CN107653518A - Continuous ultra-fine/nano aluminium oxide base ceramic fibre beam material of a kind of high-orientation and preparation method thereof - Google Patents
Continuous ultra-fine/nano aluminium oxide base ceramic fibre beam material of a kind of high-orientation and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62236—Fibres based on aluminium oxide
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- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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Abstract
The present invention relates to continuous ultra-fine/nano aluminium oxide base ceramic fibre beam material of a kind of high-orientation and preparation method thereof, belong to technical field of inorganic nonmetallic materials.The degree of orientation of continuous ultra-fine/nano oxidized aluminium base tow material of the high-orientation is more than or equal to 80%.Its preparation method is：The method being combined using conjugation electrostatic spinning technique with sol-gal process, reception device is used as by the use of rotating cylinder, obtaining, there is height-oriented continuous presoma to be spun into fiber, is spun into fiber and passes through high-temperature calcination, obtain with the continuous ultra-fine/nano aluminium oxide base ceramic fibre beam of high-orientation.Ultra-fine/nano aluminium oxide base ceramic fibre Shu Lianxu prepared by the present invention is flexible, not easy to break, available for fields such as partiting thermal insulations.Present invention process flow is simple, and equipment operation is flexible, suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of continuous ultra-fine/nano aluminium oxide base ceramic fibre beam material of high-orientation and its preparation side
Method, belong to technical field of inorganic nonmetallic materials.
Background technology
As a kind of common refractory material, aluminium oxide base ceramic fibre due to thermal conductivity factor is low, heat endurance is good,
The advantages that specific heat is small, the fields such as chemical industry, metallurgy, electric power, Aeronautics and Astronautics are widely used in, wherein, the production of common alumina based fibre
Product have long fibre, chopped fiber and whisker, and its middle short fiber and whisker make it in the high-end fields such as Aero-Space due to its size
Application be limited.And alumina base long fibre, some special constructions and the thermal protection product of shape can be obtained by braiding, opened up
Its wide application.Therefore, it is significant to prepare the continuous alumina based fibre product for being adapted to braiding.
Electrostatic spinning most starts to be only used for polymer fiber as a kind of emerging method for preparing micro nano-scale fiber
Prepare, recently as the development of electrostatic spinning technique, ultra-fine/nano ceramic fibers are also successfully developed, wherein
Also include alumina base it is ultra-fine/nanofiber.Compared to micron-sized ceramic fiber products, ultra-fine/nano ceramic fibers have
Higher specific surface area, lower density and thermal conductivity factor, these advantages improve the use valency of ultra-fine/nano ceramic fibers
Value.But due to the moulding draw-wire machine system of electrostatic spinning in itself, it is fine to prepare continuous ultra-fine/nano oxidized aluminium base of the high-orientation suitably woven
Dimension has larger difficulty.Pan etc. reports one kind and prepares orientated polymer using the positive and negative electrode electrostatic spinning staggered relatively that carries out
The method of bundles of nanofibers, make the polymer nanofiber product of available endless in this way, the country is referred to as
It is conjugated electrostatic spinning.Domestic and foreign scholars profit has prepared many nanofiber products in this way, and these products have certain
The degree of orientation, but the degree of orientation is only 70% or so, but it is there is not yet ultra-fine/nano oxidized on making to prepare high-orientation in this way
The research of aluminium base fiber.With reference to the active demand of market aluminium base fiber strand product ultra-fine to high-orientation/nano oxidized, exploitation one
The method that kind prepares ultra-fine/nano oxidized aluminium base fibre bundle of high-orientation is significant.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of continuous ultra-fine/nano oxidized aluminium base fiber of high-orientation
Beam material and preparation method thereof.
A kind of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation of the present invention；The high-orientation continuously surpasses
The degree of orientation of carefully/nano oxidized aluminium base tow material is more than or equal to 80%.
The method of testing of the degree of orientation is in the present invention：The scanning electron microscope (SEM) photograph of 5 same batch products is taken, is swept at each
One reference line of setting, the reference line in electron microscope is retouched then to compare parallel in taken scanning electron microscope (SEM) photograph 50% fiber
Any one fiber and reference line in taken scanning electron microscope (SEM) photograph, then think that the fiber is qualified fibre when the angle of the two is 5-0 °
Dimension, 200 fibers are randomly selected in 5 scanning electron microscope (SEM) photographs and measures and determines the number of acceptable fiber, use acceptable fiber
Number/200*100%, that is, obtain the degree of orientation of the batch sample.
A kind of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation of the present invention；The high-orientation continuously surpasses
The density of carefully/nano oxidized aluminium base tow material is 2.41~2.86g/cm3, single fiber diameter is 290~680nm.
A kind of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation of the present invention；The high-orientation continuously surpasses
Carefully/nano oxidized aluminium base tow material, Al and Si mol ratio are 2.98-3.05:1st, it is preferably 3:1.
Preferably, continuous ultra-fine/nano oxidized aluminium base tow material of a kind of high-orientation of the present invention；The height
Continuous ultra-fine/nano oxidized aluminium base tow material of the degree of orientation, by percentage to the quality, is made up of following components：
Al2O355~62%；
SiO224~34.5%；
B2O312.5~14%.
A kind of preparation method of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation of the present invention；Including following
Step：
The preparation of step 1 precursor sol
It is 2.98-3.05 by Al and Si mol ratio:1st, it is preferably 3:1 by setting constituent content with taking boron source, silicon source, aluminium
Source；It will be dissolved in the boron source, silicon source, silicon source that take in solvent, the molar concentration for obtaining silicon is 0.35-0.45mol/L, is preferably
0.4-0.42mol/L precursor sol；The silicon source is esters of silicon acis, source of aluminium is organic acid aluminium salt；
The preparation of step 2 spinning solution
Spin finish aid is dissolved in organic solvent, stirred, it is molten to obtain the spin finish aid that spin finish aid concentration is 12-18wt%
Liquid, then, in mass ratio, precursor sol：Spin finish aid solution=(1~2):3, by precursor sol and spin finish aid solution
It is well mixed, obtain spinning solution；
Step triple conjugation electrostatic spinning prepares precursor fibre
Spinning solution prepared by step 2 is subjected to electrostatic spinning, spinning electrode positive pole by the way of positive and negative electrode conjugation
With negative pole provide voltage value it is identical, respectively 3.45~7.00kV, be preferably 5kV and -3.45~-7.00kV, be preferably -
Between 5kV, it is also identical that both positive and negative polarity injects speed, and in the range of 0.25~0.45ml/min, the distance between both positive and negative polarity syringe needle is 16
~20cm, it is spun into precursor fibre and is collected with the roller being placed on immediately below both positive and negative polarity point midway, rotate the line of roller
Speed is 2.56~3.2m/min；
Step 4 sintering processes
Precursor fibre obtained by step 3 is placed and is incubated 3~6h in an oven, then takes out and is placed in Muffle furnace from room
Temperature rise is incubated 1~2h after taking out cooling under conditions of 800~1200 DEG C, obtains height and take to 600~800 DEG C of 1~2h of insulation
To continuous ultra-fine/nano oxidized aluminium base fibre bundle of degree.
Preferably, boron source described in step 1, silicon source are provided by boracic time aluminium acetate.As further preferred
Scheme, the chemical formula of the boracic time aluminium acetate is Al (OH)2(OOCCH3)·1/3H3BO3。
Preferably, in step 1, the silicon source is tetraethyl orthosilicate.
It is 2.98-3.05 by Al and Si mol ratio in step 1 as further preferred scheme:1st, it is preferably
3:1 by setting constituent content with taking boracic time aluminium acetate, tetraethyl orthosilicate；By with the boracic taken time aluminium acetate, tetraethyl orthosilicate
Add in solvent, 12h is stirred under 40 DEG C of water bath conditions and obtains transparent aluminium silicon composite sol, that is, obtains precursor sol.Institute
Solvent is stated by water and ethanol in mass ratio 1:1 composition.
Preferably, in step 2, the spin finish aid is polyvinylpyrrolidone (PVP).As further
Preferred scheme, in step 2, PVP powder is poured into alcohol, stirring at normal temperature 3h, obtain the spinning that PVP concentration is 16-18wt%
Compounding agent solution.The PVP preferred 1000000-1500000 of molecular weight.
The present invention, gained spinning solution is the spinning solution of water white transparency in step 2.
Preferably, of the invention, the pin hole of both positive and negative polarity syringe needle is 330-600nm, is preferably 500- in step 3
530nm.As further preferred scheme, in the present invention, both positive and negative polarity needle sizes are identical, pinhole aperture phase of both positive and negative polarity syringe needle
Together.
Preferably, it is of the invention, in step 4, the heating rate of 600~800 DEG C of sintering process is risen to from room temperature
For 5 DEG C/min.
In optimal technical scheme of the present invention, from boracic time aluminium acetate be silicon source and boron source, tetraethyl orthosilicate are silicon source, water
With alcohol as solvent, aluminium silicon composite sol is prepared using sol-gal process, by with mixed as the PVP of spin finish aid after
The stable spinning solution of property is obtained, is prepared by the conjugation electrostatic spinning technique of specified conditions parameter and is spun into precursor fibre,
Continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation is obtained after sintered processing again.The high-orientation continuously surpasses
The degree of orientation of carefully/nano oxidized aluminium base tow material is more than or equal to 80%.Preferably greater than it is equal to 85%；More preferably
85-93%.
It is of the invention designed and prepare highly oriented alumina base it is ultra-fine/nano ceramic fibers can be in its table by modification
The metallic particles such as face supported copper, zinc, nickel, iron are prepared into cermet fibres, and this product with good activity because urging
Change field is widely used.
It is of the invention designed and prepare highly oriented alumina base it is ultra-fine/nano ceramic fibers, due to PVP decomposition inside it
And producing a certain amount of fine hole and crackle so that this highly oriented nanofiber product has higher specific surface area, because
This, this product can apply to filter adsorbing domain, for example, the filter assemblies of high-temperature filter can be prepared into.
It is of the invention designed and prepare highly oriented alumina base it is ultra-fine/nano ceramic fibers, its intensity is compared with non-woven fabrics form
Product there is more excellent mechanical property, can mutually be used as the enhancing of composite.
It is of the invention designed and prepares highly oriented alumina base it is ultra-fine/nano ceramic fibers, its can be used for preparing it is ceramic-
Polymer composite fibrous, this product and Kafra fiber (Kevlar fibers) have good binding ability, and both are fine
Dimension carries out shuffling, can prepare lighter more high-strength composite fiber product.
The technology of the present invention feature is as follows：
1st, boron element, boron member can be introduced in aluminium-silicon binary system ceramics fiber for silicon source using the secondary aluminium acetate of boracic
The presence of element can improve the pliability of sintered fiber, reduce the density of final product, prevent fiber crystal grain in sintering process
Fast growth.
2nd, it is molten can to obtain forerunner's bluk recombination that uniformity is high, stability is good for the method together hydrolyzed using silicon source and silicon source
Glue.
3rd, selected PVP alcoholic solution and presoma complex sol compatibility are good, and it is anti-that violent chemistry will not occur
Answer, the excellent spinning solution of uniform component, segregation-free, the mobility that can be obtained.
4th, the conjugation electrostatic spinning technique that uses, the highly oriented (degree of orientation prepared by the synergy of each conditional parameter
More than continuous nano-fibre beam 80%) (its length can be indefinite length in theory).
Brief description of the drawings
Fig. 1 is conjugation electrostatic spinning apparatus schematic diagram.
Fig. 2 is that the continuous presoma of high-orientation that the collection of embodiment 1 obtains is spun into fiber SEM photograph.
Fig. 3 is the low power SEM photograph of continuous ultra-fine/nano oxidized aluminium base fibre bundle of gained high-orientation of embodiment 1.
Fig. 4 is the high power SEM photograph of continuous ultra-fine/nano oxidized aluminium base fibre bundle of gained high-orientation of embodiment 1.
Fig. 5 is the high power SEM photograph of continuous ultra-fine/nano oxidized aluminium base fibre bundle of the gained of comparative example 3.
Fig. 6 is the high power SEM photograph of continuous ultra-fine/nano oxidized aluminium base fibre bundle of the gained of comparative example 4.
Fig. 7 is the high power SEM photograph of continuous ultra-fine/nano oxidized aluminium base fibre bundle of the gained of comparative example 5.
Fig. 8 is the high power SEM photograph of continuous ultra-fine/nano oxidized aluminium base fibre bundle of the gained of comparative example 6.
Embodiment
The boracic time aluminium acetate chemical formula used in embodiment is Al (OH)2(OOCCH3)·1/3H3BO3, by the U.S.
Strem Chemicals, Inc. offers.Tetraethyl orthosilicate used is provided by Xilong Chemical Co., Ltd.Electrostatic spinning
Machine is known device, by Beijing Yongkang work in peace and contentment Science and Technology Ltd. provide, conjugation electrostatic spinning apparatus schematic diagram see Fig. 1.
Embodiment 1
Step 1：The preparation of precursor sol
1.5g aluminium acetate, 0.72g tetraethyl orthosilicates are added to what is be made up of 3.89g deionized waters and 3.89g alcohol
In the mixed solvent and under 40 DEG C of water bath conditions stir 12h obtain transparent aluminium silicon composite sol product.
Step 2：Uniform alcoholic solution and molten with presoma is made in spin finish aid PVP (molecular weight is about 1300000)
Glue mixes and spinning solution is made.
PVP powder is poured into alcohol, the concentration of stirring at normal temperature 3h, PVP solution is 16%.Aluminium silicon described in step 1 is answered
Close colloidal sol and press 1 with PVP solution:3 are mixed, and obtain the water white transparency spinning solution of stable performance.
Step 3：It is conjugated electrostatic spinning and prepares precursor fibre
Water white transparency spinning solution prepared by step 2 is subjected to electrostatic spinning, spinning by the way of positive and negative electrode conjugation
The voltage that electrode anode and negative pole provide is respectively 6.5kV and -6.5kV, both positive and negative polarity inject speed be 0.45ml/min, it is positive and negative
Distance between the syringe needle of pole is 20cm, both positive and negative polarity needle aperture is 0.54 micron, is spun into precursor fibre with being placed in both positive and negative polarity
Rotation roller immediately below point position is collected, and the linear velocity for rotating roller is 3.2m/min, be collected into be spun into fiber equal
It is even continuous, degree of orientation height (see Fig. 2).
Step 4：Precursor fibre is spun into be sintered after drying
Precursor fibre described in step 3 is placed and is incubated 6h in an oven, then takes out and is placed in Muffle furnace from room temperature
800 DEG C of insulation 1h are risen to, 1h is incubated under conditions of 900 DEG C after taking out cooling, obtain the continuous ultra-fine/nano oxygen of high-orientation
Change aluminium base fibre bundle.
Ultra-fine/nano oxidized aluminium base fibre bundle degree of orientation of gained is high, uniformly continuous, and there is preferably orientation to close between fiber
System, its degree of orientation are 86%, and fibre diameter is between 550~640nm (see Fig. 2,3,4).
Embodiment 2
With embodiment 1, difference is for steps 1 and 2,3：After 800 DEG C of insulation 1h fiber is taken out into cooling in step 4
1h is incubated under conditions of 1200 DEG C.
Ultra-fine/nano oxidized aluminium base fibre bundle degree of orientation of gained is high, uniformly continuous, and there is preferably orientation to close between fiber
System, its degree of orientation are 89%, and fibre diameter is between 430~610nm.
Embodiment 3
Step 1 is the same as embodiment 1.
Step 2：PVP solution preparing process embodiment 1, difference is：By aluminium silicon composite sol described in step 1 with
PVP solution presses 2:3 are mixed, and obtain the water white transparency spinning solution of stable performance.
Step 3：It is conjugated electrostatic spinning and prepares precursor fibre
Water white transparency spinning solution prepared by step 2 is subjected to electrostatic spinning, spinning by the way of positive and negative electrode conjugation
The voltage that electrode anode and negative pole provide is respectively 3.45kV and -3.45kV, and it is 0.25ml/min, just that both positive and negative polarity, which injects speed,
Distance between negative pole syringe needle is 16cm, and both positive and negative polarity needle aperture is 0.54 micron, is spun into precursor fibre with being placed on both positive and negative polarity
Rotation roller immediately below point midway is collected, and the linear velocity for rotating roller is 2.56m/min.
Step 4：
Precursor fibre described in step 3 is placed and is incubated 6h in an oven, then takes out and is placed in Muffle furnace from room temperature
800 DEG C of insulation 1h are risen to, 1h is incubated under conditions of 1000 DEG C after taking out cooling, obtains the continuous mullite nano of high-orientation
Fibre bundle.
Ultra-fine/nano oxidized aluminium base fibre bundle degree of orientation of gained is high, uniformly continuous, has between single fiber and preferably takes
To relation, its degree of orientation is 80%, and fibre diameter is between 330~490nm.
Embodiment 4
Step 1 is the same as embodiment 1.
Step 2：Aluminium silicon composite sol described in step 1 and PVP solution are pressed 1:3 are mixed, and obtain the nothing of stable performance
The transparent spinning solution of color, difference are：The concentration of PVP solution is 18%.
Step 3：It is conjugated electrostatic spinning and prepares precursor fibre
Water white transparency spinning solution prepared by step 2 is subjected to electrostatic spinning, spinning by the way of positive and negative electrode conjugation
The voltage that electrode anode and negative pole provide is respectively 5kV and -5kV, and it is 0.35ml/min, both positive and negative polarity pin that both positive and negative polarity, which injects speed,
Distance between head be 16cm, and both positive and negative polarity needle aperture is 0.54 micron, is spun into precursor fibre with being placed on both positive and negative polarity midpoint position
Rotation roller immediately below putting is collected, and the linear velocity for rotating roller is 2.92m/min.
Step 4：
Precursor fibre described in step 3 is placed and is incubated 3h in an oven, then takes out and is placed in Muffle furnace from room temperature
600 DEG C of insulation 2h are risen to, 2h is incubated under conditions of 1000 DEG C after taking out cooling, obtains the continuous mullite nano of high-orientation
Fibre bundle.
Ultra-fine/nano oxidized aluminium base fibre bundle degree of orientation of gained is high, uniformly continuous, has between single fiber and preferably takes
To relation, its degree of orientation is 93%, and fibre diameter is between 410~530nm.
Embodiment 5
Step 1 is the same as embodiment 1.
Step 2：Aluminium silicon composite sol described in step 1 and PVP solution are pressed 1:3 are mixed, and obtain the nothing of stable performance
The transparent spinning solution of color, difference are：The concentration of PVP solution is 12%.
Step 3：It is conjugated electrostatic spinning and prepares precursor fibre
Water white transparency spinning solution prepared by step 2 is subjected to electrostatic spinning, spinning by the way of positive and negative electrode conjugation
The voltage that electrode anode and negative pole provide is respectively 4.5kV and -4.5kV, both positive and negative polarity inject speed be 0.45ml/min, it is positive and negative
Distance between the syringe needle of pole is 18cm, and both positive and negative polarity needle aperture is 0.54 micron, is spun into precursor fibre with being placed in both positive and negative polarity
Rotation roller immediately below point position is collected, and the linear velocity for rotating roller is 2.56m/min.
Step 4：
Precursor fibre described in step 3 is placed and is incubated 3h in an oven, then takes out and is placed in Muffle furnace from room temperature
600 DEG C of insulation 2h are risen to, 2h is incubated under conditions of 1000 DEG C after taking out cooling, obtains the continuous mullite nano of high-orientation
Fibre bundle.
Ultra-fine/nano oxidized aluminium base fibre bundle degree of orientation of gained is high, uniformly continuous, has between single fiber and preferably takes
To relation, its degree of orientation is 87%, and fibre diameter is between 270~400nm.
Comparative example 1
Other conditions are consistent in embodiment 1；Difference is：By aluminium silicon composite sol described in step 1 and PVP solution
By 4:3 are mixed, and obtain the spinning solution of water white transparency；Precursor fibre is spun into being placed on immediately below both positive and negative polarity point midway
Rotation roller be collected, the linear velocity for rotating roller is 2.56m/min.
Because PVP dosages are relatively low, it is poor to be spun into fibre strength, is often broken during being collected with roller；
Meanwhile although gained continuous aluminium oxide base it is ultra-fine/nanofiber diameter is uniform, the orientation relationship between single fiber is relatively
Difference, the degree of orientation are only 52%.
Comparative example 2
Other conditions are consistent in embodiment 1；Difference is：By aluminium silicon composite sol described in step 1 and PVP solution
By 0.5:3 are mixed, and obtain the spinning solution of water white transparency；Precursor fibre is spun into under being placed on both positive and negative polarity point midway just
The rotation roller of side is collected, and the linear velocity for rotating roller is 3.2m/min.
Because PVP dosages are higher, for the electrical conductivity of spinning solution with respect to step-down, the whip for being spun into fiber moves scope and amplitude reduction,
Although gained continuous aluminium oxide base is ultra-fine/nanofiber single fiber between the degree of orientation can reach 83%, the diameter of fiber
Have increased between 1360~1570nm, the yield reduction of fiber, cost rise.
Comparative example 3
Other conditions are consistent in embodiment 1；Difference is：The voltage point that positive pole and negative pole provide in spinning process
Not Wei 8.5kV and -8.5kV, it is that distance between 0.45ml/min, both positive and negative polarity syringe needle is 16cm that both positive and negative polarity, which injects speed, is spun into
Precursor fibre is collected with the rotation roller being placed on immediately below both positive and negative polarity point midway, and the linear velocity for rotating roller is
2.56m/min。
As shown in figure 5, gained continuous aluminium oxide based nano-fiber uniformly continuous, but the orientation relationship phase between single fiber
To poor.The degree of orientation is about 72%.
Comparative example 4
Other conditions are consistent in embodiment 1；Difference is：Distance between both positive and negative polarity syringe needle is 16cm, before being spun into
Drive body fiber to be collected with the rotation roller being placed on immediately below both positive and negative polarity point midway, the linear velocity for rotating roller is
1.98m/min。
As shown in fig. 6, gained continuous aluminium oxide based nano-fiber uniformly continuous, but fiber is relatively thick and single fiber it
Between orientation relationship it is relatively poor.After this linear velocity for mainly rotating roller reduces, the speed that fiber is collected by traction is spun into
Diminish, when the dynamic speed of speed and fiber the generation whip that traction is collected is more or less the same, the degree of orientation of fiber will be deteriorated；Together
When, the pulling force being axially subject in fiber during collection also diminishes, and causes the diameter of fiber can't fully to refine, so
To fibre diameter can become big.But the linear velocity for rotating roller is also unsuitable excessive, and crossing conference causes fibrous fracture, must not obtain continuous
Fiber product.The degree of orientation of institute's product is measured, its degree of orientation is about 58%.
Comparative example 5
Other conditions are consistent in embodiment 1；Difference is：Both positive and negative polarity inject speed be 0.6ml/min, it is positive and negative
Distance between the syringe needle of pole is 20cm, is spun into precursor fibre and is carried out with the rotation roller being placed on immediately below both positive and negative polarity point midway
Collect, the linear velocity for rotating roller is 3.2m/min.
As shown in fig. 7, gained continuous aluminium oxide based nano-fiber keeps continuous, but fibre diameter is relatively large and thickness not
, the orientation relationship between single fiber is relatively poor.This mainly due to it is larger inject speed improve it is powered at syringe needle
The amount of centrum so that the jet ejected contains more spinning solutions, such jet in the presence of electric field force very
Difficulty, which is stretched to refine, forms the nanofiber with homogeneous diameter, so the fiber product degree of orientation prepared is poor, is relatively large in diameter
It is and uneven.The degree of orientation of institute's product is measured, its degree of orientation is about 53%.
Comparative example 6
Other conditions are consistent in embodiment 1；Difference is：The voltage point that positive pole and negative pole provide in spinning process
Not Wei 4.5kV and -4.5kV, it is that distance between 0.6ml/min, both positive and negative polarity syringe needle is 12cm that both positive and negative polarity, which injects speed, before being spun into
Drive body fiber to be collected with the rotation roller being placed on immediately below both positive and negative polarity point midway, the linear velocity for rotating roller is
2.56m/min。
As shown in figure 8, gained continuous aluminium oxide based nano-fiber uniformly continuous, fibre diameter is larger, between single fiber
Orientation relationship it is relatively poor.This fiber mainly due to the distance condition lower band xenogenesis electric charge between less both positive and negative polarity syringe needle
Between attraction it is excessive, both positive and negative polarity fibre merges when being not yet stretched the effect of traction, has just been collected afterwards
Come, the fiber-wall-element model degree obtained under such circumstances is very poor；Meanwhile fiber moves space and amplitude is smaller due to whip, so not
There is being sufficiently tensile by electric field force, therefore obtain the thicker fiber product of diameter.The degree of orientation of institute's product is measured, its degree of orientation is about
For 73%.
Claims (10)
- A kind of 1. continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation；It is characterized in that：The high-orientation is continuous The degree of orientation of ultra-fine/nano oxidized aluminium base tow material is more than or equal to 80%.
- A kind of 2. continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 1；Its feature exists In：The density of continuous ultra-fine/nano oxidized aluminium base tow material of the high-orientation is 2.41~2.86g/cm3, single fiber A diameter of 290~680nm.
- A kind of 3. continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 1；Its feature exists In：Continuous ultra-fine/nano oxidized aluminium base tow material of the high-orientation, Al and Si mol ratio are 2.98-3.05:1.
- A kind of 4. continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 3；Its feature exists In：Continuous ultra-fine/nano oxidized aluminium base tow material of the high-orientation, by percentage to the quality, is made up of following components：Al2O355~62%；SiO224~34.5%；B2O312.5~14%.
- A kind of 5. preparation method of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation；It is characterized in that；Including under State step：The preparation of step 1 precursor solIt is 2.98-3.05 by Al and Si mol ratio:1 by setting constituent content with taking boron source, silicon source, silicon source；By with the boron taken Source, silicon source, silicon source are dissolved in solvent, and the molar concentration for obtaining silicon is 0.35-0.45mol/L precursor sol；The silicon source It is organic acid aluminium salt for esters of silicon acis, source of aluminium；The preparation of step 2 spinning solutionSpin finish aid is dissolved in organic solvent, stirred, obtains the spin finish aid solution that spin finish aid concentration is 12-18wt%, Then, in mass ratio, precursor sol：Spin finish aid solution=(1~2):3, precursor sol and spin finish aid solution are mixed Close uniformly, obtain spinning solution；Step triple conjugation electrostatic spinning prepares precursor fibreSpinning solution prepared by step 2 is subjected to electrostatic spinning by the way of positive and negative electrode conjugation, spinning electrode positive pole and negative The voltage value that pole provides is identical, and respectively between 3.45~7.00kV and -3.45~-7.00kV, both positive and negative polarity injects speed Identical, in the range of 0.25~0.45ml/min, the distance between both positive and negative polarity syringe needle is 16~20cm, is spun into precursor fibre with putting Put the roller immediately below both positive and negative polarity point midway to be collected, the linear velocity for rotating roller is 2.56~3.2m/min；Step 4 sintering processesPrecursor fibre obtained by step 3 is placed and is incubated 3~6h in an oven, then takes out and is placed in Muffle furnace from room temperature liter To 600~800 DEG C of 1~2h of insulation, 1~2h is incubated under conditions of 800~1200 DEG C after taking out cooling, obtains high-orientation Continuous ultra-fine/nano oxidized aluminium base fibre bundle.
- A kind of 6. preparation side of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 5 Method；It is characterized in that：Boron source described in step 1, silicon source are provided by boracic time aluminium acetate；The silicon source is tetraethyl orthosilicate；Institute The chemical formula for stating boracic time aluminium acetate is Al (OH)2(OOCCH3)·1/3H3BO3。
- A kind of 7. preparation side of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 6 Method；It is characterized in that：It is 2.98-3.05 by Al and Si mol ratio in step 1:1st, match somebody with somebody by setting constituent content and take boracic Aluminium acetate, tetraethyl orthosilicate；It will be added with the boracic taken time aluminium acetate, tetraethyl orthosilicate in solvent, under 40 DEG C of water bath conditions Stirring 12h obtains transparent aluminium silicon composite sol, that is, obtains precursor sol；The solvent is by water and ethanol in mass ratio 1:1 Composition.
- A kind of 8. preparation side of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 5 Method；It is characterized in that：In step 2, the spin finish aid is polyvinylpyrrolidone.
- A kind of 9. preparation side of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 5 Method；It is characterized in that：In step 2, polyvinylpyrrolidonepowder powder is poured into alcohol, stirring at normal temperature 3h, obtains PVP concentration For 16-18wt% spin finish aid solution.
- A kind of 10. preparation side of continuous ultra-fine/nano oxidized aluminium base tow material of high-orientation according to claim 5 Method；It is characterized in that：In step 3, the pin hole of both positive and negative polarity syringe needle is 330-600nm；And both positive and negative polarity needle sizes are identical, the pin of both positive and negative polarity syringe needle Hole aperture is identical；In step 4, the heating rate that 600~800 DEG C of sintering process is risen to from room temperature is 5 DEG C/min.
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| 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 |
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| CN111850818A (en) * | 2019-04-30 | 2020-10-30 | 深圳市罗湖区人民医院 | Preparation method and product of conjugate electrospun nanofiber artificial small-caliber intravascular stent |
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| CN114455846A (en) * | 2022-01-19 | 2022-05-10 | 东华大学 | Porous mullite nanofiber-based flocculus material with vertical orientation structure and preparation method thereof |
| CN114455846B (en) * | 2022-01-19 | 2024-01-23 | 东华大学 | Porous mullite nanofiber-based flocculus material with vertical orientation structure and preparation method thereof |
| CN115386973A (en) * | 2022-09-07 | 2022-11-25 | 兰州大学 | Method for preparing side-by-side heterojunction nano fibers through single-source double-field electrostatic spinning |
| CN116163040A (en) * | 2023-02-27 | 2023-05-26 | 东华大学 | Preparation method of flexible titanium dioxide ceramic nanofiber yarn |
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