CN106609404A - Low-density high-performance alumina-based ceramic fiber and preparation method thereof - Google Patents
Low-density high-performance alumina-based ceramic fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method for a low-density high-performance alumina-based ceramic fiber. The method comprises the following steps: preparing spinnable alumina-based fiber precursor sol from an inorganic aluminum salt, a boron-containing additive, a silicone-containing additive and the like by using a sol-gel process; carrying out dry-process spinning so as to obtain alumina-based continuous green fibrous filaments; and subjecting the filaments to drying and sintering so as to obtain the alumina-based continuous ceramic fiber. The sol fiber prepared in the invention has good stability; preparation process is simple; the filaments can be formed without a high-molecular auxiliary agent; and the sintered fiber has low density and high strength and can be applied to high-tech fields like aviation and aerospace.
Description
Technical field
The present invention relates to a kind of preparation method of low density and high performance aluminium oxide base ceramic fibre, belongs to inorfil technology
Field.
Background technology
Aluminium oxide base ceramic fibre is a kind of development situation of high-performance inorganic fibers for receiving much concern in recent years, and its outstanding advantages is that have
It is excellent physics, chemical property, such as low croop property, low-density, low heat conductivity, good tensile strength, anticorrosive
And antioxygenic property, high temperature resistant etc., compared with the non-oxidized substance fiber such as carborundum, carbon fiber, oxidation resistent susceptibility is more preferable, Ke Yi
Good mechanical strength is kept at a temperature of higher use, is widely used in the high-tech areas such as space flight and aviation.
Aluminium oxide base ceramic fibre is with Al2O3For the monocrystalline or polycrystalline fibre of main component, sometimes containing a certain amount of
Additive, such as SiO2、B2O3、Y2O3Deng.It is appropriate to add although high purity aluminium oxide fibre machinery intensity is high, its more crisp, easy fracture
Entering one or more additive can reduce sintering temperature, improve tenacity of fibre as the second phase, and addition excessively can affect on the contrary
Fibre property.A certain amount of B2O3Addition can to a certain extent improve the pliability of fiber and drop low-fiber density, from
And fiber is become lighter and is easy to braiding.For example, the low (ginseng of standby other kinds of fibers containing its density ratio of boron fibre of 3M company systems
See：Ceramic Industry,1995,144(4):45-50.).Zhang etc. with aluminium chlorohydrate as silicon source, nanometer titanium dioxide
Used as the second phase, PVA is spin finish aid to Si powder, first prepares Alumina gel, obtains alumina-based ceramic by dry spinning fine
Dimension, with the addition of nano grade silica particles, fibre diameter and hole take the lead in being raised after reduction, and sintering temperature is 1250 DEG C
When, fiber surface is smooth, complete, 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 process etc..
Fusion method, slurry process, foretell the method such as inside door method and have that preparation process temperature is high because of it, water soluble organic substance macromolecule must be added with
The features such as control spinning viscosity, gained chopped fiber is in the majority.Sol-gel process is easy to because reacting in its process is simple, preparation process
Control, mild condition (reaction temperature be less than 100 DEG C, sintering temperature is lower than slurry process 400-500 DEG C), precursor mixed solution can
Up to molecular level, obtained Fiber Uniformity be good, designability is strong, product diversification etc., it has also become prepare alumina base continuous
The main method of ceramic fibre.With nine water aluminum nitrates as silicon source, tartaric acid, PVP are auxiliary agent to Tan etc., by sol-gel legal system
It is standby go out aluminium oxide continuous ceramic fiber, diameter be about 9-10 μm (referring to：International Journal of Minerals,
Metallurgy and Materials.2011,18,691).Venkatesh etc. is combined with sol-gel process and is got rid of a technology system
Standby alumina fibre, wherein SiO2Content about 4%, intensity and pliability it is all preferable, but fiber it is shorter (referring to：
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：One is
Add macromolecule spin finish aid in Alumina gel preparation process mostly, pluronic polymer becomes after firing bubble effusion, fiber
Compactness is deteriorated, intensity decreases；Two is that at present at home the aluminium oxide base ceramic fibre of industrialization is chopped fiber, technique productions master
If high-temperature fusion gets rid of a technology, for research of the sol-gel technology with reference to dry spinning technology is also in the exploratory stage.
The content of the invention
It is an object of the invention to overcome the shortcomings of that current alumina based fibre technology of preparing is present, there is provided a kind of low-density
The preparation method of high-performance aluminium oxide base ceramic fibre.A kind of sol-gel technology that the present invention is developed combines dry spinning
The method that technology prepares low density and high performance aluminium oxide base ceramic fibre.Compared with former report, the present invention is high without the need for adding
Molecule spin finish aid can just obtain the precursor sol of stable performance, good spinnability；The alumina base obtained by dry spinning
Ceramic fibre compactness is good, density is little, tensile strength is high.
A kind of low density and high performance aluminium oxide base ceramic fibre of the present invention, its density is 2.6-2.67g/cm3, tensile strength
More than or equal to 1.4Gpa, more preferably preferably 1.4-1.65Gpa, 1.65GPa.
Preferably, a kind of low density and high performance aluminium oxide base ceramic fibre of the invention, its a diameter of 6-18 μm, excellent
6～10 μm are selected, its elastic modelling quantity is 145-150GPa.
Preferably, a kind of low density and high performance aluminium oxide base ceramic fibre of the invention, by percentage to the quality, has
Following component compositions：Al2O362%, SiO224%, B2O314%.
Preferably, a kind of low density and high performance aluminium oxide base ceramic fibre of the invention, constitutes the granule of the fiber
Mean diameter be 30-45nm, be preferably 30-40nm.
A kind of preparation method of low density and high performance aluminium oxide base ceramic fibre of the present invention；Comprise the steps：
Step 1：The preparation of Alumina gel
In molar ratio, water-soluble inorganic aluminium salt：Aluminum subacetate=1：1～20, boron-containing additive：Aluminum subacetate=(0.01
～0.1)：1st, aluminum subacetate：Water=0.01～0.09：1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；Will be with taking
Inorganic aluminate, aluminum subacetate, boron-containing additive, water mix homogeneously, obtain Alumina gel；
Step 2：The preparation of precursor sol can be spun
Silicon-containing additive is added toward step 1 gained Alumina gel, the addition 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 uniform mixing, obtain spinnable oxygen
Change aluminium base precursor sol；
Step 3：Dry spinning
The spinnable alumina base precursor sol of step 2 gained is put in the reservoir with shower nozzle, using dry spinning
Technology obtains alumina based fibre element silk；
Step 4：It is dried, sinters
The cellulose silk that step 3 is obtained is dried in atmosphere or in calorstat, 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
DEG C being warming up to 850～1200 DEG C burns till, and is incubated 10min～4h, obtains alumina-based continuous fiber.
Preferably, a kind of preparation method of low density and high performance aluminium oxide base ceramic fibre of the invention；In step 1, aluminum
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 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 invention；In molar ratio, water
Insoluble inorganic aluminium salt：Aluminum subacetate=1：1～20, boron-containing additive：Aluminum subacetate=(0.01～0.1)：1st, aluminum subacetate：Water
=0.01～0.09：1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；By with take inorganic aluminate, aluminum subacetate,
Boron-containing additive, water 3～48h of continuous stirring, mix homogeneously under the conditions of 25～100 DEG C, obtain Alumina gel.
Preferably, aluminum subacetate and the mol ratio of inorganic aluminate are 4～10, wherein aluminum subacetate and water in step 1
Mol ratio is 0.04～0.07, and boron-containing additive is (0.01～0.1) with the mol ratio of aluminum subacetate:1.
Preferably, inorganic aluminate is selected from aluminum chloride, aluminum nitrate, aluminum sulfate in step 1.
Preferably, silicon-containing additive is selected from tetraethyl orthosilicate, Ludox, water-soluble silicon oil, silane extremely in step 2
Few one kind.
Preferably, in step 4, the cellulose silk that step 3 is obtained is dried under room temperature in atmosphere, or is 30 in temperature
It is dried in～60 DEG C of calorstat.
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, be warming up to 900～1100 DEG C from 600 DEG C with the speed of 8～10 DEG C/min in step 4 burning till, it is incubated
2h。
A kind of sol-gel technology that is based on of the invention prepares low density and high performance alumina base pottery with reference to dry spinning technology
The method of porcelain fiber；It utilizes inorganic aluminate, aluminum subacetate for silicon source, a small amount of boron-containing additive of addition, silicon-containing additive, water work
For solvent, gelatinous fibre element silk is obtained with reference to dry spinning technology by sol-gel technology, eventually pass and be dried, sinter
To continuous aluminium oxide base ceramic fibre.
The present invention is compared to the prior art compared with having the advantage that：
1st, inorganic aluminate and aluminum subacetate are adopted for silicon source, it is pollution-free.The present invention need not add other macromolecule spinning and help
Agent can just obtain the good colloidal sol of spinnability；Colloidal sol stable performance, pH value is 3～4.5, can long storage time.
2nd, it is process is simple, easy to operate using dry spinning technology.The performances such as the viscosity according to colloidal sol, can select suitable
Orifice diameter, and adjust the conditions such as pressure, collecting drum rotating speed, path temperature.
3rd, burning till for cellulose silk adopts following steps：With the speed of 0.5～6 DEG C/min from room temperature to 550～650
DEG C, and slowly volatilize in this temperature 30min～4h, water, Organic substance, acid in cellulose silk etc., make cellulose silk uniform
Shrink, it is to avoid moisture content and Organic substance etc. volatilize too fast and forms hole, so as to affect 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, appropriate temperature retention time makes fiber finer and close, finally obtains alumina based continuous ceramic fibers.
Description of the drawings
Fig. 1 is the magnification at high multiple SEM photograph of the gained aluminium oxide base ceramic fibre of embodiment 3；
Fig. 2 is the magnification at high multiple SEM photograph of the gained aluminium oxide base ceramic fibre fracture of embodiment 3；
Fig. 3 is the magnification at high multiple SEM photograph on the gained aluminium oxide base ceramic fibre surface of embodiment 3；
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) preparation of colloidal sol：28.14g Al (NO are added in 90.00g deionized waters3)·9H2O, is dissolved as transparent molten
Liquid, adds 42.20g CH3COOAl(OH)2·1/3H3BO3, stirring under mixed solution room temperature is until transparent, addition 25.04g silicon
Colloidal sol, mixed solution is aging in 45 DEG C of water-baths.
(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 burns till：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, the continuous ceramics of alumina base is obtained fine
Dimension.
The colloidal sol prepared using said method need not add spin finish aid, and ropiness is good, stable, and the resting period is long.Institute
A diameter of 6-18 μm of alumina based continuous ceramic fibers is obtained, density is 2.62g/cm3, tensile strength is 1.45GPa, springform
Measure as 147GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%, constitutes the granule of the fiber
Mean diameter is about 38nm.Fibre diameter is determined by SEM, and tensile strength and elastic modelling quantity are surveyed by monofilament strength tester
It is fixed.
Embodiment 2
(1) preparation of colloidal sol：11.35g AlCl are added in 90.00g deionized waters3·6H2O, is dissolved as clear solution,
Add 42.20g CH3COOAl(OH)2·1/3H3BO3, stirring under mixed solution room temperature is until transparent, and addition 25.04g silicon is molten
Glue, mixed solution is aging in 45 DEG C of water-baths.
It is identical in step (2) embodiment 1.
(3) cellulose silk burns till：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, alumina based continuous ceramic fibers is obtained.
A diameter of 6-15 μm of gained alumina based continuous ceramic fibers, density is 2.6g/cm3, tensile strength is
1.4GPa, elastic modelling quantity is 145GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%, composition
The mean diameter of the granule of the fiber is about 32nm.Fibre diameter is determined by SEM, and tensile strength and elastic modelling quantity pass through single fiber
Dimension strength tester is determined.
Embodiment 3
As described in Example 1, except that：Al(NO3)·9H2O additions are 15.00g, add 42.20g
CH3COOAl(OH)2·1/3H3BO3, Ludox addition be 22.70g, the other the same as in Example 1.
A diameter of 6-15 μm of gained alumina based continuous ceramic fibers, density is 2.67g/cm3, tensile strength is
1.65GPa, elastic modelling quantity is 150GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%, composition
The mean diameter of the granule of the fiber is about 35nm.Fibre diameter is determined by SEM, and tensile strength and elastic modelling quantity pass through single fiber
Dimension strength tester is determined.
Comparative example 1
Other conditions are completely the same with embodiment 3, only difference is that only with 127.6g Al (NO3)·
9H2O；A diameter of 7-20 μm of gained alumina based continuous ceramic fibers, density is 2.32g/cm3, tensile strength is 0.2GPa,
Elastic modelling quantity is 26GPa, wherein Al2O3Content is 62%, SiO2Content is 24%, B2O3Content is 14%.By the He of comparative example 1
As can be seen that of the invention because raw material chooses suitable, the performance of its products obtained therefrom is significantly larger than the gained of comparative example 1 and produces embodiment 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；A diameter of 7-18 μm of gained alumina based continuous ceramic fibers, density is 2.52g/cm3, stretching is by force
Spend for 1.0GPa, elastic modelling quantity is 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 chooses suitable due to raw material, the performance of its 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；A diameter of 8-17 μm of gained alumina based continuous ceramic fibers, density
For 2.40g/cm3, tensile strength is 0.5GPa, and elastic modelling quantity is 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
Material chooses suitable, and the performance of its products obtained therefrom is significantly larger than the performance of the products obtained therefrom of comparative example 1,2,3.The effect also well beyond
It is estimated before experiment.
Comparative example 4
Other conditions are completely the same with embodiment 3, and difference is to substitute CH using aluminum isopropylate.3COOAl
(OH)2·1/3H3BO3, while add equivalent boric acid to make up aluminum subacetate in lack Boron contents, gained alumina base connect
A diameter of 7-16 μm of continuous ceramic fibre, density is 2.45g/cm3, tensile strength is 0.7GPa, and elastic modelling quantity is 82GPa, its
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 of the invention because raw material chooses suitable, the performance of its products obtained therefrom is significantly larger than comparative example for ratio 4 and embodiment 3
1st, the performance of 2,3,4 products obtained therefroms.The effect is also well beyond being expected before experiment.Also illustrate that simultaneously not all has
Machine silicon source is suitable for the present invention.
Claims (10)
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 2.6-2.67g/cm3, tensile strength is more than or equal to 1.4GPa.
2. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 1, it is characterised in that：It is described low close
Degree a diameter of 6-18 μm of high-performance aluminium oxide base ceramic fibre, elastic modelling quantity are 145-150GPa.
3. a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 2, it is characterised in that：It is described low close
Degree high-performance aluminium oxide base ceramic fibre by percentage to the quality, is made up of following components：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：Constitute the fibre
The mean diameter of the granule of dimension is 30-45nm.
5. a kind of method for preparing the low density and high performance aluminium oxide base ceramic fibre as described in claim 1-4 any one；Its
It is characterised by comprising the steps：
Step 1：The preparation of Alumina gel
In molar ratio, water-soluble inorganic aluminium salt：Aluminum subacetate=1：1～20, boron-containing additive：Aluminum subacetate=(0.01～
0.1)：1st, aluminum subacetate：Water=0.01～0.09：1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；To match somebody with somebody what is taken
Inorganic aluminate, aluminum subacetate, boron-containing additive, water mix homogeneously, obtain Alumina gel；
Step 2：The preparation of precursor sol can be spun
Silicon-containing additive is added toward step 1 gained Alumina gel, the addition of silicon-containing additive is with SiO2Content account for finished fiber
Quality 5～40% calculated, after uniform mixing deaeration is concentrated under the conditions of 40-100 DEG C, obtain spinnable alumina base
Precursor sol；
Step 3：Dry spinning
The spinnable alumina base precursor sol of step 2 gained is put in the reservoir with shower nozzle, using dry spinning technology
Obtain alumina based fibre element silk；
Step 4：It is dried, sinters
The cellulose silk that step 3 is obtained is dried in atmosphere or in calorstat, then with the speed of 0.5～6 DEG C/min from room
Temperature is warming up to 550～650 DEG C, and is incubated 0.5～2h, then 850 are warming up to from 550～650 DEG C with the speed of 5～15 DEG C/min～
1200 DEG C are burnt till, and are incubated 10min～4h, obtain alumina-based continuous fiber.
6. the preparation method of a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 5；Its feature exists
In：In step 1, the pH value of Alumina gel is 3～4.5.
7. the preparation method of a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 5；Its feature exists
In：In step 1, in molar ratio, water-soluble inorganic aluminium salt：Aluminum subacetate=1：1～20, boron-containing additive：Aluminum subacetate=
(0.01～0.1)：1st, aluminum subacetate：Water=0.01～0.09：1, with taking inorganic aluminate, aluminum subacetate, boron-containing additive, water；
The inorganic aluminate, aluminum subacetate, boron-containing additive, the water that take 3～48h of continuous stirring under the conditions of 25～100 DEG C will be matched somebody with somebody, mixing is equal
It is even, obtain Alumina gel.
8. the preparation method of a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 5；Its feature exists
In：In step 1, aluminum subacetate and the mol ratio of inorganic aluminate are 4～10 in step 1, wherein the mol ratio of aluminum subacetate and water
For 0.04～0.07, boron-containing additive is (0.01～0.1) with the mol ratio of aluminum subacetate:1.
9. the preparation method of a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 5；Its feature exists
In：
At least one of the inorganic aluminate in aluminum chloride, aluminum nitrate, aluminum sulfate in step 1；
At least one of the silicon-containing additive in tetraethyl orthosilicate, Ludox, water-soluble silicon oil, silane in step 2；
In step 4, the cellulose silk that step 3 is obtained is dried under room temperature in atmosphere, or in the constant temperature that temperature is 30～60 DEG C
It is dried in case.
10. the preparation method of a kind of low density and high performance aluminium oxide base ceramic fibre according to claim 9；Its feature exists
In：
With the speed of 1～5 DEG C/min from room temperature to 600 DEG C in step 4, and it is incubated 1h；
900～1100 DEG C are warming up in step 4 from 600 DEG C with the speed of 8～10 DEG C/min to burn till, be incubated 2h.
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