CN107904697A - The poly- aikyiaiurnirsoxan beta of solid-state, the preparation method of the poly- aikyiaiurnirsoxan beta of solid-state, alumina fibre cotton and preparation method thereof - Google Patents
The poly- aikyiaiurnirsoxan beta of solid-state, the preparation method of the poly- aikyiaiurnirsoxan beta of solid-state, alumina fibre cotton and preparation method thereof Download PDFInfo
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- 229920000742 Cotton Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 139
- 238000009987 spinning Methods 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000005336 cracking Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 67
- 239000002994 raw material Substances 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 39
- 239000012298 atmosphere Substances 0.000 claims description 30
- 239000003570 air Substances 0.000 claims description 28
- 238000007664 blowing Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003034 coal gas Substances 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 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 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 210000002268 wool Anatomy 0.000 claims 9
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract description 2
- 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
- 239000007788 liquid Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 239000006060 molten glass Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 210000003456 pulmonary alveoli Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
-
- 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
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Fibers (AREA)
Abstract
The present invention relates to a kind of poly- aikyiaiurnirsoxan beta of solid-state, the preparation method of the poly- aikyiaiurnirsoxan beta of solid-state, alumina fibre cotton and preparation method thereof, first pass through high temperature bunching and poly- aikyiaiurnirsoxan beta is prepared as the poly- aikyiaiurnirsoxan beta of solid-state, then cellucotton precursor is prepared into fibre by centrifugal drying silk or injection, further by curing, cracking, the technique such as sintering and prepare alumina fibre cotton.The poly- aikyiaiurnirsoxan beta softening point of solid-state and rheological characteristic being prepared are adjustable, and cost is relatively low, and solvent-free, environmentally protective in follow-up spinning operations, fiber precursor is insensitive to humidity in air, easy to large-scale production.And preparation-obtained alumina fibre cotton pliability 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 solid polyaluminoxane, a preparation method of the solid polyaluminoxane, alumina fiber cotton and a preparation method of the alumina fiber cotton.
Background
The alumina cellucotton is a high-performance inorganic fiber, has the outstanding characteristics of high strength, high modulus, excellent mechanical property in an air atmosphere at 1000-1200 ℃, and also has the advantages of small thermal conductivity, low thermal expansion coefficient, good thermal shock resistance and the like. Compared with non-oxide fibers such as carbon fibers and silicon carbide fibers, the alumina fibers have the advantages of high strength, heat resistance and high-temperature oxidation resistance, and maintain good tensile strength at higher temperature; and the material is easy to be compounded with metal and ceramic matrixes to form a plurality of composite materials with excellent performance and wide application.
The alumina fiber cotton has great market prospect in the fields of aerospace and civil high-end materials as a high-temperature heat-insulating material. Such as the insulating tiles of space shuttles, the insulating housings of solid engine combustors, the nozzles in supersonic jet aircraft, the gaskets in rocket motors, the thermal insulation of nuclear reactors, the thermal structural connections between the solid engine nozzles and combustors, and the nozzle exit cone related components, have largely used alumina fibers.
At present, the automobile exhaust heat insulation liner in the civil field is commonly made of high temperature resistant fibers such as glass fibers, aluminum silicate fibers, alumina ceramic fibers and the like. This is because the temperature of the exhaust gas is relatively high and is maintained at 600 ℃ to 800 ℃ for a long time. The glass fiber has the advantages of flame retardance, corrosion resistance, small volume weight, low heat conductivity coefficient, low moisture absorption rate and the like, so that the glass fiber is widely applied to the field. However, the glass fiber has poor high temperature resistance, poor flexibility, and hard and brittle texture, and is easy to break under the condition of continuous vibration, so that the sound insulation and heat insulation performance is affected, and the aluminum silicate fiber also has the defect. And the glass fiber is prepared by centrifugally blowing and forming fiber by using molten glass, and once the fiber generated in the preparation process is inoculated into alveolus, the risk of carcinogenesis is easily generated. The high temperature resistance of the alumina ceramic fiber is better than that of the aluminum silicate fiber and the glass fiber, and the flexibility of the alumina fiber can be improved by adjusting the crystallization condition of the fiber, so that the alumina ceramic fiber can be used for a long time without breaking in a continuous thermal shock environment. At present, no commercial chemical fiber cotton product suitable for the high-temperature heat-insulating liner of the automobile exhaust is available in China.
The alumina ceramic has high melting point and low viscosity after melting, and can not be produced by the traditional melting and wire drawing process. For this reason, researchers in various countries develop several different production routes successively by using chemical methods, wherein the precursor method is the main method for industrially preparing alumina continuous fibers. The method can be classified into an organic fiber impregnation method, an inorganic salt method, a sol-gel method, an organic polymer precursor method, a slurry solution method, and the like, according to the difference in the kind of the precursor raw material.
The sol-gel method is a method which is commonly adopted in the preparation and production process of the alumina fiber at present, and Chinese patent CN104005115A discloses a preparation method of alumina ceramic fiber, which mainly comprises the following steps: the spinnable precursor sol is prepared from alumina sol and silica sol containing Al13 colloidal particles, the gel fiber is prepared by adopting a blowing fiber-forming process, and the alumina ceramic fiber with the diameter of 1-7um is obtained by heat treatment. But the cellosilk is sensitive to the humidity of the spinning environment, is easy to be adhered and doubled, even is pasty, leads to the scrapping of the protofilament, and has poor stability of a spinning system.
The electrostatic spinning method is an effective technical approach for preparing the nano-fiber. Chinese patent CN101982581A discloses that aluminum oxide fiber with a diameter of hundred nanometers is prepared by taking aluminum acetylacetonate as an aluminum source and polyacrylonitrile or polyurethane as a spinning auxiliary agent and combining electrostatic spinning with 1200 ℃ high-temperature carbon thermal reduction. Chinese patent CN102167567A discloses a spinning raw material containing aluminum sol prepared by a sol-gel method, and finally prepares alumina fibers with good flexibility and different diameters of 400nm-800nm by an electrostatic spinning process and a two-stage sintering process. But the electrostatic spinning method has low preparation efficiency and higher cost, and is difficult to realize mass production.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
The invention aims to provide solid polyaluminoxane, a preparation method of the solid polyaluminoxane, alumina fiber cotton and a preparation method of the alumina fiber cotton.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing solid polyaluminoxane comprises the following steps:
providing polyaluminoxane, and performing high-temperature polycondensation on the polyaluminoxane to obtain the solid polyaluminoxane.
Further, in the high-temperature polycondensation process, the temperature is 150-220 ℃.
Further, reduced pressure distillation is simultaneously carried out in the high-temperature polycondensation process.
In order to achieve the purpose, the invention provides the following technical scheme: the solid polyaluminoxane prepared by the preparation method of the solid polyaluminoxane has a softening point of 50-125 ℃.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of alumina cellucotton comprises the following steps:
s1, providing a spinning raw material, wherein the spinning raw material comprises the solid polyaluminoxane according to claim 4, and performing a spinning process on the spinning raw material to obtain fiber cotton protofilaments;
s2, solidifying and cracking the cellucotton protofilament to obtain a cellucotton fabric;
and S3, sintering and ultrahigh-temperature treating the cracked fiber cotton fabric to obtain the alumina fiber cotton.
Further, in step S1, the spinning process includes centrifugal spinning, and the specific steps of the centrifugal spinning include:
and (2) placing the spinning raw material in a centrifugal spinning machine, heating in a nitrogen atmosphere, and after the 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 high speed to obtain the cellucotton precursor.
Further, the conditions of the centrifugal spinning comprise: the temperature of the temperature rise and heating is 110-180 ℃, the rotating speed of the centrifugal wire throwing machine is 4000-20000r/min, and the aperture of a wire throwing disc of the centrifugal wire 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 (3) placing the spinning raw material into blowing equipment, heating until the spinning raw material is completely melted, and blowing the spinning raw material into fibers in the blowing equipment to obtain the cellucotton precursor.
Further, the adjusting of blown fiber comprises: the air pressure is 0.05-0.6MPa, the hydraulic pressure is 0.05-0.15MPa, and the included angle between the direction of the spinning solution and the direction of the air flow is 20-70 degrees.
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 fiber cotton 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 the heating rate of 0.15-100 ℃/min in the 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 cellucotton fabric in a combustible atmosphere by using gas flame generated by a burner to obtain the alumina cellucotton.
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 above purpose, the present invention provides the following technical solutions: the alumina cellucotton prepared by the preparation method of the alumina cellucotton is provided.
The invention has the beneficial effects that:
(1) the solid polyaluminoxane is obtained by high-temperature polycondensation of polyaluminoxane, is used as a spinning raw material, is low in price, and has adjustable softening point and rheological property. Meanwhile, the spinning raw materials adopted by the invention do not contain spinning auxiliary agents, so that the adverse effects of fiber volume shrinkage and mechanical property loss caused by leaving of the spinning auxiliary agents at high temperature are avoided.
(2) The preparation method of the alumina cellucotton adopts a centrifugal spinning or blowing fiber forming process to prepare the cellucotton, the spinning process system is stable, the fibril is insensitive to the humidity of the spinning environment, and the problem that the fibril prepared by the solution spinning process is easy to adhere, silks and even pastes is solved.
(3) The whole process is green and environment-friendly, large-scale production can be rapidly realized, and finally prepared cellucotton samples are excellent in flexibility and high-temperature mechanical properties.
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 method for preparing alumina fiber cotton according to the present invention;
FIGS. 2a and 2b are SEM images of alumina fiber cotton according to one embodiment of the present invention;
FIG. 3 is an XRD pattern of alumina fiber cotton according to a first embodiment of the present invention;
FIG. 4 is an SEM photograph of alumina fiber cotton according to a sixth embodiment of the present invention;
FIG. 5 is an XRD pattern of alumina cellucotton according to the sixth 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.
The preparation method of the solid polyaluminoxane comprises the following steps:
providing polyaluminoxane, performing high-temperature polycondensation on the polyaluminoxane at the temperature of 150-220 ℃ to obtain the solid polyaluminoxane, and performing reduced pressure distillation simultaneously in the high-temperature polycondensation process.
The solid polyaluminoxane prepared by the preparation method of the solid polyaluminoxane has a softening point of 50-125 ℃ and a structural formula as follows:
referring to fig. 1, the method for preparing alumina fiber cotton of the present invention comprises the following steps:
s1, providing a spinning raw material, wherein the spinning raw material comprises the solid polyaluminoxane as defined in claim 4, placing the spinning raw material in a centrifugal spinning machine, heating to 110-;
or,
providing a spinning raw material, wherein the spinning raw material comprises the solid polyaluminoxane as defined in claim 4, placing the spinning raw material in a blowing device, heating to 110-200 ℃, and after the spinning raw material is completely melted, blowing the spinning raw material into fibers under the conditions that the air pressure is 0.05-0.6MPa, the hydraulic pressure is 0.05-0.15MPa and the included angle between the flow direction of a spinning solution and the direction of an air flow is 20-70 ℃ to obtain the fiber cotton protofilament.
S2, 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;
s3, placing the cured fiber cotton 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, wherein the gas for forming the cracking atmosphere comprises one or more of nitrogen, argon, helium and air;
s4, heating the cracked fiber cotton fabric to 1800 ℃ at a heating rate of 0.15-100 ℃/min in the air atmosphere, and sintering for 1min-10h to obtain the alumina fiber cotton.
And S5, 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 alumina fiber cotton, wherein the gas for forming the combustible atmosphere comprises one or more than one of ethylene, propane, acetylene and coal gas. The temperature, gas and apparatus of the ultra-high temperature treatment are selected based on the actual conditions.
The present invention will be described in further detail with reference to specific examples.
Example one
1. Preparation of solid polyaluminoxane:
putting 500g of Polyaluminoxane (PAO) into a reaction kettle, heating to 80 ℃ under stirring, carrying out reduced pressure distillation for 1h, continuously heating to 120 ℃, keeping the temperature for 1h, finally heating to 150 ℃, 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 solid polyaluminoxane;
2. preparing alumina cellucotton:
s1, placing the spinning raw materials in a three-neck bottle, heating to 130 ℃ under the protection of nitrogen, rapidly and uniformly pouring the spinning raw materials into a throwing machine with the rotating speed of 4000r/min and the aperture of a throwing disc of 0.4mm after the spinning raw materials are melted into a uniform melt and residual bubbles are removed, and throwing the molten spinning raw materials out of the throwing holes at a high speed to obtain fiber protofilaments;
s2, placing the alumina fiber precursor obtained in the step 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;
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;
and S5, performing ultrahigh temperature treatment on the sintered fiber obtained in the S4 for 5S by using propane gas flame generated by a 12cm burner. Thus obtaining the gamma-Al 2O3 ceramic fiber in the form of white cellucotton.
Referring to fig. 2a, fig. 2b and fig. 3, SEM photographs and XRD spectra of the alumina fiber cotton prepared according to the method for preparing alumina fiber cotton are shown. As can be seen from the figure, the fiber has smooth surface and uniform size, and the diameter of the fiber is 2-5 μm; XRD results show that the crystal phase composition of the fiber is gamma-Al 2O 3.
Example two
1. Preparation of solid polyaluminoxane:
and (2) placing 500g of PAO in a reaction kettle, heating to 80 ℃ under stirring, carrying out reduced pressure distillation for 1h, continuously heating to 120 ℃, carrying out heat preservation for 1h, finally heating to 150 ℃, sampling every 10min, measuring a softening point, stopping heating when the softening point reaches 85 ℃, and cooling to room temperature under the protection of nitrogen to obtain the solid polyaluminoxane.
2. Preparing alumina cellucotton:
s1, pouring a spinning raw material into a liquid pipe of a blowing spinning device, adjusting the temperature of the liquid pipe to 125 ℃, carrying out melting blowing at 125 ℃ after the liquid pipe 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 fiber precursors, wherein the fiber length is about 15cm, the size is uniform and no slag balls exist;
s2, placing the alumina fiber precursor obtained in the step 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;
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;
and S5, performing ultrahigh-temperature treatment on the sintered fibers obtained in the S4 for 5S by using propane gas flame generated by a 12cm burner to obtain white α -Al2O3 ceramic fiber cotton with the length of 10 cm.
EXAMPLE III
1. Preparation of solid polyaluminoxane:
500g Polyaluminoxane (PAO) is placed in a reaction kettle, heated to 180 ℃ under stirring, distilled under reduced pressure, sampled every 10min to measure the softening point, when the softening point reaches 105 ℃, the heating is stopped, and the temperature is reduced to room temperature under the protection of nitrogen to obtain the high molecular solid polyaluminoxane.
2. Preparing alumina cellucotton:
s1, placing the spinning raw materials in a three-neck bottle, heating to 150 ℃ under the protection of nitrogen, rapidly and uniformly pouring the spinning raw materials into a throwing machine with the rotating speed of 5000r/min and the aperture of a throwing disc of 0.4mm after the spinning raw materials are melted into a uniform melt and residual bubbles are removed, and throwing the molten spinning raw materials out of the throwing holes at a high speed to obtain fiber protofilaments;
s2, placing the alumina fiber precursor obtained in the step 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 cured 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;
s4, heating the cracked fiber obtained in the S3 to 1200 ℃ at a heating rate of 10 ℃/min, and treating for 30min, wherein the sintering atmosphere is air;
and S5, performing ultra-high temperature treatment on the sintered fibers obtained in the S4 for 5S by using propane gas flame generated by a 12cm burner to obtain white α -Al2O3 ceramic fiber cotton.
Example four
1. Preparation of solid polyaluminoxane:
500g Polyaluminoxane (PAO) is placed in a reaction kettle, heated to 180 ℃ under stirring, distilled under reduced pressure, sampled every 10min to measure the softening point, when the softening point reaches 105 ℃, the heating is stopped, and the temperature is reduced to room temperature under the protection of nitrogen to obtain the high molecular solid polyaluminoxane.
2. Preparing alumina cellucotton:
s1, pouring the spinning raw materials into a liquid pipe of a blowing spinning device, adjusting the temperature of the liquid pipe to 145 ℃, carrying out melting blowing at 145 ℃ after the liquid pipe 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 fiber precursors, wherein the fiber length is about 20cm, the size is uniform and no slag balls exist;
s2, placing the alumina fiber precursor obtained in the step 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;
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 S5, carrying out ultrahigh temperature treatment on the sintered fibers obtained in the S4 for 5S by using ethylene gas flame generated by a 12cm burner to obtain white α -Al2O3 ceramic fiber cotton with the length of 10 cm.
EXAMPLE five
1. Preparation of solid polyaluminoxane:
500g Polyaluminoxane (PAO) is placed in a reaction kettle, heated to 220 ℃ under stirring, decompressed and distilled for 30min, then the heating is stopped, and the nitrogen protective atmosphere is reduced to room temperature to obtain the high molecular solid polyaluminoxane with the softening point of 113 ℃.
2. Preparing alumina cellucotton:
s1, placing the spinning raw materials in a three-neck bottle, heating to 160 ℃ under the protection of nitrogen, rapidly and uniformly pouring the spinning raw materials into a spinning machine with the rotating speed of 7000r/min and the aperture of a spinning disc of 0.4mm after the spinning raw materials are melted into a uniform melt and residual bubbles are removed, and spinning the molten spinning raw materials out of the spinning holes at a high speed to obtain fiber protofilaments;
s2, placing the alumina fiber precursor obtained in the step 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 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;
s4, heating the cracked fiber obtained in the S3 to 1400 ℃ at the heating rate of 10 ℃/min, and treating for 20min, wherein the sintering atmosphere is air;
and S5, carrying out ultra-high temperature treatment on the sintered fibers obtained in the S4 for 5S by using ethylene gas flame generated by a 12cm burner to obtain white α -Al2O3 ceramic fiber cotton.
EXAMPLE six
1. Preparation of solid polyaluminoxane:
500g Polyaluminoxane (PAO) is placed in a reaction kettle, heated to 220 ℃ under stirring, decompressed and distilled for 30min, then the heating is stopped, and the nitrogen protective atmosphere is reduced to room temperature to obtain the high molecular solid polyaluminoxane with the softening point of 113 ℃.
2. Preparing alumina cellucotton:
s1, pouring the spinning raw materials into a liquid pipe of a blowing spinning device, adjusting the temperature of the liquid pipe to 165 ℃, carrying out melting blowing at 165 ℃ after the liquid pipe 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 35 degrees, and blowing precursor fiber precursors, wherein the fiber length is about 30cm, the size is uniform and no slag balls exist;
s2, placing the alumina fiber precursor obtained in the step 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 step S2 in a high-temperature furnace, heating to 700 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1h, wherein the cracking atmosphere is air;
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;
and S5, performing ultrahigh-temperature treatment on the sintered fibers obtained in the S4 for 5S by using ethylene gas flame generated by a 12cm burner to obtain white α -Al2O3 ceramic fiber cotton with the length of 15cm, wherein SEM pictures and XRD spectrograms of the obtained alumina fiber cotton are shown in figures 4 and 5.
In summary, the following steps: the solid polyaluminoxane is obtained by high-temperature polycondensation of polyaluminoxane, is used as a spinning raw material, is low in price, and has adjustable softening point and rheological property. Meanwhile, the spinning raw materials adopted by the invention do not contain spinning auxiliary agents, so that the adverse effects of fiber volume shrinkage and mechanical property loss caused by leaving of the spinning auxiliary agents at high temperature are avoided.
In addition, the preparation method of the alumina fiber cotton adopts the spinning and blowing fiber forming process to prepare the fiber cotton, the spinning process system is stable, the fiber protofilament is insensitive to the humidity of the spinning environment, and the problem that the fiber protofilament prepared by the solution spinning process is easy to adhere, silk and even paste is solved.
Meanwhile, the whole process is green and environment-friendly, large-scale production can be rapidly realized, and finally prepared cellucotton samples are excellent in flexibility and high-temperature mechanical properties.
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 (16)
1. A method for preparing solid polyaluminoxane is characterized by comprising the following steps:
providing polyaluminoxane, and performing high-temperature polycondensation on the polyaluminoxane to obtain the solid polyaluminoxane.
2. The method of claim 1, wherein the temperature during the high temperature polycondensation is 150-220 ℃.
3. The process for preparing polyaluminoxane according to claim 2, wherein vacuum distillation is simultaneously performed during the high-temperature polycondensation.
4. A solid polyaluminoxane prepared by the method for preparing a solid polyaluminoxane according to any one of claims 1 to 3, wherein the softening point of the solid polyaluminoxane is 50 to 125 ℃.
5. The preparation method of the alumina cellucotton is characterized by comprising the following steps:
s1, providing a spinning raw material, wherein the spinning raw material comprises the solid polyaluminoxane according to claim 4, and performing a spinning process on the spinning raw material to obtain fiber cotton protofilaments;
s2, solidifying and cracking the cellucotton protofilament to obtain a cellucotton fabric;
and S3, sintering and ultrahigh-temperature treating the cracked fiber cotton fabric to obtain the alumina fiber cotton.
6. The method for preparing alumina fiber wool according to claim 5, wherein in step S1, the spinning process comprises centrifugal spinning, and the specific steps of the centrifugal spinning comprise:
and (2) placing the spinning raw material in a centrifugal spinning machine, heating in a nitrogen atmosphere, and after the 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 high speed to obtain the cellucotton precursor.
7. The method for preparing alumina fiber wool according to claim 6, wherein the conditions of centrifugal spinning comprise: the temperature of the temperature rise and heating is 110-180 ℃, the rotating speed of the centrifugal wire throwing machine is 4000-20000r/min, and the aperture of a wire throwing disc of the centrifugal wire throwing machine is 0.1-0.5 mm.
8. The method for preparing alumina fiber wool according to claim 5, wherein in step S1, the spinning process comprises blowing fiber, and the specific steps of blowing fiber comprise:
and (3) placing the spinning raw material into blowing equipment, heating until the spinning raw material is completely melted, and blowing the spinning raw material into fibers in the blowing equipment to obtain the cellucotton precursor.
9. The method of producing alumina fiber wool according to claim 8, wherein the adjusting of the blown fibers comprises: the air pressure is 0.05-0.6MPa, the hydraulic pressure is 0.05-0.15MPa, and the included angle between the direction of the spinning solution and the direction of the air flow is 20-70 degrees.
10. The method for preparing alumina fiber wool according to claim 5, wherein in step S2, the concrete step of curing comprises:
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.
11. The method for preparing alumina fiber wool according to claim 5, wherein in step S2, the specific steps of the splitting include:
and (3) placing the cured fiber cotton 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.
12. The method of claim 11, wherein the gas for forming the cracking atmosphere comprises one or more of nitrogen, argon, helium, and air.
13. The method for preparing alumina fiber wool according to claim 5, wherein in step S3, the sintering comprises the following steps:
heating the cracked fiber cotton fabric to 1000-1800 ℃ at the heating rate of 0.15-100 ℃/min in the air atmosphere, and sintering for 1min-10 h.
14. The method for preparing alumina fiber wool according to claim 5, wherein in step S3, the specific steps of the ultra-high temperature treatment include:
and carrying out ultrahigh-temperature treatment on the sintered cellucotton fabric in a combustible atmosphere by using gas flame generated by a burner to obtain the alumina cellucotton.
15. The method of producing alumina fiber wool according to claim 14 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.
16. An alumina fiber cotton obtained by the method for preparing alumina fiber cotton according to any one of claims 5 to 15.
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