CN103046166A - Chemical gas-phase crosslinking method of polycarbosilane fibers - Google Patents
Chemical gas-phase crosslinking method of polycarbosilane fibers Download PDFInfo
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Abstract
The invention discloses a chemical gas-phase crosslinking method of polycarbosilane fibers. The chemical gas-phase crosslinking method comprises the following steps of: 1, placing polycarbosilane protofibers into a chemical gas-phase crosslinking system tubular furnace, vacuumizing, replacing gas in the system to normal pressure by using nitrogen or argon, repeating the operations at least two times; 2, vacuumizing and then introducing a borane compound gas to a normal pressure; 3, carrying out temperature programming to 170-250 DEG C, reacting for 0.5-25h; and 4, carrying out temperature programming to 350-500 DEG C, insulating heat for 0.5-14h, and then cooling to room temperature. The chemical gas-phase crosslinking method has the advantages that no catalyst is needed, oxygen does not need to be introduced, a dehydrogenation coupling reaction can generated at a temperature being lower than a melting point of polycarbosilane (PCS) to realize the crosslinking of polycarbosilane fibers; the introduction of an element B is beneficial to improvement of the high-temperature resistant performance of silicon carbide fibers; and no equipment modification is needed for the existing chemical gas-phase crosslinking system, and the process is convenient and is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of cross-linking method of polycarbosilane fiber, especially relate to a kind of chemical vapor curing method of polycarbosilane fiber.
Background technology
The characteristics such as carborundum (SiC) fiber has that density is little, specific strength is large, specific modulus is high, linear expansion coefficient is little, high temperature resistant, corrosion-resistant, high strength, having good compound phase capacitive with metal, pottery, polymer, is the desirable fortifying fibre of high-performance composite materials.Structure set-stealthy-solar heat protection is multi-functional for the SiC fiber simultaneously, is with a wide range of applications in high-tech sectors such as space flight, aviation, weapons, the energy.
The organic precursor method conversion method is take organic polymer (mostly being organometallic polymer) as raw material, utilize its characteristic such as solvable, fusible to realize moulding after, through the high temperature thermal decomposition process, make it to change into from organic matter the method for inorganic ceramic material.
The organic precursor method conversion method prepares the SiC fiber and has following distinguishing feature: the fiber that (1) can prepare continuously, diameter is less (＜20 μ m), and the stitchability of fiber is good, is easy to weave the prefabricated component that becomes complicated shape; (2) lower preparation temperature (＜1250 ℃); (3) can carry out MOLECULE DESIGN to precursor, the composition of control precursor contains the functionality ceramic fiber of different element etc. such as preparation; (4) be suitable for suitability for industrialized production, production efficiency is high, and its cost only is about 1/10 of the standby SiC fiber cost of CVD legal system.Therefore, the organic precursor method conversion method has become the present comparatively desirable method of continuous SiC fiber for preparing.The organic precursor method conversion method is that the main method for preparing at present the SiC fiber is (referring to 1. Riedel, R., Mera, G., Hauser, H. and Klongczynski, A., Silicon-based polymer-derived ceramics synthesis properties and applications-A review. "
J. Ceram. Soc. Japan, ", 2006,
114, 425 – 444; 2. Miele, P., Bernard, S., Cornu, D. and Toury, B., Recent developments in polymer-derived ceramic fibers (PDCFs): Preparation, properties and applications-A review. "
Soft Mater.", 2006,4,249 – 286; 3. Bunsell, R. and Piant, A., A review of the development of three generations of small diameter silicon carbide fibers.
J. Mater. Sci., 2006,
41, 823 – 839; 4. Okamura, K., Shimoo, T., Suzuya, K., Suzuki, K., SiC-based ceramic fibers prepared via organic-to-inorganic conversion process-a review. "
J. Ceram. Soc. Japan.", 2006,
114, 445-454; 5. Chen Jianjun, Peng Zhiqin, Dong Wenjun, etc. development course and the progress of the standby SiC fiber of precursor. "
Tec fiber and application", 2010,35 (1): 35-52; 6. Zhao Dafang, Wang Haizhe, Li Xiaodong. the precursor conversion method prepares the progress of SiC fiber. "
Journal of Inorganic Materials", 2009,24 (6): 1097-1100; 7. poplar is auspicious greatly, Song Yongcai. the status and prospects of the standby continuous carbofrax fibre suitability for industrialized production of precursor legal system. "
Mechanical engineering material", 2007,31 (1): 1-4; 8. poplar is auspicious greatly, Song Yongcai. characteristic and the application thereof of the standby continuous SiC fiber of precursor legal system. "
The Arms Material scientific and engineering", 2007,30 (6): 64-69.; 9. Chu increases bravely, Feng Chunxiang, and Song Yongcai, the domestic and international research and development present situation of precursor method SiC fiber, "
Journal of Inorganic Materials" 2002,17 (2): 193-201)
The organic precursor method conversion method prepares the SiC fiber can be divided into following four step operations: step 1: precursor is synthetic, i.e. synthetic polymer-Polycarbosilane (PCS) take Si, C element as key component; Step 2: spinning, namely the PCS precursor prepares the PCS fibrillation by the method for melting or solution spinning; Step 3: crosslinked, thermoplastic PCS fibrillation is converted into heat cured PCS cross filament by proper method; Step 4: high temperature burns till, and namely makes the inorganic ceramic fibre that changes into of PCS cross filament under the high temperature.
PCS fibriilar crosslinked be one of the key technology of SiC fiber preparation.After the fibril formation, lose fiber shape for avoiding fiber melting in inorganicization process, make the molecule in the fibrillation form three-dimensional net structure, it is fibriilar crosslinked that Here it is.Crosslinked process is the process that thermoplastic PCS fibrillation is transformed into heat cured PCS cross filament.From in essence, be that the PCS molecule with numerous molecular weights is combined into the larger build molecule of molecular weight by chemical reaction.Fibrillation is after crosslinked, and no longer dissolving or melting can keep fiber shape in inorganicization process.Crosslinking method and cross-linking process have significant impact to productive rate, composition, structure and the performance of SiC fiber.
The fibriilar cross-linking method of PCS is existing multiple, as air cross-linking method, electron beam, ion beam, ultraviolet ray and gamma-radiation irradiation crosslinking, chemical vapor curing method and heat cross-linking method etc. (referring to: 1. Wu Yi primary, Zhang Guojian, Liu Chunjia etc. Polycarbosilane prepares the not melt processed technical study progress of continuous SiC fiber. " material Leader ", 2006,20 (7): 80-87; 2. remaining illuminate imperial or royal seal, Li Xiaodong, Cao Feng etc. the crosslinking method of polycarbosilane fiber in the standby SiC ceramic fibre process of precursor legal system. " aerospace material technique ", 2002, (6): 10-13; 3. Ichikawa H. Development of high performance SiC fibers derived from polycarbosilane using electron beam irradition curing-a review. "
J. Ceram. Soc. Jpn, ", 2006,114 (6): 454-460; 4. Okamura K., Seguchi T., Application of radiation curing in the preparation of polycarbosilane derived SiC fibers, "
J. Inorg. Organomet. P"
,1992,
2(1): 171-179; 5. K.Okamura, T.Matsuzawa, Y.Hasegawa. γ – irradiation curing on polycarbosilane fibers as the precursor of SiC fibers. "
J.Mater.Sci.Lett", 1985,4:55-57.; 6. Rabe J. A., Lipowitz J., Lu P. P. Curing preceramic polymers by exposure to nitrogen dioxide. US Patent, 5,051,215; 7. Hasegawa Y., New curing method for polycarbosilane with unsaturated hydrocarbons and application to thermally stable SiC fibre, "
Compos. Sci. Technol", 1994,
51(2): 161-166; 8. Hasegawa Y., SiC fiber prepared from polycarbosilane cured without oxygen, "
J. Inorg. Organomet. P."
,1992,
2(1): 161-169; 9. Lipowitz J., Barnard T., Bujalski D., Rabe J., Zank G., Zangvil A., Xu Y., Fine-diameter polycrystalline SiC fibers, "
Compos. Sci. Technol"
.,1994,
51(2): 167-171; 10. Lipowitz J., Rabe J. A., Zangvil A., Xu Y., Structure and properties of sylramic
TMSilicon carbide fiber-A polycrystalline, stoichiometric β-SiC composition, "
Ceramic Eng. Sci. Proc."
,1997,
18(3): 147-157).
Wherein, the air cross-linking method is to adopt the earliest the most simple cross-linking method, and its essence is that active group Si-H key and the oxygen reaction among the PCS forms the Si-O-Si bridge crosslinking structure and realize that fiber is crosslinked.
The deficiency of the method is: introduce a large amount of oxygen (generally greater than 12wt%) in the SiC fiber, after high temperature burns till, form the unsettled SiC of a large amount of high temperature
xO
yCompound phase has a strong impact on resistance to elevated temperatures and the antioxygenic property of fiber.Studies show that, owing to introduce too much oxygen in the cross-linking process, decomposition reaction occurs during high temperature makes mass loss serious, in fiber, produce a large amount of defectives, cause the element of prepared SiC fiber to form and the microstructure imperfection, fundamentally restrict the mechanical behavior under high temperature of final SiC fiber, limited the use field of SiC fiber.Therefore, non-oxygen cross-linking method becomes the main cross-linking method of high temperature resistant SiC fiber.Comprise: irradiation crosslinking, chemical vapor curing method, heat cross-linking method etc.
The crosslinking with radiation method is to utilize the energy emission initiation PCS fiber of high energy particle crosslinked, method commonly used has electron beam irradiation, ionizing radiation, neutron irradiation, gamma Rays, ultraviolet radiation, laser emission, microwave etc., it is characterized in that under the environment of anhydrous and oxygen-free, carrying out, crosslinking agent need be do not added, the SiC fiber of low oxygen content can be prepared in this way.Electron beam irradiation method makes the oxygen content of Hi-Nicalon S be reduced to about 0.2wt% under the inert atmosphere that Japan carbon company, emerging product company of space section adopt, and the purity of fiber improves greatly, shows excellent mechanical property and resistance to elevated temperatures.But it is slower that the process of cross-linking reaction occurs under electron beam irradiation the PCS fiber, reaching necessary crosslinking degree (gel content 〉=80%) must be with high dose rate more than irradiation 10MGy under vacuum or the oxygen-free atmosphere, the manufacturing cost of material is significantly risen, and will bring harsh requirement to irradiation technique, therefore, the Radiation Crosslinking Method apparatus expensive, cost is higher.
The heat cross-linking method is in fact improving one's methods to the air cross-linking method; its principle is the PCS fiber carries out low degree in air pre-oxidation; make fiber surface form crosslinked protective layer; then heat cross-linking a few hours in higher temperature inert atmosphere; it is good crosslinked that the PCS fibrous inside is realized, thereby realize the pre-oxidation treatment of fiber in the situation of the least possible introducing oxygen.The heat cross-linking method is simple for requirements such as equipment, and shortcoming is the processing step that has increased the fiber preparation, and oxygen content reduces limited, and the heat cross-linking time is longer, greatly reduces the efficient of fiber preparation.
Chemical vapor curing method (CVC) is a kind ofly to realize crosslinked method by PCS fibrillation and reactive atmosphere chemical gas phase reaction.The people such as Lipowitz with the PCS fibrillation through NO
2Not after the melt processed again through BCl
3Process, finally made the SiC fiber that contains B that oxygen content is less than 0.1wt%.This method adopts NO
2And BCl
3Be reactive atmosphere, wherein BCl
3Have stronger corrosivity, higher to equipment requirement, larger to environmental hazard.
Japan's special inorganic material research chief Gu Chuan good hero can with the steam replacement air of the chemically reactive substance of PCS reaction, carry out at a certain temperature gas-phase chemical reaction, make the PCS fibrillation crosslinked.The chemically reactive substance that uses mainly is divided into two classes: chlorine-containing compound and unsaturated hydrocarbon.Representative material wherein, the former is such as carbon tetrachloride, chlorobenzene; The latter such as cyclohexene, 1-hexin, 1-octyne etc.Be that 2060 PCS(fusing point is about 270 ℃ with number-average molecular weight) be melt-spun into fiber at 370 ℃, under specific temperature, passing into the steam that contains unsaturated hydro carbons, under blanket of nitrogen, carry out crosslinkedly, crosslinked rear fiber is at N
2Middlely make the SiC fiber of oxygen content＜2wt% through 1300 ℃ of thermal crackings, its tensile strength be 1400 ℃ of lower can declines rapidly, and modulus is until still change 1550 ℃ the time little.With the SiC Fiber Phase ratio that the air cross-linking treatment method makes, with the rising of heat treatment temperature, its β-SiC crystallite grain growth speed is slowed down greatly.Illustrate that the CVC cross-linking method can suppress the coarsening rate of β-SiC crystal grain, thus Effective Raise the mechanical behavior under high temperature of SiC fiber.PCS fibrillation CVC reaction is the radical reaction that is similar to electron beam irradiation.Take cyclohexene as example, the cyclohexene rear formation free radical that is heated causes Si-H and Si-CH in the PCS molecule
3Bond fission generates Si free radical and Si-CH
2Free radical promotes the further crosslinked of PCS molecule, finally forms Si-CH
2-Si structure.
The advantage of chemical vapor curing is that the product oxygen content is lower, the fire-resistant oxidation resistant better performances, and equipment is simple, and cost is low, is suitable for large-scale production.Yet the chemical vapor curing reaction temperature is more than 250 ℃, and this just requires the fusing point (softening point) of PCS must be higher than 250 ℃, otherwise the PCS fibrillation is melting and lose fiber shape before chemical vapor curing occurs.But, contain more side chain in the PCS molecular structure, except along the major axis of oblate spheroid shape PCS molecule is arranged, the macromolecular orientation as the PAN fiber not, precursor intensity is extremely low.When its fusing point (softening point) was higher than 250 ℃, melt spinning was especially responsive to temperature, is difficult to spin continuous fibrillation.For solving above-mentioned contradiction, generally adopt the PCS melt spinning of fusing point below 230 ℃, spinning continuous P CS fibrillation.Afterwards the PCS fiber is carried out the pre-oxidation of low degree in air, make PCS fusing point wherein be higher than 250 ℃, carry out again chemical vapor curing.Therefore, existing chemical vapor curing method is actually low pre-oxidation+chemical gas phase reaction process.The SiC fiber oxygen content of preparation is 6wt%～9wt%, and SiC fibre fire resistant performance still is restricted.
Chinese patent application 201210013751.8 discloses a kind of catalytic crosslinking method of polycarbosilane fiber, adopting platinum compounds, rhodium compound or palladium compound is catalyst, 1, the 3-butadiene, or 1, the alkadienes such as 4-pentadiene, or the alkynes such as acetylene, propine are reactive atmosphere, catalytic crosslinking PCS fiber.But the introducing of catalyst is inconvenient.In addition, reactive atmosphere is carbon-rich compounds, and the high-temperature oxidation resistance of final fiber is had certain negative effect.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the defective of above-mentioned prior art, provides a kind of technology controlling and process easy, need not catalyst, is attainable Polycarbosilane (PCS) fibrillation cross-linking method under the temperature that is lower than Polycarbosilane (PCS) fusing point.
The present invention solves the technical scheme that its technical problem adopts, and take borane compound as reactive atmosphere, under the temperature that is lower than the Polycarbosilane fusing point, carries out the dehydrogenation coupling reaction, forms three-dimensional net structure, realizes that PCS is fibriilar crosslinked.
The present invention specifically comprises following operating procedure: (1) places chemical vapor curing system tube furnace with the Polycarbosilane fibrillation, vacuumizes, and then repeats at least secondary with gas in nitrogen or the argon replaces system to normal pressure; (2) vacuumize after, pass into and have high chemically active borane compound gas to normal pressure; (3) temperature programming to 170 ℃～250 ℃, reaction time 0.5 h～25h; (4) temperature programming to 350 ℃～500 ℃, then temperature retention time 0.5 h～12h is cooled to room temperature.
Further, in the step (2), described to have high chemically active borane compound be to be selected from a kind of in diborane, tetraborane, pentaborane, own borine, the decaborane etc.
Further, in the step (3), temperature programming to 180 ℃～200 ℃, the described reaction time is 12～24h.
Further, in the step (4), temperature programming to 400 ℃～450 ℃, described temperature retention time is 2-12h.
Further, in step (1) and (2), described vacuumizing, vacuum preferably is evacuated to 5 * 10
-2Pa-7 * 10
-2Pa; More preferably be evacuated to 6 * 10
-2Pa.
When described borane compound is solid compounds (for example decaborane), also can adopt following methods:
(1) Polycarbosilane fibrillation and borane compound (for example decaborane) are placed the chemical vapor curing system, be evacuated to 5 * 10
-2Pa-7 * 10
-2Pa, then with gas in nitrogen or the argon replaces system to normal pressure, triplicate; (2) be evacuated to 5 * 10
-2Pa-7 * 10
-2Behind the Pa, pass into nitrogen to normal pressure; (3) temperature programming to 180～200 ℃, reaction time 20～25h; (4) temperature programming to 400～500 ℃, temperature retention time 10～15h is cooled to room temperature.
The present invention is on mechanism of crosslinking, and is fully different from traditional chemical vapor curing mechanism.It is reactive atmosphere that the present invention has high chemically active borane compound by introducing, greatly reduces reaction temperature, so that the fibriilar cross-linking reaction of PCS (generally be lower than 200 ℃, the highest be no more than 250 ℃) under lower temperature can be finished.Therefore, realized the anaerobic chemical vapor curing fully.
The present invention has following advantage: (1) need not catalyst, need not to introduce oxygen, under the temperature that is lower than Polycarbosilane (PCS) fusing point, the dehydrogenation coupling reaction can occur, and realizes the crosslinked of polycarbosilane fiber; (2) introduce the B element, be conducive to improve the silicon carbide fibre resistance to elevated temperatures; (3) do not need that any equipment is done by existing chemical vapor curing system and change, simple process is suitable for large-scale production.
Description of drawings
Fig. 1 is the fibriilar infrared spectrum of PCS (FT IR);
Fig. 2 is the infrared spectrum (FT IR) of embodiment 1 gained PCS cross filament.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) the Polycarbosilane fibrillation is placed existing chemical vapor curing system tube furnace, be evacuated to vacuum and reach 6 * 10
-2Then Pa uses in the nitrogen replacement system gas to normal pressure, triplicate; (2) be evacuated to vacuum and reach 6 * 10
-2Behind the Pa, pass into diborane gas to normal pressure; (3) temperature programming to 180 ℃, reaction time 24h; (4) temperature programming to 400 ℃, temperature retention time 2h is cooled to room temperature.
By 2100cm in the FT IR spectrogram
-1Si-H absworption peak and 1250cm
-1Si-CH
3Absorbance ratio (the A of absworption peak
Si-H/ A
Si-CH3) characterize the Si-H linkage content of PCS and cross filament.According to the FT IR of Fig. 1 as can be known, the fibriilar SiH content of PCS is 0.982.From the FTIR of Fig. 2 as can be known, the Si-H linkage content of cross filament is that 0.321, the Si-H key extent of reaction is 67.3%, and gel content is 99.97%.Oxygen analysis shows that PCS fibrillation oxygen content is 0.72wt%, and PCS cross filament oxygen content is 0.73wt%, can think and not introduce extra oxygen.
Embodiment 2
(1) the Polycarbosilane fibrillation is placed existing chemical vapor curing system tube furnace, be evacuated to 6 * 10
-2Pa) and with gas in the argon replaces system to normal pressure, triplicate; (2) be evacuated to 6 * 10
-2Pa, after, pass into tetraborane gas to normal pressure; (3) temperature programming to 200 ℃, reaction time 12h; (4) temperature programming to 450 ℃, temperature retention time 6h.Be cooled to room temperature.
FT IR spectrogram and Fig. 2 of gained PCS cross filament are basically identical, and only absorption peak strength is slightly different.According to FT IR spectrogram, the fibriilar SiH content of PCS is 0.982, and the Si-H linkage content of cross filament is 0.385, and the Si-H key extent of reaction of cross filament is 60.8%.
Embodiment 3
(1) the Polycarbosilane fibrillation is placed the tube furnace that has the chemical vapor curing system now, be evacuated to 6 * 10
-2Pa), then use in the nitrogen replacement system gas to normal pressure, triplicate; (2) be evacuated to 6 * 10
-2Behind the Pa, pass into the pentaborane of gasification to normal pressure; (3) temperature programming to 200 ℃, reaction time 20h; (4) temperature programming to 450 ℃, temperature retention time 12h.Be cooled to room temperature.
FT IR spectrogram and Fig. 2 of PCS cross filament are basically identical, and only absorption peak strength is slightly different.According to FT IR spectrogram, the fibriilar SiH content of PCS is 0.982, and the Si-H linkage content of cross filament is that 0.398, the Si-H key extent of reaction is 59.4%.
Embodiment 4
(1) the Polycarbosilane fibrillation is placed existing chemical vapor curing system tube furnace, be evacuated to vacuum and reach 6 * 10
-2Then Pa uses in the nitrogen replacement system gas to normal pressure, triplicate; (2) pass into the borine of gasification to normal pressure after vacuumizing; (3) temperature programming to 200 ℃, reaction time 24h; (4) temperature programming to 450 ℃, temperature retention time 12h.Be cooled to room temperature.
FT IR spectrogram and Fig. 2 of PCS cross filament are basically identical, and only absorption peak strength is slightly different.According to FT IR spectrogram, the fibriilar SiH content of PCS is 0.982, and the Si-H linkage content of cross filament is that 0.379, the Si-H key extent of reaction is 61.4%.
Embodiment 5
(1) Polycarbosilane fibrillation and decaborane are placed existing chemical vapor curing system tube furnace, be evacuated to 6 * 10
-2Then Pa uses in the nitrogen replacement system gas to normal pressure, triplicate; (2) be evacuated to 6 * 10
-2Behind the Pa, pass into nitrogen to normal pressure; (3) temperature programming to 200 ℃, reaction time 24h; (4) temperature programming to 450 ℃, temperature retention time 12h is cooled to room temperature again.
FT IR spectrogram and Fig. 2 of PCS cross filament are basically identical, and only absorption peak strength is slightly different.According to FT IR spectrogram, the fibriilar SiH content of PCS is 0.982, and the Si-H linkage content of cross filament is that 0.342, the Si-H key extent of reaction is 65.2%.
From the above embodiment as seen, take borane compound as reactive atmosphere, can in the dehydrogenation coupling reaction that is not higher than under 200 ℃ by B-H and Si-H, realize that PCS is fibriilar crosslinked.The present invention need not catalyst, under the temperature that is lower than Polycarbosilane (PCS) fusing point, the dehydrogenation coupling reaction can occur, and forms three-dimensional net structure, realizes that PCS is fibriilar crosslinked, has introduced simultaneously the B element of the resistance to elevated temperatures that is conducive to the SiC fiber.Simple process of the present invention is suitable for large-scale production.
Claims (8)
1. the chemical vapor curing method of a polycarbosilane fiber, it is characterized in that, may further comprise the steps: (1) places chemical vapor curing system tube furnace with the Polycarbosilane fibrillation, vacuumizes, then repeat at least secondary with gas in nitrogen or the argon replaces system to normal pressure; (2) vacuumize, then pass into and have high chemically active borane compound gas to normal pressure; (3) temperature programming to 170 ℃～250 ℃, reaction time 0.5 h～25h; (4) temperature programming to 350 ℃～500 ℃, then temperature retention time 0.5 h～14h is cooled to room temperature.
2. the chemical vapor curing method of polycarbosilane fiber according to claim 1 is characterized in that, in the step (2), described to have high chemically active borane compound be to be selected from a kind of in diborane, tetraborane, pentaborane, own borine, the decaborane.
3. the chemical vapor curing method of polycarbosilane fiber according to claim 1 and 2 is characterized in that, in the step (3), and temperature programming to 180 ℃～200 ℃, the described reaction time is 12-24 h.
4. the chemical vapor curing method of polycarbosilane fiber according to claim 1 and 2 is characterized in that, in the step (4), and temperature programming to 400 ℃～450 ℃, described temperature retention time is 2-12 h.
5. the chemical vapor curing method of polycarbosilane fiber according to claim 3 is characterized in that, in the step (4), described temperature retention time is 2-12 h.
6. the chemical vapor curing method of polycarbosilane fiber according to claim 1 and 2 is characterized in that, in step (1), (2), and described vacuumizing, vacuum is evacuated to 5 * 10
-2Pa-7 * 10
-2Pa.
7. the chemical vapor curing method of polycarbosilane fiber according to claim 6 is characterized in that vacuum is evacuated to 6 * 10
-2Pa.
8. the chemical vapor curing method of a polycarbosilane fiber is characterized in that, may further comprise the steps: (1) places chemical vapor curing system tube furnace with Polycarbosilane fibrillation and borane compound, is evacuated to vacuum and reaches 5 * 10
-2Pa-7 * 10
-2Then Pa repeats at least secondary with gas in nitrogen or the argon replaces system to normal pressure; (2) be evacuated to vacuum and reach 5 * 10
-2Pa-7 * 10
-2Behind the Pa, pass into nitrogen to normal pressure; (3) temperature programming to 180～200 ℃, reaction time 20～25h; (4) temperature programming to 400～500 ℃, temperature retention time 10～14h is cooled to room temperature.
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