CN106609404B - A kind of low density and high performance aluminium oxide base ceramic fibre and preparation method thereof - Google Patents
A kind of low density and high performance aluminium oxide base ceramic fibre and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of low density and high performance aluminium oxide base ceramic fibre.This method prepares spinnable alumina based fibre precursor sol using sol-gel method using raw materials such as inorganic aluminate, aluminum subacetate, boron-containing additive, silicon-containing additives；By dry spinning, alumina-based continuous fiber element silk is obtained, plain silk is dried, is sintered, alumina based continuous ceramic fibers are obtained.Colloidal sol stability of fiber prepared by the present invention is good, and preparation process is simple, can be at silk without adding pluronic polymer；Fibre density after firing is low, intensity is high, can be used for the high-tech areas such as aerospace.
Description
Technical field
The present invention relates to a kind of preparation methods of low density and high performance aluminium oxide base ceramic fibre, belong to inorfil technology
Field.
Background technique
Aluminium oxide base ceramic fibre is a kind of development situation of high-performance inorganic fibers being concerned in recent years, and outstanding advantages are that have
It is excellent physics, chemical property, such as low croop property, low-density, low thermal coefficient, good tensile strength, anticorrosive
And antioxygenic property, high temperature resistant etc., compared with the non-oxidized substances fiber such as silicon carbide, carbon fiber, oxidation resistent susceptibility is more preferable, Ke Yi
It is higher to keep good mechanical strength at use temperature, it is widely used in the high-tech areas such as space flight and aviation.
Aluminium oxide base ceramic fibre is with Al2O3Monocrystalline or polycrystalline fibre as main component, sometimes containing a certain amount of
Additive, such as SiO2、B2O3、Y2O3Deng.Although high purity aluminium oxide fiber high mechanical strength, its more crisp, easy fracture is appropriate to add
Sintering temperature can be reduced, improve tenacity of fibre by entering one or more additives as the second phase, and addition excessively will affect instead
Fibre property.A certain amount of B2O3Addition can improve the flexibility and the low-fiber density of drop of fiber to a certain extent, from
And so that fiber is become lighter and be easy to weave.For example, low (the ginseng of other kinds of fibers containing its density ratio of boron fibre that 3M corporation is standby
See: Ceramic Industry, 1995,144 (4): 45-50.).Zhang etc. is using aluminium chlorohydrate as silicon source, nanometer titanium dioxide
For Si powder as the second phase, PVA is spin finish aid, first prepares Aluminum sol, obtains alumina-based ceramic fibre by dry spinning
Dimension, with the addition of nano grade silica particles, fibre diameter and hole take the lead in increasing after reducing, and sintering temperature is 1250 DEG C
When, fiber surface is smooth, complete, and uniform diameter (referring to: Journal of the European Ceramic
Society.2014,34,465)。
The preparation method of aluminium oxide base ceramic fibre mainly has fusion method, slurry process, foretells inside door method and sol-gel method
Deng.Fusion method, slurry process foretell the methods of inside door method because it is high with preparation process temperature, water soluble organic substance high score must be added
The features such as son is to control spinning viscosity, gained staple fiber are in the majority.Sol-gel method in its simple process, preparation process because reacting
Easily controllable, mild condition (reaction temperature is lower than 100 DEG C, and sintering temperature is 400-500 DEG C lower than slurry process), presoma mixing are molten
Liquid up to molecular level, Fiber Uniformity obtained is good, designability is strong, product diversification etc., it has also become prepare alumina base
The main method of continuous ceramic fiber.For Tan etc. using nine water aluminum nitrates as silicon source, tartaric acid, PVP are auxiliary agent, pass through sol-gel
Method prepares aluminium oxide continuous ceramic fiber, and diameter is about 9-10 μm (referring to International Journal of
Minerals,Metallurgy and Materials.2011,18,691).Venkatesh etc. is combined with sol-gel method and is got rid of
The alumina fibre of silk technology preparation, wherein SiO2Content about 4%, intensity and flexibility are all preferable, but the shorter (ginseng of fiber
See: Ceram.Int.1999,25,539).
As can be seen that the preparation method of current alumina based fibre comes with some shortcomings from numerous research reports: first is that
It joined macromolecule spin finish aid in Aluminum sol preparation process mostly, pluronic polymer becomes bubble evolution, fiber after firing
Compactness is deteriorated, strength reduction；Second is that the aluminium oxide base ceramic fibre of industrialization is staple fiber, technique production master at home at present
If high-temperature fusion gets rid of a technology, is also in for the research of sol-gel technology combination dry spinning technology the exploratory stage.
Summary of the invention
It is an object of the invention to overcome deficiency existing for current alumina based fibre technology of preparing, a kind of low-density is provided
The preparation method of high-performance aluminium oxide base ceramic fibre.A kind of sol-gel technology combination dry spinning that the present invention is developed
The method that technology prepares low density and high performance aluminium oxide base ceramic fibre.Compared with pervious report, the present invention is high without being added
Molecule spin finish aid can obtain the precursor sol of performance stabilization, good spinnability；The alumina base obtained by dry spinning
Ceramic fibre compactness is good, density is small, tensile strength is high.
A kind of low density and high performance aluminium oxide base ceramic fibre of the present invention, density 2.6-2.67g/cm3, tensile strength
More than or equal to 1.4Gpa, preferably 1.4-1.65Gpa, further preferably 1.65GPa.
Preferably, a kind of low density and high performance aluminium oxide base ceramic fibre of the present invention, a diameter of 6-18 μm, excellent
6~10 μm are selected, elasticity modulus 145-150GPa.
Preferably, a kind of low density and high performance aluminium oxide base ceramic fibre of the present invention has by percentage to the quality
Following groups are grouped as: Al2O362%, SiO224%, B2O314%.
Preferably, a kind of low density and high performance aluminium oxide base ceramic fibre of the present invention, forms the particle of the fiber
Average grain diameter be 30-45nm, preferably 30-40nm.
A kind of preparation method of low density and high performance aluminium oxide base ceramic fibre of the present invention；Include the following steps:
Step 1: the preparation of Aluminum sol
In molar ratio, water-soluble inorganic aluminium salt: aluminum subacetate=1:1~20, boron-containing additive: aluminum subacetate=(0.01
~0.1): 1, aluminum subacetate: water=0.01~0.09:1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；It will match and take
Inorganic aluminate, aluminum subacetate, boron-containing additive, water be uniformly mixed, obtain Aluminum sol；
Step 2: the preparation of precursor sol can be spun
Silicon-containing additive is added into step 1 gained Aluminum sol, the additional amount of silicon-containing additive is with SiO2Content account for into
The 5~40% of the quality of product fiber are calculated, and deaeration is concentrated under the conditions of 40-100 DEG C after evenly mixing, obtain spinnable oxygen
Change aluminium base precursor sol；
Step 3: dry spinning
Spinnable alumina base precursor sol obtained by step 2 is put into the reservoir with spray head, using dry spinning
Technology obtains alumina based fibre element silk；
Step 4: dry, sintering
The cellulose silk that step 3 is obtained is dried in air or in insulating box, then with the speed of 0.5~6 DEG C/min
From room temperature to 550~650 DEG C, and in 0.5~2h of this temperature, then with the speed of 5~15 DEG C/min from 550~650
850~1200 DEG C of firings DEG C are warming up to, 10min~4h is kept the temperature, obtain alumina-based continuous fiber.
Preferably, a kind of preparation method of low density and high performance aluminium oxide base ceramic fibre of the present invention；In step 1, aluminium
The pH value of colloidal sol is 3~4.5.
Preferably, a kind of preparation method of low density and high performance aluminium oxide base ceramic fibre of the present invention；In step 1, institute
It is deionized water with water.
Preferably, a kind of preparation method of low density and high performance aluminium oxide base ceramic fibre of the present invention；In molar ratio, water
Insoluble inorganic aluminium salt: aluminum subacetate=1:1~20, boron-containing additive: aluminum subacetate=(0.01~0.1): 1, aluminum subacetate: water
=0.01~0.09:1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；Will with take inorganic aluminate, aluminum subacetate,
Boron-containing additive, water continuously stir 3~48h under the conditions of 25~100 DEG C, are uniformly mixed, obtain Aluminum sol.
Preferably, the molar ratio of aluminum subacetate and inorganic aluminate is 4~10, wherein aluminum subacetate and water in step 1
Molar ratio is 0.04~0.07, and the molar ratio of boron-containing additive and aluminum subacetate is (0.01~0.1): 1.
Preferably, inorganic aluminate is selected from aluminium chloride, aluminum nitrate, aluminum sulfate in step 1.
Preferably, in step 2 silicon-containing additive in ethyl orthosilicate, silica solution, water-soluble silicon oil, silane extremely
Few one kind.
It preferably, dry the cellulose silk that step 3 obtains at room temperature in air in step 4, or in temperature is 30
It is dry in~60 DEG C of insulating box.
Preferably, with the speed of 1~5 DEG C/min from room temperature to 600 DEG C in step 4, and in this temperature 1h.
Preferably, being warming up to 900~1100 DEG C of firings in step 4 from 600 DEG C with the speed of 8~10 DEG C/min, keep the temperature
2h。
A kind of sol-gel technology combination dry spinning technology that is based on of the invention prepares low density and high performance alumina base pottery
The method of porcelain fiber；It is silicon source using inorganic aluminate, aluminum subacetate, and a small amount of boron-containing additive, silicon-containing additive is added, and water is made
For solvent, gelatinous fibre element silk is obtained by sol-gel technology combination dry spinning technology, finally passes through drying, be sintered
To continuous aluminium oxide base ceramic fibre.
The present invention is compared to the prior art compared with having the advantages that
1, use inorganic aluminate and aluminum subacetate for silicon source, it is pollution-free.The present invention is helped without adding other macromolecule spinning
Agent can obtain the good colloidal sol of spinnability；Colloidal sol performance is stablized, and pH value is 3~4.5, can store for a long time.
2, simple process, easy to operate using dry spinning technology.The performances such as the viscosity according to colloidal sol, it is suitable to can choose
Orifice diameter, and adjust the conditions such as pressure, collecting drum revolving speed, path temperature.
3, the firing of cellulose silk uses following steps: with the speed of 0.5~6 DEG C/min from room temperature to 550~650
DEG C, and water, organic matter, acid in this temperature 30min~4h, cellulose silk etc. slowly volatilizees, and keeps cellulose silk uniform
It shrinks, avoids the volatilization such as moisture content and organic matter too fast and form hole, to influence the compactness of fiber；Again with 5~15 DEG C/
The speed of min is warming up to 850~1200 DEG C from 550~650 DEG C, in this temperature 10min~4h, turns amorphous alumina
Crystalline state is turned to, soaking time appropriate keeps fiber finer and close, finally obtains alumina based continuous ceramic fibers.
Detailed description of the invention
Fig. 1 is the magnification at high multiple SEM photograph of 3 gained aluminium oxide base ceramic fibre of embodiment；
Fig. 2 is the magnification at high multiple SEM photograph of 3 gained aluminium oxide base ceramic fibre fracture of embodiment；
Fig. 3 is the magnification at high multiple SEM photograph on 3 gained aluminium oxide base ceramic fibre surface of embodiment；
As can be seen from Figure 1 fiber whole smooth zero defect.
As can be seen from Figure 2 fiber fracture densification zero defect.
As can be seen from Figure 3 fiber surface densification zero defect.
Specific embodiment
With reference to the accompanying drawings and detailed description, the present invention is further illustrated.
Embodiment 1
(1) 28.14g Al (NO the preparation of colloidal sol: is added in 90.00g deionized water3)·9H2O is dissolved as transparent molten
42.20g CH is added in liquid3COOAl(OH)2·1/3H3BO3, 25.04g silicon is added until transparent in stirring under mixed solution room temperature
Colloidal sol, mixed solution is in 45 DEG C of water-bath agings.
(2) dry spinning: the colloidal sol that step (1) is obtained utilizes air spinning machine spinning, obtains alumina fibre element silk.
Dry-spinning process condition: spinneret pressure 520KPa, spinneret hole diameter 0.07mm, 30 DEG C of path air themperature, collecting drum
Linear velocity is 18m/min.
(3) cellulose silk is burnt into: with the speed of 2 DEG C/min from room temperature to 600 DEG C, and in this temperature 1h, then
1000 DEG C are warming up to from 600 DEG C with the speed of 10 DEG C/min, in this temperature 30min, it is fine to obtain the continuous ceramics of alumina base
Dimension.
Using the colloidal sol of above method preparation without adding spin finish aid, ropiness is good, stablizes, and the resting period is long.Institute
The diameter for obtaining alumina based continuous ceramic fibers is 6-18 μm, density 2.62g/cm3, tensile strength 1.45GPa, springform
Amount is 147GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%, forms the particle of the fiber
Average grain diameter is about 38nm.Fibre diameter is measured by SEM, and tensile strength and elasticity modulus are surveyed by monofilament strength tester
It is fixed.
Embodiment 2
(1) 11.35g AlCl the preparation of colloidal sol: is added in 90.00g deionized water3·6H2O is dissolved as clear solution,
42.20g CH is added3COOAl(OH)2·1/3H3BO3, it is molten that 25.04g silicon is added until transparent in stirring under mixed solution room temperature
Glue, mixed solution is in 45 DEG C of water-bath agings.
It is identical in step (2) embodiment 1.
(3) cellulose silk is burnt into: with the speed of 15 DEG C/min from room temperature to 600 DEG C, and in this temperature 1h, then
1000 DEG C are warming up to from 600 DEG C with the speed of 10 DEG C/min, in this temperature 2h, obtains alumina based continuous ceramic fibers.
The diameter of gained alumina based continuous ceramic fibers is 6-15 μm, density 2.6g/cm3, tensile strength is
1.4GPa, elasticity modulus 145GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%, composition
The average grain diameter of the particle of the fiber is about 32nm.Fibre diameter is measured by SEM, and tensile strength and elasticity modulus pass through single fiber
Tie up strength tester measurement.
Embodiment 3
As described in Example 1, except that: Al (NO3)·9H2O additional amount is 15.00g, and 42.20g is added
CH3COOAl(OH)2·1/3H3BO3, silica solution additional amount is 22.70g, the other the same as in Example 1.
The diameter of gained alumina based continuous ceramic fibers is 6-15 μm, density 2.67g/cm3, tensile strength is
1.65GPa, elasticity modulus 150GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%, composition
The average grain diameter of the particle of the fiber is about 35nm.Fibre diameter is measured by SEM, and tensile strength and elasticity modulus pass through single fiber
Tie up strength tester measurement.
Comparative example 1
Other conditions are completely the same with embodiment 3, only difference is that only with 127.6g Al (NO3)·
9H2O；The diameter of gained alumina based continuous ceramic fibers is 7-20 μm, density 2.32g/cm3, tensile strength 0.2GPa,
Elasticity modulus is 26GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%.Pass through 1 He of comparative example
For embodiment 1 as can be seen that the present invention is since raw material is chosen properly, the performance of products obtained therefrom is significantly larger than production obtained by comparative example 1
The performance of product.
Comparative example 2
Other conditions are completely the same with embodiment 3, only difference is that only with 47.8g CH3COOAl
(OH)2·1/3H3BO3；The diameter of gained alumina based continuous ceramic fibers is 7-18 μm, density 2.52g/cm3, stretch strong
Degree is 1.0GPa, elasticity modulus 112GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%.
By comparative example 1,2 and embodiment 1 as can be seen that the present invention is since raw material is chosen properly, the performance of products obtained therefrom is much high
In comparative example 1, the performance of 2 products obtained therefroms.
Comparative example 3
Other conditions are completely the same with embodiment 3, only difference is that only with 114.8g Al (NO3)·
9H2O、4.78g CH3COOAl(OH)2·1/3H3BO3；The diameter of gained alumina based continuous ceramic fibers is 8-17 μm, density
For 2.40g/cm3, tensile strength 0.5GPa, elasticity modulus 68GPa, wherein Al2O3Content is 62%, SiO2Content is
24%, B2O3Content is 14%.By comparative example 1, comparative example 2, comparative example 3 and embodiment 3 as can be seen that the present invention is due to original
It is suitable that material is chosen, and the performance of products obtained therefrom is significantly larger than the performance of 1,2,3 products obtained therefrom of comparative example.The effect also well beyond
It is estimated before experiment.
Comparative example 4
Other conditions are completely the same with embodiment 3, the difference is that substituting CH using aluminium isopropoxide3COOAl
(OH)2·1/3H3BO3, while the boric acid of equivalent is added to make up the boron content lacked in aluminum subacetate, gained alumina base connects
The diameter of continuous ceramic fibre is 7-16 μm, density 2.45g/cm3, tensile strength 0.7GPa, elasticity modulus 82GPa,
Middle Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%.By comparative example 1, comparative example 2, comparative example 3, right
As can be seen that the present invention is since raw material is chosen properly, the performance of products obtained therefrom is significantly larger than comparative example for ratio 4 and embodiment 3
1, the performance of 2,3,4 products obtained therefroms.The effect is also well beyond estimated before experiment.Also illustrate not all have simultaneously
Machine silicon source is suitable for the present invention.
Claims (9)
1. a kind of low density and high performance aluminium oxide base ceramic fibre, it is characterised in that: the low density and high performance alumina base pottery
The density of porcelain fiber is 2.6-2.67 g/cm3, tensile strength is more than or equal to 1.4GPa；
The low density and high performance aluminium oxide base ceramic fibre, is prepared by following step:
Step 1: the preparation of Aluminum sol
In molar ratio, water-soluble inorganic aluminium salt: aluminum subacetate=1:1 ~ 20, boron-containing additive: aluminum subacetate=1/3:1, secondary acetic acid
Aluminium: water=0.01 ~ 0.09:1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；It will be with inorganic aluminate, the secondary acetic acid taken
Aluminium, boron-containing additive, water are uniformly mixed, and obtain Aluminum sol；
Step 2: the preparation of precursor sol can be spun
Silicon-containing additive is added into step 1 gained Aluminum sol, the additional amount of silicon-containing additive is with SiO2Content account for finished fiber
Quality 5 ~ 40% calculated, deaeration is concentrated under the conditions of 40-100 DEG C after evenly mixing, before obtaining spinnable alumina base
Drive body colloidal sol；
Step 3: dry spinning
Spinnable alumina base precursor sol obtained by step 2 is put into the reservoir with spray head, using dry spinning technology
Obtain alumina based fibre element silk；
Step 4: dry, sintering
The cellulose silk that step 3 is obtained is dry in air or in insulating box, then with the speed of 0.5 ~ 6 DEG C/min from room temperature
550 ~ 650 DEG C are warming up to, and keeps the temperature 0.5 ~ 2h, then be warming up to 850 ~ 1200 DEG C from 550 ~ 650 DEG C with the speed of 5 ~ 15 DEG C/min
Firing keeps the temperature 10min ~ 4h, obtains alumina-based continuous fiber.
2. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1, it is characterised in that: described low close
The diameter for spending high-performance aluminium oxide base ceramic fibre is 6-18 μm, elasticity modulus is 145-150 GPa.
3. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 2, it is characterised in that: described low close
It spends high-performance aluminium oxide base ceramic fibre by percentage to the quality, is grouped as by following groups: Al2O362%, SiO224%, B2O3
14%。
4. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 2, it is characterised in that: form the fibre
The average grain diameter of the particle of dimension is 30-45nm.
5. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1；It is characterized by: in step 1,
The pH value of Aluminum sol is 3 ~ 4.5.
6. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1；It is characterized by: in step 1,
In molar ratio, water-soluble inorganic aluminium salt: aluminum subacetate=1:1 ~ 20, boron-containing additive: aluminum subacetate=1/3:1, aluminum subacetate: water
=0.01 ~ 0.09:1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；The inorganic aluminate taken will be matched, aluminum subacetate, contained
Boron additive, water continuously stir 3 ~ 48h under the conditions of 25 ~ 100 DEG C, are uniformly mixed, obtain Aluminum sol.
7. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1；It is characterized by: in step 1,
The molar ratio of aluminum subacetate and inorganic aluminate is 4 ~ 10 in step 1, and wherein the molar ratio of aluminum subacetate and water is 0.04 ~ 0.07,
The molar ratio of boron-containing additive and aluminum subacetate is 1/3:1.
8. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1；It is characterized by:
Inorganic aluminate is selected from least one of aluminium chloride, aluminum nitrate, aluminum sulfate in step 1；
Silicon-containing additive is selected from least one of ethyl orthosilicate, silica solution, water-soluble silicon oil, silane in step 2；
In step 4, the cellulose silk that step 3 obtains is dried at room temperature in air, or the insulating box for being 30 ~ 60 DEG C in temperature
Middle drying.
9. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1；It is characterized by:
With the speed of 1 ~ 5 DEG C/min from room temperature to 600 DEG C in step 4, and keep the temperature 1h；
It is warming up to 900 ~ 1100 DEG C of firings in step 4 from 600 DEG C with the speed of 8 ~ 10 DEG C/min, keeps the temperature 2h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611236450.6A CN106609404B (en) | 2016-12-28 | 2016-12-28 | A kind of low density and high performance aluminium oxide base ceramic fibre and preparation method thereof |
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| CN201611236450.6A CN106609404B (en) | 2016-12-28 | 2016-12-28 | A kind of low density and high performance aluminium oxide base ceramic fibre and preparation method thereof |
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| CN107653518B (en) * | 2017-09-27 | 2020-02-14 | 中南大学 | High-orientation-degree continuous superfine/nano alumina-based ceramic fiber bundle material and preparation method thereof |
| CN107955998B (en) * | 2017-11-23 | 2020-02-18 | 中南大学 | Light high-flexibility mullite superfine/nano ceramic fiber and preparation method thereof |
| CN108395216A (en) * | 2018-04-10 | 2018-08-14 | 中南大学 | A kind of ceramics and its preparation method and application with mullite structure |
| CN108760492B (en) * | 2018-05-18 | 2021-02-23 | 中国建材检验认证集团淄博有限公司 | Method for detecting room-temperature tensile property of continuous fiber reinforced ceramic matrix composite |
| CN108956323B (en) * | 2018-05-18 | 2021-02-23 | 中国建材检验认证集团淄博有限公司 | Method for detecting room-temperature bending strength of continuous fiber reinforced ceramic matrix composite |
| CN109719829B (en) * | 2019-01-23 | 2021-09-17 | 宁波多维时空智能设备有限公司 | Method for manufacturing ceramic by using three-dimensional printing technology |
| CN110078486A (en) * | 2019-04-29 | 2019-08-02 | 江苏辉迈粉体科技有限公司 | A kind of preparation method of quartz fibre |
| CN110078482A (en) * | 2019-05-21 | 2019-08-02 | 山东大学 | A kind of α-Al2O3The preparation method of/mullite Multiphase ceramic fibre |
| CN112435718B (en) * | 2020-10-28 | 2022-04-22 | 中南大学 | Method for predicting spinnability of alumina fiber precursor sol based on density functional theory |
| CN113061041A (en) * | 2021-03-24 | 2021-07-02 | 江苏奥尼韦尔自动化科技有限公司 | Preparation method of aluminum silicate ceramic fiber precursor gel |
| CN113896551B (en) * | 2021-11-25 | 2022-09-30 | 福建师范大学泉港石化研究院 | Preparation method of alkaline earth metal reinforced continuous aluminum silicate ceramic fiber |
| CN114685149B (en) * | 2022-04-02 | 2023-05-26 | 深圳大学 | Functionalized alumina ceramic fiber and preparation method thereof |
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