CN106337217B - A kind of porous Si-B-N-O superfine fibre and preparation method thereof - Google Patents
A kind of porous Si-B-N-O superfine fibre and preparation method thereof Download PDFInfo
- Publication number
- CN106337217B CN106337217B CN201610892319.9A CN201610892319A CN106337217B CN 106337217 B CN106337217 B CN 106337217B CN 201610892319 A CN201610892319 A CN 201610892319A CN 106337217 B CN106337217 B CN 106337217B
- Authority
- CN
- China
- Prior art keywords
- porous
- superfine fibre
- spinning
- high temperature
- fibrinogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- 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
Abstract
A kind of preparation method of porous Si-B-N-O superfine fibre, this method includes (1) using small molecule boron source, siloxanes, modified siloxane as solute, diluted acid and alcohol are solvent, and spin finish aid is added and prepares obtained PBSO (polyborosiloxane) fibrinogen of spinning solution progress electrostatic spinning；(2) fibril fibrinogen is placed in baking oven and pre-treatment is dried, dry fiber is placed in NH3And/or N2High temperature furnace high temperature firing under mixed-gas atmosphere obtains diameter after being cooled to room temperature as 0.5~5 μm of porous Si-B-N-O superfine fibre.Porous Si-B-N-O superfine fibre is at fiber felted prepared by the present invention, and uniform diameter, material internal residual carbon content is low, and inside has uniform hole, and gap range is in 2~50nm.There are excellent dielectric properties and high temperature resistance, has wide practical use in aerospace.
Description
Technical field
The present invention relates to high temperature resistant wave-permeable super fine ceramic fiber technical fields, and it is super to be specifically related to a kind of porous Si-B-N-O
Fine fibre and preparation method thereof.
Background technique
Si-B-N-O ceramic fiber blanket has that high temperature resistance is good, thermal conductivity is low, wave transparent is had excellent performance, lightweight and flexibility
The advantages that good, has broad application prospects in the fields such as Aeronautics and Astronautics.
Though currently, yet there are no related diameter about Si-B-N-O ceramics or the report of thick fiber diameters and be evenly distributed
Porous Si-B-N-O superfine fibre report.
United States Patent (USP) US006180809B1 (patent No. US6180809B1) is reported to be prepared under inertia protective atmosphere
Polyborosiloxane precursor, by precursor, pyrolysis nitridation has obtained amorphous Si-B-N- under not higher than 1300 DEG C ammonias
O.Raw material activity is high, and reaction condition is harsh, but polyborosiloxane dissolves in tetrahydrofuran (THF), makes it that can be made into fiber, sheet
With the toxicity for increasing use process while bulk.
Funayama etc. reacts the preparation poly- silicon amine alkane of perhydrogenating with ammonia using dichlorosilane-pyridine, reacts with trimethyl borine
PVDF hollow fiber membrane is synthesized, pyrolysis obtains Si-B-N-O ceramic fibre in ammonia or nitrogen after spinning.Fiber high temperature (about
1600 DEG C) it is able to maintain high tensile strength.But 8-12 μm of gained fibre diameter include aperture and small hole, gained fiber quality compared with
It is low, and precursor synthetic method is complicated, it is at high cost.(O.Funayama,Development of Si-B-O-N fibres
from polyborosilazane[J].Journal of Materials Science,1994,29,2238-2244.
L.Bois etc. prepares polyborosiloxane by silicon tetrachloride and acid reaction, and polyborosiloxane is burnt into ammonia
Si-B-N-O powder is obtained, powder is appointed at 1300 DEG C so keeps amorphous state.(L.Bois,Characterization of a
boro-silicon oxynitride prepared by thermal nitridation of a polyborosiloxane
[J].Journal of Alloys and Compounds,1996,232,244-253.)
Han Ke is equal clearly to pass through the positive methyl PVDF hollow fiber membrane presoma large scale preparation for being pyrolyzed melt spinning Si-B-N fibre
Dimension, fiber is in 1600 DEG C of holding amorphous states, and fiber is uniform, and surface is smooth, flawless, steady with excellent dielectric properties and high temperature
It is qualitative.But activity is high in air for gained Precursors of Fibers, cannot use in air, and reaction condition is harsh, and preparation cost is high.
YuQing Peng,KeQing Han,Large-scale preparatio n of SiBN ceramic fibres from a
single source precursor[J].Ceramics International 40(2014)4797-4804.
To sum up, preparing Si-B-N-O fiber mainly using polymer-derived method at present has the deficiency of following three aspect: 1, closing
It is high at the raw material activity of Si-B-N-O precursor, and when synthesis SiBNO ceramics, PVDF hollow fiber membrane is generally first synthesized, is synthesized
The general activity of the raw material of PVDF hollow fiber membrane needs to operate under an inert atmosphere greatly, and reaction need to carry out under an inert atmosphere, increase
The complexity of technique.2, gained Si-B-N-O fibre diameter is thicker, and diameter is unevenly distributed.3, in the Si-B-N-O fiber synthesized
Carbon residual quantity it is higher.
Summary of the invention
The purpose of the present invention is to provide a kind of porous Si-B-N-O superfine fibres and preparation method thereof.
The present invention provides a kind of porous Si-B-N-O superfine fibre and preparation method thereof, comprising the following steps: configuration spinning
Liquid obtains PBSO fibrinogen by electrostatic spinning, obtains porous Si-B-N-O through high temperature firing after dry to PBSO fibrinogen and surpasses
Fine fibre；High temperature firing step includes: in NH3And/or N2It is warming up under mixed-gas atmosphere according to 1~10 DEG C/h of rate
200~600 DEG C, and 1-5 hours are kept the temperature, 800~1400 DEG C then are continuously heating to according to 1~10 DEG C/h, and in the temperature
Lower heat preservation 1~10 hour.According to said method preparation cost is low, and gained Si-B-N-O superfine fibre diameter is evenly distributed, carbon content is low,
Gained fibrous inside contains a large amount of uniform porous structures, low-fiber density can be further dropped, to improve Jie of fiber
Electrical property.Other steps press method and step commonly used in the art in this method.Specific high temperature firing be firing temperature be 200~
1400 DEG C, firing time is 1~15h.The diameter of gained fiber is adjustable in 0.5~5 μ m.During high temperature firing, use
Ammonia can effectively remove the carbon in raw materials used.To the carbon content being effectively reduced in gained fiber.
Further, configuring spin finish aid used in spinning solution step is polyethylene oxide, polyvinylpyrrolidone or poly-
Vinyl alcohol；Molecular weight Mw=30000~1500000 of spin finish aid.Gained spinning can be improved using the spin finish aid of the type
The uniformity of liquid, to improve the diameter uniformity of gained fiber.The mechanism of spin finish aid used, group, molecular weight are dissolved in molten
After in agent, the solution viscosity of gained spinning solution, electric conductivity, surface tension, which are conducive to be formed by subsequent electrostatic spinning, to be had
The porous Si-B-N-O superfine fibre fiber of homogeneous diameter.And for SiBNO material, the carbon in above-mentioned spin finish aid is logical
The heating schedule of above-mentioned high temperature firing is crossed, can preferably remove to obtain having ultra-fine compared with the porous Si-B-N-O of low carbon content
Fiber.
Further, the molecular weight M of spin finish aidwIt is 1300000.Using the spin finish aid of the molecular weight, gained spinning
The uniformity of liquid is optimal, and the carbon content in the ultra-fine long and slender dimension of the porous Si-B-N-O of gained is minimum.
Further, it is that 0.1~2.0:1 is mixed that configuration spinning solution step includes: by boron source and siloxanes in mass ratio, will
The spinning for accounting for spinning solution gross mass 0.5~2.0% is added after boron source and modified siloxane 0.1~2.0:1 in mass ratio mixing
Auxiliary agent is mixed 3~6 hours, ultrasonic disperse 0.5~1 hour, obtains spinning solution.Spinning solution is configured by this step, can be improved
The uniformity of gained spinning solution, to guarantee the diameter uniformity of gained fiber.The source B used herein is boric acid, borogen etc.
Boracic class presoma.Wherein siloxanes and modified siloxane used can be common siloxanes.
Further, siloxane molecule general formula: (R1O)pSi(OR2)4-p, wherein alkyl R1And R2=methyl, ethyl, third
Base, butyl；R1And R2It is identical or different；P=0,1,2,3；Modified siloxane general molecular formula: R3 mSi(OR4)4-m, wherein alkyl R3
And R4=methyl, vinyl, ethyl, propyl, butyl；R3And R4It is identical or different；M=0,1,2,3.
Further, spinning solution is using ethyl alcohol and acid solution as solvent, acid solution be concentration be 0.1~1mol/L hydrochloric acid,
Nitric acid or sulfuric acid solution.To increase acid solution in a solvent, the dissolubility of siloxanes and boron source can be improved.
Further, electrostatic spinning process parameter: spinning syringe needle internal diameter is 0.5~1.5mm, spinning voltage be 8~
25kV, receive flight lead from be 5~30 μ l/ minutes for 10~30cm, feeding rate, spinning temperature is 10~60 DEG C, air is relatively wet
Degree is 20RH%~80RH%.Electrostatic spinning is carried out by this technological parameter, adaptation of the electrostatic spinning process to spinning solution can be improved
Ability.
Further, drying steps are 5~48 hours dry at 50~120 DEG C.It is dried, can improve by this step
The aridity of gained fiber.Guarantee dry thorough.
Another aspect of the present invention additionally provides a kind of porous Si-B-N-O superfine fibre, porous Si-B-N-O superfine fibre
It is prepared for above-mentioned method.
Preparation method provided by the invention specifically includes the following steps:
(1) preparation of spinning solution: the boron source (B) and siloxanes 0.1~2.0:1 in mass ratio, the boron source (B) and modified siloxane
0.1~2.0:1 in mass ratio, ethyl alcohol and acid solution are solvent, and spin finish aid accounts for the 0.5~2.0% of solution gross mass, and mixing is stirred
3-6h, ultrasonic disperse 0.5-1h are mixed, clear spin finish aid solution is obtained；
(2) electrostatic spinning: technological parameter include: spinning syringe needle internal diameter be 0.5~1.5mm, spinning voltage be 8~25kV,
Receive flight lead from be 5~30 μ l/min for 10~30cm, feeding rate, spinning temperature is 10~60 DEG C, relative air humidity is
20RH%~80RH%.Obtain PBSO fibrinogen；
(3) dry: PBSO fibrinogen being placed in drying box and is dried, temperature is 50~120 DEG C, drying time
For 5~48h；
(4) high temperature firing: dry PBSO fibrinogen is placed in high temperature furnace, in NH3And/or N2Under mixed-gas atmosphere
200~600 DEG C are warming up to according to the rate of 1~10 DEG C/h, and keeps the temperature 1-5h, is then continuously heating to 800 according to 1~10 DEG C/h
~1400 DEG C, and 1~10h is kept the temperature at such a temperature, porous Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Technical effect of the invention:
The preparation method that the present invention provides porous Si-B-N-O superfine fibre is main with siloxanes, modified siloxane and boron source
Raw material, low raw-material cost, reaction condition is mild, and spinning technique is simple, by improving the heating and firing program of high temperature firing,
To obtain the superfine fibre with a large amount of even porous structures.
The present invention provides the preparation method of porous Si-B-N-O superfine fibre, preparation-obtained spinning solution good spinnability,
The molecule formed in solution, linearity are better.The spinning solution spinnability that SiBNO fiber is used to prepare in existing method is poor,
SiBNO electrostatic spinning raw material solution with preferable spinning properties is difficult to arrange, and optional raw material is excessive.
The present invention provides the preparation method of porous Si-B-N-O superfine fibre, by the screening to spin finish aid, and cooperates
Firing temperature is reduced remaining carbon content in the porous Si-B-N-O fiber of gained, and uniformly more in fibrous inside
Pore structure, to help to improve the dielectric properties of material.
The present invention provides porous Si-B-N-O superfine fibre, and diameter is evenly distributed, and size is adjustable in 0.5~5 μ m.
Specifically please refer to the various implementations of porous Si-B-N-O superfine fibre according to the present invention and preparation method thereof proposition
Example it is described below, will make apparent in terms of above and other of the invention.
Detailed description of the invention
Fig. 1 is the SEM photograph of the porous Si-B-N-O superfine fibre of gained in the preferred embodiment of the present invention, a) porous for gained
The whole SEM photograph of Si-B-N-O superfine fibre；B) it is shone for the local sectional cross section SEM of the porous Si-B-N-O superfine fibre of gained
Piece；
Fig. 2 is the XPS spectrum figure of the porous Si-B-N-O superfine fibre of gained in the preferred embodiment of the present invention.
Specific embodiment
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.
Embodiment 1
The present embodiment prepares the preparation method of porous Si-B-N-O superfine fibre, comprising the following steps:
(1) spinning solution is prepared: by polyethylene glycol oxide (Mw=1300000), ethyl alcohol, diluted acid (1mol/L, dilute hydrochloric acid) are pressed
Quality proportioning (1:40:20) is mixed 4 hours, and ultrasonic disperse is at PEO solution, by starting boronic acid, ethyl orthosilicate, vinyl
Trimethoxy silane is added in PEO solution, is stirred 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1, positive silicic acid second
The mass ratio of ester and ethyl alcohol is 2:1, and the mass ratio of vinyltrimethoxysilane and ethyl alcohol is 2:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.8mm, selects voltage 15kV, receives flight lead from (needle point to receiving screen
Vertical range) 12cm and 15 μ of feeding rate l/ minutes, spinning temperature is 20 DEG C, relative air humidity 60RH%, using flat
Face aluminium foil receives filament plate and carries out electrostatic spinning to spinning solution, and PBSO fibrinogen is made；
(3) dry: above-mentioned PBSO fibrinogen to be placed in baking oven, under air 60 DEG C of heat preservations drying in 12 hours；
(4) dry fiber high temperature firing: is placed at NH3And N2In the high temperature furnace of mixed-gas atmosphere, according to heating speed
It 10 DEG C/min of rate, is sloughed at 300 DEG C spin finish aid (being warming up to 300 DEG C), soaking time is 1 hour, 9 DEG C/minute of heating rate
Clock, pyrolysis temperature are 800 DEG C, and soaking time is 1 hour, and porous Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
SEM photograph such as Fig. 1 of porous Si-B-N-O superfine fibre, XPS spectrum figure obtained by this example are as shown.
As it can be seen that the diameter of the porous Si-B-N-O superfine fibre of gained is evenly distributed shown in Fig. 1 a), diameter is about
3.75μm.From in the b of Fig. 1) as it can be seen that uniformly distributed a large amount of microcellular structures in the porous Si-B-N-O superfine fibre of gained, and each hole
Structure distribution is uniform.Analyze from Fig. 2 it is found that mainly contain four kinds of elements in gained fiber, Si judged by peak intensity, O content compared with
Height, B, N content are few.The porous Si-B-N-O superfine fibre of gained is mainly made of Si, O, a small amount of B and N.Si-B- porous to gained
N-O superfine fibre is checked that C content is 0.06% in sample using the CS-444 carbon and sulphur detector of U.S. LECO company.It says
Carbon content is effectively reduced in the bright porous Si-B-N-O superfine fibre obtained using method provided by the invention.
Embodiment 2
The preparation method of the porous Si-B-N-O superfine fibre of the present embodiment, comprising the following steps:
(1) spinning solution is prepared: by polyethylene glycol oxide (Mw=1300000), ethyl alcohol, dilute hydrochloric acid (1mol/L) are matched by quality
It is mixed 4 hours than (1:40:20), ultrasonic disperse is at PEO solution, by starting boronic acid, methyl orthosilicate, methyl trimethoxy oxygroup
Silane is added in PEO solution and stirs 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1, methyl orthosilicate and ethyl alcohol
Mass ratio is 2:1, and the mass ratio of methyltrimethoxysilane and ethyl alcohol is 2:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.8mm, selects voltage 15kV, receives flight lead from 12cm and feeding rate
15 μ l/ minutes, spinning temperature be 20 DEG C, relative air humidity 60RH%, using plane aluminium foil receive filament plate to spinning solution into
PBSO fibrinogen is made in row electrostatic spinning；
(3) dry: PBSO fibrinogen obtained to be placed in baking oven, under air in 60 DEG C of heat preservations drying in 12 hours；
(4) fiber of above-mentioned drying high temperature firing: is placed at NH3In the high temperature furnace of gas atmosphere, according to heating rate
It is 9 DEG C/min, spin finish aid is sloughed at 300 DEG C, soaking time is 1 hour, and heating rate is 9 DEG C/min, high temperature pyrolysis temperature
Degree is 800 DEG C, and soaking time is 1 hour, and porous Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Si-B-N-O superfine fibre obtained by the present embodiment, diameter are evenly distributed, and diameter is about 2.8 μm, cut from fiber
Face finds out, fiber by by porous structure form.
Embodiment 3
The preparation method of the Si-B-N-O superfine fibre of the present embodiment, comprising the following steps:
(1) spinning solution is prepared: by polyethylene glycol oxide (Kw=1300000), ethyl alcohol, dilute hydrochloric acid (1mol/L) are matched by quality
4h is mixed than (1:40:20), ultrasonic disperse is at PEO solution, by starting boronic acid, ethyl orthosilicate, vinyl trimethoxy
Silane is added in PEO solution and stirs 1h；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1, the matter of ethyl orthosilicate and ethyl alcohol
Ratio is measured as 2:1, the mass ratio of vinyltrimethoxysilane and ethyl alcohol is 2:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.8mm, selects voltage 15kV, receives flight lead from (needle point to receiving screen
Vertical range) 12cm and 15 μ of feeding rate l/ minutes, spinning temperature is 20 DEG C, relative air humidity 60RH%, using flat
Face aluminium foil receives filament plate and carries out electrostatic spinning to spinning solution, and PBSO fibrinogen is made；
(3) dry: PBSO fibrinogen obtained to be placed in baking oven, under air in 60 DEG C of heat preservations drying in 12 hours；
(4) fiber of above-mentioned drying high temperature firing: is placed in N2In the high temperature furnace of gas atmosphere, it is according to heating rate
1 DEG C/min, spin finish aid is sloughed at 200 DEG C, soaking time is 1 hour, and heating rate is 2 DEG C/min, pyrolysis temperature
It is 800 DEG C, soaking time is 1 hour, and Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Fiber surface obtained by the present embodiment is smooth, and flawless is porous, and diameter is evenly distributed, and diameter is about 0.6~0.8 μm.
Embodiment 4
The preparation method of the Si-B-N-O superfine fibre of the present embodiment, includes the following steps are as follows:
(1) spinning solution is prepared: by polyethylene glycol oxide (Kw=1300000), ethyl alcohol, dilute hydrochloric acid (1mol/L) are matched by quality
It is mixed 4 hours than (1:40:20), ultrasonic disperse is at PEO solution, by starting boronic acid, ethyl orthosilicate, vinyl trimethoxy
Base silane is added in PEO solution and stirs 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1, ethyl orthosilicate and ethyl alcohol
Mass ratio be 2:1, the mass ratio of vinyltrimethoxysilane and ethyl alcohol is 2:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.8mm, selects voltage 15kV, receives flight lead from (12cm and feed speed
15 μ of rate l/ minutes, spinning temperature are 20 DEG C, relative air humidity 60RH%, and right using aluminium foil receipts silk, spinning solution carries out quiet
PBSO fibrinogen is made in Electrospun；
(3) dry: PBSO fibrinogen obtained to be placed in baking oven, under air in 60 DEG C of heat preservations drying in 12 hours；
(4) above-mentioned PBSO fibrinogen high temperature firing: is placed at NH3And N2In the high temperature furnace of mixed-gas atmosphere, according to liter
Warm rate is 3 DEG C/min, and spin finish aid is sloughed at 600 DEG C, and soaking time is 1 hour, and heating rate is 3 DEG C/min, high temperature
Pyrolysis temperature is 1000 DEG C, and soaking time is 1 hour, and Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Fiber surface obtained by the present embodiment is smooth, and flawless is porous, and diameter is evenly distributed, and diameter is about 0.6 μm.
Embodiment 5.
The present embodiment prepares the step of Si-B-N-O superfine fibre are as follows:
(1) spinning solution is prepared: by polyvinylpyrrolidone (Kw=300000), ethyl alcohol, dilute hydrochloric acid (1mol/L) press matter
Amount proportion (1:40:20) is mixed 4 hours, and ultrasonic disperse is at PVP solution, by starting boronic acid, siloxanes (R1O)pSi
(OR2)4-p(wherein, alkyl R1=butyl, R2=methyl；P=3), modified siloxane R3 mSi(OR4)4-m(alkyl R3And R4=first
Base；M=0 it) is added in PVP solution and stirs 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1, siloxanes and ethyl alcohol
Mass ratio is 2:1, and the mass ratio of modified siloxane and ethyl alcohol is 2:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.8mm, selects voltage 15kV, receives flight lead from 12cm and feeding rate
15 μ l/ minutes, spinning temperature be 20 DEG C, relative air humidity 60RH%, using plane aluminium foil receive filament plate to spinning solution into
PBSO fibrinogen is made in row electrostatic spinning；
(3) dry: PBSO fibrinogen obtained to be placed in baking oven, under air in 60 DEG C of heat preservations drying in 12 hours；
(4) fiber of above-mentioned drying high temperature firing: is placed at NH3And N2In the high temperature furnace of mixed-gas atmosphere, according to
Heating rate is 3 DEG C/min, and spin finish aid is sloughed at 300 DEG C, and soaking time is 1 hour, and heating rate is 3 DEG C/min, high
Warm pyrolysis temperature is 1000 DEG C, and soaking time is 1 hour, and Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Fiber surface obtained by the present embodiment is smooth, and flawless is porous, and diameter is evenly distributed, and diameter is about 2.5~3.5 μm.
Embodiment 6
The preparation method of the porous Si-B-N-O superfine fibre of the present embodiment, comprising the following steps:
(1) spinning solution is prepared: by polyvinyl alcohol (Mw=1500000), ethyl alcohol, dilute hydrochloric acid (1mol/L) press quality proportioning
(1:60:13) be mixed 3 hours, ultrasonic disperse 1 hour at PEO solution, by starting boronic acid, siloxanes (R1O)pSi(OR2)4-p
(wherein, alkyl R1And R2=methyl；R1And R2It is identical；P=0), modified siloxane R3 mSi(OR4)4-m(alkyl R3=vinyl and
R4=ethyl；M=1 it) is added in PEO solution and stirs 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.1:1, positive silicic acid first
The mass ratio of ester and ethyl alcohol is 1:1, and the mass ratio of modified siloxane and ethyl alcohol is 0.1:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 1.5mm, selects voltage 25kV, receives flight lead from 10cm and feeding rate
5 μ l/ minutes, spinning temperature are 10 DEG C, relative air humidity 80RH%, receive filament plate using plane aluminium foil and carry out to spinning solution
PBSO fibrinogen is made in electrostatic spinning；
(3) dry: PBSO fibrinogen obtained to be placed in baking oven, under air in 50 DEG C of heat preservations drying in 5 hours；
(4) fiber of above-mentioned drying high temperature firing: is placed at NH3And N2In the high temperature furnace of mixed-gas atmosphere, according to liter
Warm rate is 9 DEG C/min, and spin finish aid is sloughed at 300 DEG C, and soaking time is 5 hours, and heating rate is 10 DEG C/min, high temperature
Pyrolysis temperature is 800 DEG C, and soaking time is 10 hours, and porous Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Si-B-N-O superfine fibre obtained by the present embodiment, diameter are evenly distributed, and diameter is about 2.5 μm, cut from fiber
Face finds out, fiber by by porous structure form.
Embodiment 7
The present embodiment prepares the preparation method of porous Si-B-N-O superfine fibre, comprising the following steps:
(1) spinning solution is prepared: by polyethylene glycol oxide (Mw=1300000), ethyl alcohol, diluted acid (0.1mol/L, sulfuric acid) are pressed
Quality proportioning (4:30:37) be mixed 7 hours, ultrasonic disperse 0.5 hour at PEO solution, by starting boronic acid, siloxanes
(R1O)pSi(OR2)4-p(wherein, alkyl R1=methyl and R2=ethyl；P=1, modified siloxane R3 mSi(OR4)4-m(alkyl R3=
Butyl and R4=propyl；M=2 it) is added in PEO solution, stirs 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1,
The mass ratio of siloxanes and ethyl alcohol is 0.15:1, and the mass ratio of modified siloxane and ethyl alcohol is 0.15:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.5mm, selects voltage 8kV, receives flight lead from (needle point to receiving screen
Vertical range) 30cm and 30 μ of feeding rate l/ minutes, spinning temperature is 60 DEG C, relative air humidity 20RH%, using plane
Aluminium foil receives filament plate and carries out electrostatic spinning to spinning solution, and PBSO fibrinogen is made；
(3) dry: above-mentioned PBSO fibrinogen to be placed in baking oven, under air 120 DEG C of heat preservations drying in 48 hours；
(4) dry fiber high temperature firing: is placed at NH3And N2In the high temperature furnace of mixed-gas atmosphere, according to heating speed
9 DEG C/min of rate, slough spin finish aid at 300 DEG C, soaking time is 1 hour, 1 DEG C/min of heating rate, pyrolysis temperature
It is 1400 DEG C, soaking time is 1 hour, and porous Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Si-B-N-O superfine fibre obtained by the present embodiment, diameter are evenly distributed, and diameter is about 2.7 μm, cut from fiber
Face finds out, fiber by by porous structure form.
Embodiment 8
The present embodiment prepares the preparation method of porous Si-B-N-O superfine fibre, comprising the following steps:
(1) spinning solution is prepared: by polyethylene glycol oxide (Mw=1300000), ethyl alcohol, diluted acid (1mol/L, dilute hydrochloric acid) are pressed
Quality proportioning (1:40:20) is mixed 4 hours, and ultrasonic disperse is at PEO solution, by starting boronic acid, siloxanes (R1O)pSi
(OR2)4-p(wherein, alkyl R1=butyl and R2=propyl；P=2), modified siloxane R3 mSi(OR4)4-m(alkyl R3And R4=first
Base；M=3 it) is added in PEO solution, stirs 1 hour；Wherein the mass ratio of boric acid and ethyl alcohol is 0.3:1, siloxanes and ethyl alcohol
Mass ratio be 2:1, the mass ratio of modified siloxane and ethyl alcohol is 2:1；
(2) electrostatic spinning: using internal diameter for the syringe needle of 0.8mm, selects voltage 15kV, receives flight lead from (needle point to receiving screen
Vertical range) 12cm and 15 μ of feeding rate l/ minutes, spinning temperature is 20 DEG C, relative air humidity 60RH%, using flat
Face aluminium foil receives filament plate and carries out electrostatic spinning to spinning solution, and PBSO fibrinogen is made；
(3) dry: above-mentioned PBSO fibrinogen to be placed in baking oven, under air 130 DEG C of heat preservations drying in 50 hours；
(4) dry fiber high temperature firing: is placed at NH3And N2In the high temperature furnace of mixed-gas atmosphere, according to heating speed
9 DEG C/min of rate, slough spin finish aid at 300 DEG C, soaking time is 1 hour, 9 DEG C/min of heating rate, pyrolysis temperature
It is 800 DEG C, soaking time is 1 hour, and porous Si-B-N-O superfine fibre is obtained after being cooled to room temperature.
Si-B-N-O superfine fibre obtained by the present embodiment, diameter are evenly distributed, and diameter is about 3.0 μm, cut from fiber
Face finds out, fiber by by porous structure form.
Those skilled in the art will be clear that the scope of the present invention is not limited to example discussed above, it is possible to carry out to it
Several changes and modification, the scope of the present invention limited without departing from the appended claims.Although oneself is through in attached drawing and explanation
The present invention is illustrated and described in book in detail, but such illustrate and describe is only explanation or schematical, and not restrictive.
The present invention is not limited to the disclosed embodiments.
By to attached drawing, the research of specification and claims, those skilled in the art can be in carrying out the present invention
Understand and realize the deformation of the disclosed embodiments.In detail in the claims, term " includes " is not excluded for other steps or element,
And indefinite article "one" or "an" be not excluded for it is multiple.The certain measures quoted in mutually different dependent claims
The fact does not mean that the combination of these measures cannot be advantageously used.Any reference marker in claims is not constituted pair
The limitation of the scope of the present invention.
Claims (6)
1. a kind of porous Si-B-N-O superfine fibre preparation method, which comprises the following steps: configuration spinning solution leads to
It crosses electrostatic spinning and obtains PBSO fibrinogen, obtain the porous Si-B-N-O through high temperature firing to after PBSO fibrinogen drying
Superfine fibre；
The high temperature firing step includes: in NH3200 ~ 600 DEG C are warming up to according to 1 ~ 10 DEG C/h of rate under atmosphere, and is protected
It is 1-5 hours warm, 800 ~ 1400 DEG C then are continuously heating to according to 1 ~ 10 DEG C/h, and keep the temperature 1 ~ 10 hour at such a temperature；
Spin finish aid used is polyethylene oxide or polyvinyl alcohol in the configuration spinning solution step；The molecule of the spin finish aid
Measure Mw=30000~1500000；
It is that 0.1~2.0:1 is mixed that the configuration spinning solution step includes: by boron source and siloxanes in mass ratio, by boron source and is changed
Property siloxanes 0.1~2.0:1 in mass ratio mixing after, add the spin finish aid for accounting for the spinning solution gross mass 0.5~2.0%,
It is mixed 3 ~ 6 hours, ultrasonic disperse 0.5 ~ 1 hour to get spinning solution；
The siloxane molecule general formula: (R1O)pSi(OR2)4-p, wherein alkyl R1And R2=methyl, ethyl, propyl, butyl；R1And
R2It is identical or different；p = 0,1,2,3；
The modified siloxane general molecular formula: R3 mSi(OR4)4-m, wherein alkyl R3And R4=methyl, vinyl, ethyl, propyl,
Butyl；R3And R4It is identical or different；m=1,2,3.
2. porous Si-B-N-O superfine fibre preparation method according to claim 1, which is characterized in that the spin finish aid
Molecular weight MwIt is 1300000.
3. porous Si-B-N-O superfine fibre preparation method according to claim 2, which is characterized in that the spinning solution with
Ethyl alcohol and acid solution are solvent, and the acid solution is hydrochloric acid, nitric acid or the sulfuric acid solution that concentration is 0.1~1mol/L.
4. porous Si-B-N-O superfine fibre preparation method described according to claim 1 ~ any one of 3, which is characterized in that institute
State electrostatic spinning process parameter: spinning syringe needle internal diameter is 0.5~1.5mm, spinning voltage be 8~25kV, receive flight lead from for
10~30cm, feeding rate be 5~30 μ L/min, spinning temperature be 10~60 DEG C, relative air humidity be 20RH%~
80RH%。
5. porous Si-B-N-O superfine fibre preparation method according to claim 4, which is characterized in that the drying steps
It is 5~48 hours dry at 50~120 DEG C.
6. a kind of porous Si-B-N-O superfine fibre, which is characterized in that the porous Si-B-N-O superfine fibre is to want by right
Method described in asking any one of 1 ~ 5 is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610892319.9A CN106337217B (en) | 2016-10-12 | 2016-10-12 | A kind of porous Si-B-N-O superfine fibre and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610892319.9A CN106337217B (en) | 2016-10-12 | 2016-10-12 | A kind of porous Si-B-N-O superfine fibre and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106337217A CN106337217A (en) | 2017-01-18 |
| CN106337217B true CN106337217B (en) | 2018-12-28 |
Family
ID=57839300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610892319.9A Active CN106337217B (en) | 2016-10-12 | 2016-10-12 | A kind of porous Si-B-N-O superfine fibre and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106337217B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624991A (en) * | 2018-05-10 | 2018-10-09 | 浙江梵彼斯特轻纺发展有限公司 | A kind of preparation method of borosilicate ceramic fibre |
| CN112176457B (en) * | 2020-10-12 | 2022-12-06 | 中国人民解放军国防科技大学 | Flexible porous multiphase SiZrNOC micro nano heat insulation fiber and preparation method thereof |
| CN114907128B (en) * | 2022-06-24 | 2023-04-25 | 中国人民解放军国防科技大学 | SiBNO heat-insulating wave-transmitting integrated fiber and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999004073A1 (en) * | 1997-07-18 | 1999-01-28 | Japan Science And Technology Corporation | Hollow microfiber and process for preparing the same |
| CN101830706A (en) * | 2010-05-28 | 2010-09-15 | 中国人民解放军国防科学技术大学 | Method for continuously preparing Si-B-N-O fiber by using PCS (Polycarbosilane) fiber |
| CN103121847A (en) * | 2013-01-24 | 2013-05-29 | 中国地质大学（北京） | Preparation method of SiBON wave-transmitting material |
| CN104178846A (en) * | 2014-07-28 | 2014-12-03 | 中国人民解放军国防科学技术大学 | Preparation method of Si-M-O-C superfine fibers |
| CN104774015A (en) * | 2014-01-14 | 2015-07-15 | 广州市香港科大***研究院 | Controllable-morphology high-porosity porous ceramic membrane supporting body and preparation method thereof |
| US20150224468A1 (en) * | 2014-02-12 | 2015-08-13 | Ut-Battelle, Llc | Method of synthesizing silica nanofibers using sound waves |
-
2016
- 2016-10-12 CN CN201610892319.9A patent/CN106337217B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999004073A1 (en) * | 1997-07-18 | 1999-01-28 | Japan Science And Technology Corporation | Hollow microfiber and process for preparing the same |
| CN101830706A (en) * | 2010-05-28 | 2010-09-15 | 中国人民解放军国防科学技术大学 | Method for continuously preparing Si-B-N-O fiber by using PCS (Polycarbosilane) fiber |
| CN103121847A (en) * | 2013-01-24 | 2013-05-29 | 中国地质大学（北京） | Preparation method of SiBON wave-transmitting material |
| CN104774015A (en) * | 2014-01-14 | 2015-07-15 | 广州市香港科大***研究院 | Controllable-morphology high-porosity porous ceramic membrane supporting body and preparation method thereof |
| US20150224468A1 (en) * | 2014-02-12 | 2015-08-13 | Ut-Battelle, Llc | Method of synthesizing silica nanofibers using sound waves |
| CN104178846A (en) * | 2014-07-28 | 2014-12-03 | 中国人民解放军国防科学技术大学 | Preparation method of Si-M-O-C superfine fibers |
Non-Patent Citations (1)
| Title |
|---|
| "SiBON材料制备技术及反应机理研究";李建权;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20121215(第12期);第B020-35页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106337217A (en) | 2017-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106337217B (en) | A kind of porous Si-B-N-O superfine fibre and preparation method thereof | |
| CN106609404B (en) | A kind of low density and high performance aluminium oxide base ceramic fibre and preparation method thereof | |
| CN107266081B (en) | Preparation method of alumina-zirconia composite ceramic continuous fiber | |
| CN101994169B (en) | Continuous silicon carbide fiber preparation method and production device | |
| Chen et al. | Electrospun mullite fibers from the sol–gel precursor | |
| CN107653518B (en) | High-orientation-degree continuous superfine/nano alumina-based ceramic fiber bundle material and preparation method thereof | |
| US7390476B2 (en) | Carbon fiber paper construction and manufacturing process | |
| Liu et al. | Fabrication of high‐strength continuous zirconia fibers and their formation mechanism study | |
| CN102965764A (en) | Preparation method of aluminum oxide ceramic continuous fiber | |
| CN104141181B (en) | A kind of containing SiO2the ZrO of doping2the preparation method of fiber | |
| CN109437862B (en) | Containing 1-5 wt% of B2O3Preparation method of alumina-based ceramic continuous fiber | |
| CN108486689B (en) | Preparation method of high-modulus high-thermal-conductivity asphalt-based carbon fiber continuous filament | |
| CN104291812A (en) | Siloxate/metal oxide continuous multiphase ceramic fiber preparation method | |
| CN106637510B (en) | A kind of preparation method of Zirconium oxide fibre | |
| CN101428813B (en) | Process for producing ultra-fine boron nitride continuous nano-fibre | |
| CN104178846B (en) | A kind of preparation method of Si-M-O-C superfine fibre | |
| CN101949073A (en) | Preparation method of superfine zirconium oxide/silicon carbide fiber with radial and gradient distribution | |
| CN105671688A (en) | Method for preparing ultrahigh-temperature ceramic fibers by means of physically blending polycarbosilane and metal oxide | |
| CN106087112B (en) | A kind of preparation method of continuous SiC fiber of the surface with carbon-coating | |
| CN103757749A (en) | Preparation method for zirconia crystal fiber | |
| CN102180656B (en) | Technology for preparing alumina-based continuous fibers by using inorganic aluminum salts | |
| CN107740205B (en) | A kind of compound organic precursor method preparation BN-Si3N4The method of complex phase ceramic continuous fiber | |
| CN103409851B (en) | Preparation method of cobalt containing silicon carbide fiber | |
| CN105671964A (en) | Preparation method of oiling agent for polyester spinning | |
| CN107955998A (en) | A kind of high soft mullite of lightweight is ultra-fine/nano ceramic fibers and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |