre by centrifugal drying silk or injection, further by curing, cracking, the techniques such as being sintered and prepare Mullite Ceramic Fibres cotton.The mullite spinning material softening point and rheological characteristic being prepared are adjustable, and cost is relatively low, solvent-free, environmentally protective in subsequent spinning operations, and cellucotton precursor is insensitive to humidity in air, convenient for large-scale production.And preparation-obtained Mullite Ceramic Fibres cotton flexibility is splendid, mechanical behavior under high temperature is excellent, and can be widely used in the fields such as vehicle exhaust insulation blanket, high temperature filtration core carrier, Industrial Stoves heat-preservation cotton.
Description
Technical Field
The invention relates to mullite ceramic cellucotton and a preparation method thereof.
Background
The ceramic fiber with 100% alumina content has increased grain size under the environment condition of temperature higher than 1200 ℃, thereby causing the strength and mechanical property of the fiber to be reduced, and causing adverse effect on the fiber. By introducing Zr, Si and other foreign elements into the spinning raw material, the grain size growth of the alumina at high temperature can be inhibited, thereby improving the high temperature resistance of the fiber. The mullite cellucotton is Al2O3：SiO2The high-performance inorganic fiber with the mass ratio of about 72:28 is characterized by high strength, high modulus and excellent mechanical property under the air atmosphere at the temperature of more than 1200 ℃,meanwhile, the thermal conductivity is small, the thermal expansion coefficient is low, the thermal shock resistance is good, and the like.
The mullite fiber cotton has great market prospect in the fields of aerospace and civil high-end materials as a high-temperature heat-insulating material. The heat insulation tile of the space shuttle, the heat insulation shell of the combustion chamber of the solid engine, the spray pipe of the supersonic jet aircraft, the gasket of the rocket engine, the heat insulation of the nuclear reactor, the thermal structural connecting piece between the spray pipe and the combustion chamber of the solid engine and the relevant parts of the spray pipe outlet cone all use a great deal of mullite fiber.
The mullite has high melting point and low viscosity after melting, and can not be produced by the traditional melting and wire drawing process. Therefore, researchers in various countries develop a plurality of different production routes in turn by adopting a chemical method, and the sol-gel method is a method which is commonly adopted in the preparation and production process of the mullite fiber at present.
For example, the preparation method of the alumina ceramic fiber disclosed in the chinese patent CN 104005115 a mainly comprises the following steps: the method comprises the steps of preparing spinnable precursor sol by using alumina sol and silica sol containing Al13 colloidal particles, preparing gel fiber by adopting a blowing fiber forming process, and performing heat treatment to obtain the mullite ceramic fiber with the diameter of 1-7 um. However, the cellocotton raw silk is sensitive to the humidity of the spinning environment, is easy to adhere and doubling, even is pasty, leads to raw silk scrapping, and has poor stability of a spinning system.
Chinese patent CN 102465358A discloses a preparation method of polycrystalline mullite, which mainly comprises the steps of adding sodium-removed acidic silica sol into an aluminum formate and aluminum acetate sol solution, adding a spinning auxiliary agent and a surfactant, forming fibers by a blowing or spinning process to obtain cellucotton precursor fibers, and carrying out heat treatment on the cellucotton precursor fibers at 1500 ℃ to finally prepare mullite fibers. The process is sensitive to temperature and humidity, the spinning auxiliary is adopted, the cost is increased, and a large amount of volume shrinkage is easily generated in the process of removing the spinning auxiliary through later-stage heat treatment, so that the fiber strength is influenced.
Chinese patent CN 200510012723 discloses a preparation method of polycrystalline mullite, which mainly comprises the steps of preparing sol by hydrochloric acid, aluminum powder and silica sol, forming fibers by a filament throwing process to obtain cellucotton protofilaments, and performing high-temperature heat treatment on the cellucotton protofilaments to finally prepare mullite fibers. The process is sensitive to temperature and humidity, and the fibers are easy to be adhered and doubled in the spinning stage and even are pasty. However, the working idea of preparing the mullite fiber in the above work has reference significance.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
The invention aims to provide mullite ceramic cellucotton and a preparation method thereof, wherein a spinning system in the preparation method of the mullite ceramic cellucotton is stable, protofilaments of the cellucotton are insensitive to the humidity of a spinning environment, and the raw materials of the method do not contain a spinning auxiliary agent, so that the adverse effects of fiber volume shrinkage and mechanical property loss caused by leaving of the spinning auxiliary agent at high temperature are avoided.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of mullite ceramic cellucotton comprises the following steps:
s1, providing a mullite precursor, and performing high-temperature polycondensation on the mullite precursor to obtain a mullite spinning raw material;
s2, obtaining fiber cotton protofilament by the mullite spinning raw material through a spinning process, and then solidifying and cracking the fiber cotton protofilament to obtain a fiber cotton fabric;
and S3, sintering and ultrahigh-temperature treating the cracked fiber cotton fabric to obtain the mullite ceramic fiber cotton.
Further, in step S1, reduced pressure distillation is simultaneously carried out during the high temperature polycondensation, and the temperature is 150-220 ℃.
Further, the softening point of the mullite spinning raw material is 70-125 ℃.
Further, in step S2, the spinning process includes centrifugal spinning, and the specific steps of the centrifugal spinning include:
and placing the mullite spinning raw material in a centrifugal spinning machine, heating the mullite spinning raw material in a nitrogen atmosphere, and after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, throwing the melt out of a spinning hole of the centrifugal spinning machine at a high speed to obtain the cellucotton precursor.
Further, the conditions of the centrifugal spinning comprise: the temperature of the heating is 110-180 ℃, the rotating speed of the centrifugal throwing machine is 4000-20000r/min, and the aperture of a throwing disc of the centrifugal throwing machine is 0.1-0.5 mm.
Further, in step S1, the spinning process includes blowing fiber formation, and the specific steps of blowing fiber formation include:
and placing the mullite spinning raw material into blowing equipment, heating until the mullite spinning raw material is completely melted, and blowing the mullite spinning raw material into fibers in the blowing equipment to obtain the cellucotton protofilaments.
Further, the blowing fiberization conditions include: the temperature is 110-200 ℃ and the air pressure is
0.05-0.6MPa, 0.05-0.15MPa hydraulic pressure, and 20-70 degree included angle between the direction of spinning liquid and the direction of air flow.
Further, in step S2, the curing specifically includes:
and (2) placing the raw fiber cotton in a constant temperature and humidity box, heating to 30-40 ℃, preserving heat for 20min-2h at a relative humidity of 30-45%, heating to 60-95 ℃, preserving heat for 10min-2h at a humidity of 60-95%, and cooling to room temperature to obtain the solidified fiber cotton fabric.
Further, in step S2, the specific steps of cracking include:
and (3) placing the cured cellucotton fabric in a high-temperature furnace, heating to 500-800 ℃ at the speed of 0.5-30 ℃/min, and preserving the heat in a cracking atmosphere for 30min-2h for cracking.
Further, the gas for forming the cracking atmosphere includes one or more of nitrogen, argon, helium, and air.
Further, in step S3, the sintering specifically includes:
heating the cracked fiber cotton fabric to 1000-1800 ℃ at a heating rate of 0.15-100 ℃/min in air atmosphere, and sintering for 1min-10 h.
Further, in step S3, the specific steps of the ultra-high temperature treatment include:
and carrying out ultrahigh-temperature treatment on the sintered fiber cotton fabric in a combustible atmosphere by using gas flame generated by a burner to obtain the mullite ceramic fiber cotton.
Further, the gas for forming the combustible atmosphere includes one or more gases of ethylene, propane, acetylene, and coal gas.
In order to achieve the aim, the invention also provides the mullite ceramic fiber cotton prepared by the preparation method of the mullite ceramic fiber cotton.
The invention has the beneficial effects that:
(1) the mullite ceramic fiber cotton is prepared by high-temperature polycondensation of a mullite precursor, and the mullite spinning raw material is used as the mullite spinning raw material, so that the mullite ceramic fiber cotton is low in price, and the softening point and the rheological property of the mullite ceramic fiber cotton are adjustable. Meanwhile, the mullite spinning raw material adopted by the invention does not contain a spinning auxiliary agent, so that the adverse effects of fiber volume shrinkage and mechanical property loss caused by the leaving of the spinning auxiliary agent at high temperature are avoided.
(2) The preparation method of the mullite ceramic cellucotton adopts a centrifugal spinning or blowing fiber forming process to prepare the cellucotton precursor, the spinning process system is stable, the cellucotton precursor is insensitive to the humidity of the spinning environment, and the problem that the cellucotton precursor prepared by a solution spinning process is easily adhered, silked and even pasty is solved. Meanwhile, the diameter of the prepared mullite ceramic fiber cotton is 0.5-3 mu m, the grain size is less than 50nm, the Al and Si elements in the mullite ceramic fiber cotton are uniformly distributed in a molecular level, and the stability and spinnability of the mullite spinning raw material are excellent.
(3) The whole process is green and environment-friendly, large-scale production can be rapidly realized, and the finally prepared mullite ceramic fiber cotton has excellent flexibility and high-temperature mechanical property.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a flow chart of the mullite ceramic cellucotton preparation method of the present invention;
FIG. 2 is an SEM image of mullite ceramic fiber wool in accordance with one embodiment of the present invention;
fig. 3 is an XRD pattern of mullite ceramic cellucotton in accordance with the first embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Referring to fig. 1, the preparation method of mullite ceramic cellucotton disclosed by the invention comprises the following steps:
s1, providing a mullite precursor, performing high-temperature polycondensation on the mullite precursor at 150-220 ℃ to obtain a mullite spinning raw material, and performing reduced pressure distillation simultaneously in the high-temperature polycondensation process;
s2, placing the mullite spinning raw material into a centrifugal spinning machine, wherein the aperture diameter of a spinning disc of the centrifugal spinning machine is preferably 0.1-0.5mm, heating the mullite spinning raw material to a preferred temperature of 110-180 ℃ in a nitrogen atmosphere, and after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, spinning the melt out of a spinning hole of the centrifugal spinning machine at a preferred rotating speed of 4000-20000r/min at a high speed to obtain fiber cotton precursor;
or,
placing the mullite spinning raw material into blowing equipment, heating to the optimal temperature of 110-200 ℃, after the mullite spinning raw material is completely melted, blowing the mullite spinning raw material into fibers under the conditions that the air pressure is preferably 0.05-0.6MPa, the hydraulic pressure is preferably 0.05-0.15MPa, and the included angle between the flow direction of a spinning liquid and the direction of an air flow is preferably 20-70 degrees, so as to obtain fiber cotton protofilaments;
s3, placing the raw fiber cotton in a constant temperature and humidity box, heating to 30-40 ℃, preserving heat for 20min-2h at a relative humidity of 30-45%, heating to 60-95 ℃, preserving heat for 10min-2h at a humidity of 60-95%, and cooling to room temperature to obtain a solidified fiber cotton fabric;
s4, placing the cured fiber cotton fabric in a high temperature furnace, heating to 500-800 ℃ at a speed of 0.5-30 ℃/min, and preserving heat in a cracking atmosphere for 30min-2h for cracking, wherein the gas for forming the cracking atmosphere comprises one or more of nitrogen, argon, helium and air;
s5, heating the cracked fiber cotton fabric to 1000-1800 ℃ at a heating rate of 0.15-100 ℃/min in the air atmosphere, sintering for 1min-10h, and then carrying out ultrahigh temperature treatment to obtain the mullite ceramic fiber cotton.
Wherein, the structural formula of the mullite precursor is as follows:
and the softening point of the mullite spinning raw material prepared by the step S1 is 70-125 ℃.
The present invention will be described in further detail with reference to specific examples.
Example one
1. Preparing a mullite spinning raw material:
placing 500g of mullite precursor into a reaction kettle, heating to 80 ℃ under stirring, carrying out reduced pressure distillation for 1h, removing most of solvent, continuing to heat to 120 ℃, keeping the temperature for 1h, heating to 160 ℃, sampling every 10min, measuring the softening point, stopping heating when the softening point reaches 85 ℃, and cooling to room temperature under the protection of nitrogen to obtain the high molecular mullite spinning raw material with the softening point of 85 ℃.
2. Preparing mullite ceramic cellucotton:
s1, placing the prepared mullite spinning raw material into a three-neck bottle, heating to 130 ℃ under the protection of nitrogen, quickly and uniformly pouring the mullite spinning raw material into a spinning machine with the rotating speed of 3000r/min and the aperture of a spinning disc of 0.4mm after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, and spinning the molten spinning raw material out of the spinning hole at a high speed to obtain fiber cotton protofilaments;
s2, placing the raw fiber cotton yarn obtained in the S1 in a constant temperature and humidity box, heating to 40 ℃, preserving heat for 30min at 30% relative humidity, heating to 90 ℃, preserving heat for 20min at 80% humidity, and cooling to room temperature to obtain cured fiber;
s3, placing the solidified fiber obtained in the S2 in a high-temperature furnace, heating to 600 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1h, wherein the cracking atmosphere is air;
and S4, heating the cracked fiber cotton fabric obtained in the S3 to 1000 ℃ at the heating rate of 30 ℃/min, and treating for 20min, wherein the sintering atmosphere is air, so that the mullite ceramic fiber cotton can be obtained.
Referring to fig. 2 and fig. 3, SEM photographs and XRD spectra of the mullite ceramic fiber cotton prepared by the method are shown. As can be seen from the figure, the fiber has smooth surface and uniform size, and the diameter of the fiber is 0.5-3 μm; XRD result shows that the crystal phase composition of the fiber is t-ZrO2And the crystal size is less than 50 nm.
Example two
1. Preparing a mullite spinning raw material:
placing 500g of mullite precursor into a reaction kettle, heating to 80 ℃ under stirring, carrying out reduced pressure distillation for 1h, removing most of solvent, continuing to heat to 120 ℃, keeping the temperature for 1h, heating to 160 ℃, sampling every 10min, measuring the softening point, stopping heating when the softening point reaches 85 ℃, and cooling to room temperature under the protection of nitrogen to obtain the high molecular mullite spinning raw material with the softening point of 85 ℃.
2. Preparing mullite ceramic cellucotton:
s1, pouring the prepared mullite spinning raw material into a liquid pipe of a blowing spinning device, adjusting the temperature of the liquid pipe to 125 ℃, carrying out melt blowing at 125 ℃ after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, controlling the air pressure to be 0.45MPa and the hydraulic pressure to be 0.08MPa, keeping the liquid flow direction and the air flow direction to form an angle of about 60 degrees, and blowing precursor cellucotton precursor fibers, wherein the fiber length is about 15cm, the size is uniform, and the fibers are free of slag balls;
s2, placing the raw fiber cotton yarn obtained in the S1 in a constant temperature and humidity box, heating to 40 ℃, preserving heat for 20min at 30% relative humidity, heating to 90 ℃, preserving heat for 20min at 80% humidity, and cooling to room temperature to obtain cured fiber;
s3, placing the solidified fiber obtained in the S2 in a high-temperature furnace, heating to 600 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1h, wherein the cracking atmosphere is air;
and S4, heating the cracked fiber cotton fabric obtained in the S3 to 1400 ℃ at the heating rate of 30 ℃/min, and treating for 10min, wherein the sintering atmosphere is air, so that the yttrium-stabilized mullite ceramic fiber cotton with a white tetragonal crystal phase structure can be obtained, and the length of the yttrium-stabilized mullite ceramic fiber cotton is 10 cm.
EXAMPLE III
1. Preparing a mullite spinning raw material:
and (3) placing 500g of mullite ceramic precursor into a reaction kettle, heating to 180 ℃ under stirring, carrying out reduced pressure distillation, sampling every 10min, measuring the softening point, stopping heating when the softening point reaches 105 ℃, and cooling to room temperature under the protection of nitrogen to obtain the high-molecular solid mullite ceramic precursor.
2. Preparing mullite ceramic cellucotton:
s1, placing the prepared mullite spinning raw material into a three-neck bottle, heating to 150 ℃ under the protection of nitrogen, quickly and uniformly pouring the mullite spinning raw material into a spinning machine with the rotating speed of 5000r/min and the aperture of a spinning disc of 0.4mm after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, and spinning the molten spinning raw material out of the spinning hole at a high speed to obtain fiber cotton protofilaments;
s2, placing the raw fiber of the cellucotton obtained in the S1 in a constant temperature and humidity box, heating to 85 ℃, preserving heat for 10min at 90% humidity, and cooling to room temperature to obtain solidified fiber;
s3, placing the solidified fiber obtained in the S2 in a high-temperature furnace, heating to 600 ℃ at the speed of 5 ℃/min, and preserving heat for 1h, wherein the cracking atmosphere is air;
and S4, heating the cracked fiber obtained in the S3 to 1200 ℃ at the heating rate of 10 ℃/min, treating for 30min, and obtaining the white mullite ceramic cellucotton by taking the sintering atmosphere as air.
Example four
1. Preparing a mullite spinning raw material:
and (3) placing 500g of mullite ceramic precursor into a reaction kettle, heating to 180 ℃ under stirring, carrying out reduced pressure distillation, sampling every 10min, measuring the softening point, stopping heating when the softening point reaches 105 ℃, and cooling to room temperature under the protection of nitrogen to obtain the high-molecular solid mullite ceramic precursor.
2. Preparing mullite cellucotton:
s1, pouring the prepared mullite spinning raw material into a liquid pipe of a blowing spinning device, adjusting the temperature of the liquid pipe to 145 ℃, carrying out melt blowing at 145 ℃ after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, controlling the air pressure to be 0.56MPa and the hydraulic pressure to be 0.06MPa, keeping the liquid flow direction and the air flow direction to form an angle of about 55 degrees, and blowing precursor cellucotton precursor fibers, wherein the fibers are about 20cm in length, uniform in size and free of slag balls;
s2, placing the raw fiber cotton yarn obtained in the S1 in a constant temperature and humidity box, heating to 50 ℃, preserving heat for 1h at 30% relative humidity, heating to 90 ℃, preserving heat for 20min at 80% humidity, and cooling to room temperature to obtain cured fiber;
s3, placing the solidified fiber obtained in the S2 in a high-temperature furnace, heating to 600 ℃ at the speed of 2 ℃/min, and preserving heat for 2h, wherein the cracking atmosphere is air;
and S4, heating the cracked fiber obtained in the S3 to 1400 ℃ at the heating rate of 30 ℃/min, and treating for 10min, wherein the sintering atmosphere is air, and then the white mullite ceramic fiber cotton can be obtained.
In summary, the following steps: the mullite ceramic cellucotton preparation method provided by the invention has the advantages that the mullite spinning raw material is obtained by high-temperature polycondensation of the mullite precursor, the mullite spinning raw material is used as the spinning raw material, the price is low, and the softening point and the rheological property of the mullite spinning raw material are adjustable. Meanwhile, the mullite spinning raw material adopted by the invention does not contain spinning auxiliary agents and chloride ions, so that the manufacturing cost is reduced, the adverse effects of fiber volume shrinkage and mechanical property loss caused by the leaving of the spinning auxiliary agents at high temperature are avoided, and the whole process flow is green and environment-friendly and is friendly to experimenters and environment.
In addition, the preparation method of the mullite ceramic cellucotton adopts a centrifugal spinning or blowing fiber forming process to prepare the cellucotton precursor, the spinning process system is stable, the cellucotton precursor is insensitive to the humidity of the spinning environment, and the problem that the cellucotton precursor prepared by a solution spinning process is easily adhered, spun and even pasty is solved. Meanwhile, the diameter of the prepared mullite ceramic fiber cotton is 0.5-3 mu m, the grain size is less than 50nm, the Al and Si elements in the mullite ceramic fiber cotton are uniformly distributed in a molecular level, and the stability and spinnability of the mullite spinning raw material are excellent.
Meanwhile, the whole process is green and environment-friendly, large-scale production can be rapidly realized, and finally prepared mullite ceramic fiber cotton has excellent flexibility and high-temperature mechanical property, and can be widely applied to the fields of automobile exhaust heat insulation gaskets, high-temperature filter element carriers, industrial kiln heat insulation cotton and the like.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. The preparation method of the mullite ceramic cellucotton is characterized by comprising the following steps:
s1, providing a mullite precursor, and performing high-temperature polycondensation on the mullite precursor to obtain a mullite spinning raw material;
s2, obtaining fiber cotton protofilament by the mullite spinning raw material through a spinning process, and then solidifying and cracking the fiber cotton protofilament to obtain a fiber cotton fabric;
and S3, sintering and ultrahigh-temperature treating the cracked fiber cotton fabric to obtain the mullite ceramic fiber cotton.
2. The mullite ceramic fiber wool according to claim 1 wherein, in step S1, reduced pressure distillation is simultaneously performed during the high temperature polycondensation, and the temperature is 150 to 220 ℃.
3. The mullite ceramic fiber wool according to claim 1 wherein the mullite spin pack has a softening point in the range of 70 to 125 ℃.
4. The mullite ceramic fiber wool according to claim 1, wherein in step S2, the spinning process comprises centrifugal spinning, and the specific steps of the centrifugal spinning comprise:
and placing the mullite spinning raw material in a centrifugal spinning machine, heating the mullite spinning raw material in a nitrogen atmosphere, and after the mullite spinning raw material is melted into a uniform melt and residual bubbles are removed, throwing the melt out of a spinning hole of the centrifugal spinning machine at a high speed to obtain the cellucotton precursor.
5. The method for preparing mullite ceramic fiber cotton according to claim 4, wherein the conditions of centrifugal spinning comprise: the temperature of the heating is 110-180 ℃, the rotating speed of the centrifugal throwing machine is 4000-20000r/min, and the aperture of a throwing disc of the centrifugal throwing machine is 0.1-0.5 mm.
6. The method for preparing mullite ceramic fiber cotton according to claim 1, wherein in step S1, the spinning process comprises fiber blowing, and the specific steps of fiber blowing comprise:
and placing the mullite spinning raw material into blowing equipment, heating until the mullite spinning raw material is completely melted, and blowing the mullite spinning raw material into fibers in the blowing equipment to obtain the cellucotton protofilaments.
7. The method for preparing mullite ceramic fiber cotton as claimed in claim 6, wherein the blowing fiberizing conditions comprise: the temperature is 110-200 deg.C, the air pressure is 0.05-0.6MPa, the hydraulic pressure is 0.05-0.15MPa, and the angle between the spinning liquid direction and the air flow direction is 20-70 deg.
8. The method for preparing mullite ceramic fiber wool as claimed in claim 1, wherein in step S2, the concrete steps of curing include:
and (2) placing the raw fiber cotton in a constant temperature and humidity box, heating to 30-40 ℃, preserving heat for 20min-2h at a relative humidity of 30-45%, heating to 60-95 ℃, preserving heat for 10min-2h at a humidity of 60-95%, and cooling to room temperature to obtain the solidified fiber cotton fabric.
9. The method for preparing mullite ceramic fiber wool as claimed in claim 1, wherein in step S2, the cracking comprises the following specific steps:
and (3) placing the cured cellucotton fabric in a high-temperature furnace, heating to 500-800 ℃ at the speed of 0.5-30 ℃/min, and preserving the heat in a cracking atmosphere for 30min-2h for cracking.
10. The method according to claim 9, wherein the gas used to form the cracking atmosphere comprises one or more of nitrogen, argon, helium, and air.
11. The method for preparing mullite ceramic fiber wool as claimed in claim 1, wherein in step S3, the sintering comprises the following specific steps:
heating the cracked fiber cotton fabric to 1000-1800 ℃ at a heating rate of 0.15-100 ℃/min in air atmosphere, and sintering for 1min-10 h.
12. The method for preparing mullite ceramic fiber wool as claimed in claim 1, wherein in step S3, the specific steps of the ultrahigh temperature treatment include:
and carrying out ultrahigh-temperature treatment on the sintered fiber cotton fabric in a combustible atmosphere by using gas flame generated by a burner to obtain the mullite ceramic fiber cotton.
13. The method according to claim 12, wherein the gas for forming the combustible atmosphere comprises one or more gases selected from the group consisting of ethylene, propane, acetylene, and coal gas.
14. Mullite ceramic fiber wool produced by the method of producing mullite ceramic fiber wool according to any one of claims 1 to 13.
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