CN104178846A - Preparation method of Si-M-O-C superfine fibers - Google Patents
Preparation method of Si-M-O-C superfine fibers Download PDFInfo
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- CN104178846A CN104178846A CN201410360261.4A CN201410360261A CN104178846A CN 104178846 A CN104178846 A CN 104178846A CN 201410360261 A CN201410360261 A CN 201410360261A CN 104178846 A CN104178846 A CN 104178846A
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Abstract
The invention relates to a preparation method of Si-M-O-C superfine fibers. The preparation method comprises the following steps: (1) performing spinning solution preparation: adding raw materials in a reactor sequentially for preparing the spinning solution; (2) carrying out electrostatic spinning: adjusting the appropriate electrostatic spinning parameters for carrying out electrostatic spinning on the spinning solution, so as to prepare Si-M-O-C fibrils; (3) drying: drying the Si-M-O-C fibrils in a drying oven; and (4) firing at high temperature: firing the dried Si-M-O-C fibrils in inert atmosphere at high temperature, and cooling to be at room temperature. According to the preparation method, all raw materials are derived from a wealth of sources and have low cost; the spinning solution has good spinnability during electrostatic spinning, the production cycle is short, and expansive production can be realized conveniently; the Si-M-O-C fibers are distributed in a non-woven fabric state and have uniform diameter distribution, the diameter control range is within 0.5-5mum, the specific surface area is large, and the Si-M-O-C superfine fiber has wide application prospect in the fields of thermal insulation, sound insulation, catalyst support, high-temperature catalysis and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Si-M-O-C superfine fibre.
Background technology
Silica carbon (Si-O-C) pottery because it is high temperature resistant, corrosion-resistant, conduction and the easy feature of machine-shaping, be widely used in fields such as coating, MEMS, industrial accessories.Research shows, compared to Si-O-C fiber, by introducing heterogeneous element M(M=B, Zr, Hf, Ti, Ta, Nb etc.) silica carbon (Si-M-O-C) fiber that obtains adulterating, can effectively improve the heat resistance of Si-O-C fiber.It is high that Si-M-O-C fiber has overcome the shortcoming and the oxide high-temperature creep rate that under carbide high temperature, are easily oxidized, and the significantly reduced deficiency of mechanical performance, has caused numerous researchers' extensive concern.Fibrous and the structure of having precursor conversion method can design and the advantage such as regulation and control, moulding and handling ease, is one of main method of preparing at present in fiber and composite thereof.Utilize precursor conversion method to prepare Si-M-O-C fiber, synthesis technique is simple, and reaction condition requires lower, can in atmospheric environment, operate, and is therefore considered to the Perfected process that low cost is prepared high-performance ceramic based composites.Method of electrostatic spinning is to rely on the high-pressure electrostatic of several thousand to several ten thousand volts to stretch to prepare the effective ways of fiber, and except the advantage such as possess that equipment is simple, cost is low and applicability is wide, employing electrospinning process is also expected to realize the large-scale production of fiber.
The people such as Li
[1]in polysiloxanes (PSO), introduce boron element, obtain the Si-B-O-C fiber of diameter 5 μ m, fiber surface is rough, in high temperature sintering process between fiber and fiber easily bonding (doubling), low ([1] the Xia Li of gained fibre strength, G Wen, Tao Zhang, Long Xia, Bo Zhang, Shaoyu Fan. Large-scale Synthesis of Si-B-O-C Fibers Produced By Elecetrospinning[J]. Physcis Procedia, 2012,25:189-193).
G. D. Soraru seminar
[2]smooth surface, flawless Si-B-O-C ceramic fibre are prepared taking modified siloxane as raw material by the method for manual Pick Wire, but its diameter slightly (is about 10 μ m), little ([2] the Raquel Pena-Alonso of specific area, G. D. Soraru, Synthesis and characterization of hybrid borosiloxane gels as precursors for Si – B – O – C fibers[J]. J. Sol-Gel Sci. Technol, 2007,43:313-319).
A.Tamayo etc.
[3]people adopts spin processes to obtain Si-B-O-C fiber, but because precursor molecular weight is low, spinning effect is poor, gained fiber surface has hole, and distribution of fiber diameters is extremely inhomogeneous, mainly ([3] A. Tamayo more than 5 μ m of diameter distribution, R. Pena-Alonso, F. Rubio, J. Rubio, J. L. Oteo, Synthesis and characterization of boron oxycarbide glass fibers[J]. J. Non-Cyst. Solids, 2012,358:155-162).
CN101805171A discloses a kind of preparation method of Si-B-O-C precursor, adopts the method for manual Pick Wire to prepare Si-B-O-C fiber, but its fibre diameter is thick, (be about 10 μ m), specific area is little, and is unsuitable for large-scale production.
Cao Shuwei etc.
[4]people is to gather silicon-carbon silane and acetylacetone,2,4-pentanedione zirconium as the synthetic poly-zirconium carbon silane of raw material, adopt melt-spinning technology to prepare Si-Zr-O-C fiber, average fibre diameter 11 μ m([4] Cao Shuwei, Xie Zhengfang, Wang Jun, Wang Hao, Xue Jingen, Niu Jiaxin, the fire-resistant oxidation resistant performance study [J] of Si-Zr-C-O fiber. chemical journal, 2010,68 (5): 418-424).
Wang Yifei etc.
[5]people is with the synthetic different poly-titanium carbon silane precursor of phosphorus content of polysilane, polyvinyl chloride and butyl titanate, adopt melt-spinning technology to prepare rich carbon tensile strength (Si-Ti-O-C fiber), diameter is about 14 μ m([5] Wang Yifei, Zhao Peng, Song Yongcai, Feng Chunxiang, the development [J] of rich carbon tensile strength. novel charcoal material, 2000,15 (2): 57-60).
Ox pay rise etc.
[6]the product liquid polysilane that people makes with poly dimethyl silane pyrolysis reacts with columbium pentachloride, prepare the poly-niobium carbon silane of precursor containing niobium SiC ceramic fibre, adopt melt-spinning technology to prepare Si-Nb-O-C fiber, average diameter 12 μ m([6] Niu Jiaxin, Xie Zhengfang, Xue Jingen, Wang Hao, synthetic and sign, the silicate journal [J] of the poly-niobium carbon silane of SiC (Nb) ceramic fiber precursor. 2009,37 (2): 171-175).
In general, the preparation of Si-M-O-C fiber at present mainly contains the deficiency of following two aspects: 1, the raw material ratio of synthetic Si-M-O-C precursor is more limited, and preparation cost is higher.2, preparation method is mainly melt spinning method or manual Pick Wire method, and the diameter of gained fiber is thicker, and specific area is little, and the distribution of fiber diameters that especially manually Pick Wire method obtains is inhomogeneous.
Summary of the invention
Technical problem to be solved by this invention is, a kind of low cost of manufacture is provided, gained fiber surface is smooth, flawless, without hole, the preparation method of the Si-M-O-C superfine fibre that diameter is evenly distributed.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of Si-M-O-C superfine fibre, comprises the following steps:
(1) be preferably 0.8～1.5:10:6 of 0.5～2.0:10:6(by polyvinylpyrrolidone, ethanol, acid solution in quality proportioning) the preferred 4h of ratio mix and blend 3-6h(), the ultrasonic PVP solution that is dispersed into;
Raw material M source, siloxanes, modified siloxane are joined in PVP solution, stir the preferred 1.0h of 0.5-2.0h(), wherein the mass ratio of M source and ethanol is preferably 0.3～0.7:1.0 of 0.1～2.0:1.0(), the mass ratio of siloxanes and ethanol is the preferred 2:1 of 1～3:1(), the mass ratio of modified siloxane and ethanol is the preferred 2:1 of 1～3:1(), be mixed with spinning solution:
Described M source is the presoma of doped chemical M, and element M can be B, Ti, Zr, Hf, Ta or Nb;
The general molecular formula of described siloxanes is as follows:
(R
1O)
pSi(OR
2)
4-p
Wherein, alkyl R
1and R
2=methyl, ethyl, propyl group, butyl; R
1and R
2identical or different; P=0,1,2,3;
The general molecular formula of described modified siloxane is as follows:
R
3 mSi(OR
4)
4-m
Wherein, alkyl R
3and R
4=methyl, vinyl, ethyl, propyl group, butyl; R
3and R
4identical or different; M=0,1,2,3;
(2) spinning solution of step (1) gained is carried out to electrostatic spinning, collect Si-M-O-C fibrillation;
(3) the Si-M-O-C fibrillation of step (2) gained is placed in to drying box and is dried processing;
(4) the dry Si-M-O-C fibrillation of step (3) gained is placed in to the high temperature furnace under inert atmosphere protection, heats up according to 1～10 DEG C/h, be warming up to 800～1600 DEG C, insulation 1～10h, is cooled to room temperature, obtains ultra-fine Si-M-O-C fiber.
Further, in step (1), in the time of M=B, M source is boric acid (B (OH)
3), borogen (B (OEt)
3) etc. boracic presoma; In the time of M=Ti, M source is butyl titanate (Ti (O
nbu)
4), isopropyl titanate (Ti (O
ipr)
4) etc. titaniferous presoma; In the time of M=Zr, M source is tetrabutyl zirconate (Zr (O
nbu)
4), the zirconic acid tert-butyl ester (Zr (O
tbu)
4) etc. containing zirconium precursor body; In the time of M=Hf, M source is hafnium acetoacetic ester (Hf (O
net)
4), hafnium tert-butyl acrylate (Hf (O
tbu)
4) etc. containing hafnium presoma; In the time of M=Ta, M source is tantalic acid ethyl ester (Ta (OEt)
5), the tantalic acid tert-butyl ester (Ta (O
tbu)
5) etc. containing tantalum presoma; In the time of M=Nb, M source is niobic acid ethyl ester (Nb (OEt)
5), niobic acid isopropyl ester (Nb (O
ipr)
5) etc. containing niobium presoma.
Further, in step (1), the molecular weight M of described polyvinylpyrrolidone
w=30000～1500000(preferably 1300000).
Further, in step (1), hydrochloric acid, nitric acid or sulfuric acid that described acid solution is 0.1～1mol/L, the preferably hydrochloric acid of 1mol/L.
Further, in step (2), electrostatic spinning process parameter comprises: to adopt internal diameter be 0.5～1.5mm syringe needle, preferably 15～20kV of spinning voltage 12～30kV(), to receive flight lead be that 10～60 DEG C of (preferably 20～30 DEG C), relative air humidities are the preferred 40RH%～70RH% of 20RH%～80RH%(from (needle point is to the vertical range of receiving screen) 10～30cm, feeding rate 5～30 μ l/min, spinning temperature).
Further, in step (3), dry temperature is 50～120 DEG C, and the dry time is 12～30h.
It is hydrolytie polycondensation under catalyst by little molecule siloxanes and M source that the present invention prepares Si-M-O-C superfine fibre, burn till through electrostatic spinning, dry and high temperature, obtain diameter controlled range be about 0.5～5 μ m smooth surface, flawless, without empty ceramic fibre.The method by add high molecular polymer (PVP) as spin finish aid with regulation and control spinning solution spinning properties, obtain the Si-M-O-C fibrillation that diameter is evenly distributed.Can obtain by electrostatic spinning technique the superfine fibre that specific area is large, the advantage that in addition, that electrostatic spinning technique has is simple to operate, be convenient to large-scale production.
Compared with prior art, the present invention has the following advantages: the raw materials such as siloxanes used, modified siloxane and M source are all commercial reagent, and wide material sources are with low cost; Spinning solution good spinnability in electrostatic spinning process, meanwhile, the production cycle is shorter, is convenient to realize extension and produces; Si-M-O-C superfine fibre has a wide range of applications in fields such as heat-and sound-insulating, catalyst carrier, high-temperature catalytics.
Brief description of the drawings
Fig. 1 is the SEM figure of the embodiment of the present invention 1 gained Si-B-O-C superfine fibre;
Fig. 2 is the amplification SEM figure in the cross section of Si-B-O-C superfine fibre shown in Fig. 1;
Fig. 3 is the XPS spectrum figure of the embodiment of the present invention 1 gained Si-B-O-C superfine fibre.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
embodiment 1
The preparation method of the Si-B-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material boric acid, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; The mass ratio of its mesoboric acid and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from (needle point is to the vertical range of receiving screen) 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-B-O-C fibrillation;
(3) dry: the Si-B-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain Si-B-O-C superfine fibre after being cooled to room temperature.
The SEM of the ultra-fine Si-B-O-C fiber of the present embodiment gained schemes as shown in Figure 1 and Figure 2, XPS spectrum figure as shown in Figure 3, the element set prejudice table 1 of XPS test.
Table 1
Can find out from Fig. 1, Fig. 2, fiber is nonwoven fabric distributions, surfacing, and diameter is evenly distributed, and diameter is about 1.0 μ m, finds out fiber flawless, without hole from fibre section; Show from the xps energy spectrum analysis of Fig. 3 and table 1, target fibers is mainly made up of Si, O, C and a small amount of B.
embodiment 2
The preparation method of the Si-B-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material boric acid, methyl silicate, MTMS are joined in PVP solution, stir 1h; The mass ratio of its mesoboric acid and ethanol is 0.3:1, and the mass ratio of methyl silicate and ethanol is 2:1, and the mass ratio of MTMS and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, and relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-B-O-C fibrillation;
(3) dry: the Si-B-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain Si-B-O-C superfine fibre after being cooled to room temperature.
The present embodiment gained Si-B-O-C superfine fibre, surfacing, diameter is evenly distributed, and diameter is about 0.8 μ m, finds out fiber flawless, without hole from fibre section.
embodiment 3
The preparation method of the Si-B-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material boric acid, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; The mass ratio of its mesoboric acid and ethanol is 0.7:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, and relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-B-O-C fibrillation;
(3) dry: the Si-B-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain Si-B-O-C superfine fibre after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, and without hole, diameter is evenly distributed, and diameter is about 0.6～0.8 μ m.
embodiment 4
The preparation method of the Si-B-O-C superfine fibre of the present embodiment, comprise the following steps into:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio, mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material boric acid, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; The mass ratio of its mesoboric acid and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, and relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-B-O-C fibrillation;
(3) dry: the Si-B-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1500 DEG C, and be incubated 1h at this temperature, obtain Si-B-O-C superfine fibre after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, without hole, diameter is evenly distributed, diameter is about 0.6 μ m.
embodiment 5
The preparation method of the Si-B-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=300000), ethanol, watery hydrochloric acid (1mol/L) be 2:10:6 in quality proportioning ratio mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material boric acid, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; The mass ratio of its mesoboric acid and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, and relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-B-O-C fibrillation;
(3) dry: the Si-B-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain Si-B-O-C superfine fibre after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, without hole, diameter is evenly distributed, diameter is about 2.5～3.5 μ m.
embodiment 6
The preparation method of the Si-Zr-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material tetrabutyl zirconate, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; Wherein the mass ratio of tetrabutyl zirconate and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-Zr-O-C fibrillation;
(3) dry: the Si-Zr-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain ultra-fine Si-Zr-O-C fiber after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, without hole, diameter is evenly distributed, fibre diameter 1.5～2.5 μ m.
embodiment 7
The preparation method of the Si-Ti-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material butyl titanate, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; Wherein the mass ratio of butyl titanate and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-Ti-O-C fibrillation;
(3) dry: the Si-Ti-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain ultra-fine Si-Ti-O-C fiber after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, without hole, diameter is evenly distributed, fibre diameter 2 μ m.
embodiment 8
The preparation method of the Si-Ta-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio, mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material tantalum acetoacetic ester, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; Wherein the mass ratio of tantalic acid ethyl ester and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-Ta-O-C fibrillation;
(3) dry: the Si-Ta-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain ultra-fine Si-Ta-O-C fiber after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, without hole, diameter is evenly distributed, fibre diameter 1.5～2.5 μ m.
embodiment 9
The preparation method of the Si-Nb-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio, mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material niobic acid ethyl ester, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; Wherein the mass ratio of niobic acid ethyl ester and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-Nb-O-C fibrillation;
(3) dry: the Si-Nb-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain ultra-fine Si-Nb-O-C fiber after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, and without hole, diameter is evenly distributed, fibre diameter 2.5～3.5 μ m.
embodiment 10
The preparation method of the Si-Hf-O-C superfine fibre of the present embodiment, comprises the following steps:
(1) preparation spinning solution: by polyvinylpyrrolidone (M
w=1300000), ethanol, watery hydrochloric acid (1mol/L) be 1:10:6 in quality proportioning ratio, mix and blend 4h, the ultrasonic PVP solution that is dispersed into;
Raw material hafnium acetoacetic ester, ethyl orthosilicate, vinyltrimethoxy silane are joined in PVP solution, stir 1h; Wherein the mass ratio of hafnium acetoacetic ester and ethanol is 0.3:1, and the mass ratio of ethyl orthosilicate and ethanol is 2:1, and the mass ratio of vinyltrimethoxy silane and ethanol is 2:1;
(2) electrostatic spinning: adopt the syringe needle that internal diameter is 0.8mm, select voltage 15kV, receive flight lead from 12cm and feeding rate 15 μ l/min, spinning temperature is 20 DEG C, relative air humidity is 60RH%, adopt plane aluminium foil to receive filament plate spinning solution is carried out to electrostatic spinning, make Si-Hf-O-C fibrillation;
(3) dry: the Si-Hf-O-C fibrillation making is placed in to baking oven, dry in 60 DEG C of insulation 12h under air;
(4) high temperature burns till: dry fiber is placed in to the high temperature furnace under argon shield, heats up according to 3 DEG C/h, be warming up to 1000 DEG C, and be incubated 1h at this temperature, obtain ultra-fine Si-Hf-O-C fiber after being cooled to room temperature.
The present embodiment gained fiber surface is smooth, flawless, without hole, diameter is evenly distributed, fibre diameter 2.5～3.5 μ m.
Claims (10)
1. a preparation method for Si-M-O-C superfine fibre, is characterized in that, comprises the following steps:
(1) the ratio mix and blend 3-6h that is 0.5～2.0:10:6 by polyvinylpyrrolidone, ethanol, acid solution in quality proportioning, the ultrasonic PVP solution that is dispersed into;
Raw material M source, siloxanes, modified siloxane are joined in PVP solution, stir 0.5-2.0h, wherein the mass ratio of M source and ethanol is 0.1～2.0:1.0, and the mass ratio of siloxanes and ethanol is 1～3:1, the mass ratio of modified siloxane and ethanol is 1～3:1, is mixed with spinning solution:
Described M source is the presoma of doped chemical M, and element M is B, Ti, Zr, Hf, Ta or Nb;
The general molecular formula of described siloxanes is as follows:
(R
1O)
pSi(OR
2)
4-p
Wherein, alkyl R
1and R
2=methyl, ethyl, propyl group, butyl; R
1and R
2identical or different; P=0,1,2,3;
The general molecular formula of described modified siloxane is as follows:
R
3 mSi(OR
4)
4-m
Wherein, alkyl R
3and R
4=methyl, vinyl, ethyl, propyl group, butyl; R
3and R
4identical or different; M=0,1,2,3;
(2) spinning solution of step (1) gained is carried out to electrostatic spinning, collect Si-M-O-C fibrillation;
(3) the Si-M-O-C fibrillation of step (2) gained is placed in to drying box and is dried processing;
(4) the dry Si-M-O-C fibrillation of step (3) gained is placed in to the high temperature furnace under inert atmosphere protection, heats up according to 1～10 DEG C/h, be warming up to 800～1600 DEG C, insulation 1～10h, is cooled to room temperature, obtains ultra-fine Si-M-O-C fiber.
2. the preparation method of Si-M-O-C superfine fibre according to claim 1, is characterized in that: in step (1), in the time of M=B, M source is boric acid or borogen; In the time of M=Ti, M source is butyl titanate or isopropyl titanate; In the time of M=Zr, M source is tetrabutyl zirconate or the zirconic acid tert-butyl ester; In the time of M=Hf, M source is hafnium acetoacetic ester or hafnium tert-butyl acrylate; In the time of M=Ta, M source is tantalic acid ethyl ester or the tantalic acid tert-butyl ester; In the time of M=Nb, M source is niobic acid ethyl ester or niobic acid isopropyl ester.
3. the preparation method of Si-M-O-C superfine fibre according to claim 1 and 2, is characterized in that, in step (1), and the molecular weight M of described polyvinylpyrrolidone
w=30000～1500000.
4. the preparation method of Si-M-O-C superfine fibre according to claim 1 and 2, is characterized in that, in step (1), and hydrochloric acid, nitric acid or sulfuric acid that described acid solution is 0.1～1mol/L.
5. the preparation method of Si-M-O-C superfine fibre according to claim 3, is characterized in that, in step (1), and hydrochloric acid, nitric acid or sulfuric acid that described acid solution is 0.1～1mol/L.
6. the preparation method of Si-M-O-C superfine fibre according to claim 1 and 2, is characterized in that, in step (1), the quality proportioning of polyvinylpyrrolidone, ethanol, acid solution is 0.8～1.5:10:6.
7. the preparation method of Si-M-O-C superfine fibre according to claim 1 and 2, is characterized in that, in step (1), the mass ratio of M source and ethanol is 0.3～0.7:1.0.
8. the preparation method of Si-M-O-C superfine fibre according to claim 1 and 2, it is characterized in that, in step (2), electrostatic spinning process parameter comprises: to adopt internal diameter be 0.5～1.5mm syringe needle, spinning voltage 12～30kV, to receive flight lead be that 10～60 DEG C, relative air humidity are 20RH%～80RH% from 10～30cm, feeding rate 5～30 μ l/min, spinning temperature.
9. the preparation method of Si-M-O-C superfine fibre according to claim 5, it is characterized in that, in step (2), electrostatic spinning process parameter comprises: to adopt internal diameter be 0.5～1.5mm syringe needle, spinning voltage 12～30kV, to receive flight lead be that 10～60 DEG C, relative air humidity are 20RH%～80RH% from 10～30cm, feeding rate 5～30 μ l/min, spinning temperature.
10. the preparation method of Si-M-O-C superfine fibre according to claim 1 and 2, is characterized in that, in step (3), dry temperature is 50～120 DEG C, and the dry time is 12～30h.
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| CN106337217A (en) * | 2016-10-12 | 2017-01-18 | 中国人民解放军国防科学技术大学 | Porous Si-B-N-O ultra-fine fiber preparation method |
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| 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 |
| CN115286382A (en) * | 2022-07-28 | 2022-11-04 | 中国人民解放军国防科技大学 | Lanthanum zirconate nano heat-insulation fiber film and preparation method and application thereof |
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