CN104532549A - Method for rapidly obtaining carbon/silicon carbide coaxial fiber by reducing plasma based on microwave and application - Google Patents
Method for rapidly obtaining carbon/silicon carbide coaxial fiber by reducing plasma based on microwave and application Download PDFInfo
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Abstract
The invention discloses a carbon/silicon carbide coaxial fiber which is prepared according to the following steps: fully mixing carbon fibers, silicon powder and silicon dioxide powder to obtain a mixture; arranging in vacuum or at a normal-pressure protection condition of an inertia gas; and heating the mixture by microwave to activate the surfaces of the carbon fibers and trigger a high-temperature reaction to obtain the carbon/silicon carbide coaxial fiber. The preparation method can be used for simply, conveniently, rapidly and efficiently preparing the C/SiC coaxial fiber which is ideal in structure and excellent in oxidation resistance. The C/SiC coaxial fiber is uniform, pure, free of impurities and controllable in shape. Besides, by adopting a technology in which the microwave is used for inducing plasma radiation, the preparation method has the advantages of high heating speed, uniform heating, small thermal inertia, short production period and the like, and the preparation cost is further lowered.
Description
Technical field
The present invention relates to a kind of fast synthesis method field of coaxial fiber, be specifically related to a kind of method based on the coaxial fiber of Microwave Induced Plasma quick obtaining carbon/carborundum (C/SiC) and application.
Background technology
Carbon fiber is the Typical Representative of reinforcement in advanced composite material, in view of the high-temperature hot physical property of its excellence, the peculiar property that particularly intensity improves along with the raising of usage temperature, makes it have the status of irreplaceability in the application of the high-tech sector such as Aero-Space, nuclear industry.But carbon fiber, under high temperature oxidative atmosphere, is easy to deterioration failure, become the fatal restriction of puzzlement carbon-fiber high-temperature application.For improving the high-temperature oxidation resistant application performance of carbon fiber and reinforced composite thereof, people must develop the various method such as surface protection, matrix modification, to overcome or to alleviate the high-temperature oxydation of carbon fiber.
Carborundum (SiC) is important thermal structure and function ceramics; with carbon fiber, there is good compatibility; and the oxidation product silica under its high temperature is easy to form continuous print glassy phase; to the diffusion of oxidizing atmosphere, infiltration, there is good restriction, thus protection carbon fiber core or composite.Therefore, form carborundum (SiC) protective layer at carbon fiber surface, the coaxial fiber of Synthesis and applications carbon/carborundum (C/SiC), causes the broad interest of people.So far, people successively develop multiple method, achieve the coated of carborundum protective layer at carbon fiber surface, have acquired the coaxial fiber of carbon/carborundum (C/SiC).As (the Kim J W such as Jae-Won Kim of Korea S Changwonnational university, Lee S S, Jung Y G, et al.Synthesisof SiC microtube with villus-like morphology and SiC fiber [J] .Journal of MaterialsReseauch, 2005,20 (2): 409-416.), in process based on gas-solid (VS) mechanism synthesis SiC micron tube, achieve the acquisition of C/SiC Coaxial Nanofibers, the oxidation initial temperature of carbon fiber is increased to about 600 DEG C from less than 500 DEG C.But the C/SiC Coaxial Nanofibers that this method obtains, SiC protects the interface cohesion of shell and carbon fiber core bad, is difficult to realize the defense-in-depth under high temperature.
China has also carried out a lot of work in the surface protection of carbon fiber, as Beijing Research Inst. of Aeronautic Material, Aerospace Material & Technology Inst., the National University of Defense technology, Hunan University, Shandong University, Deng Duojia unit of Metal Inst., Chinese Academy of Sciences have all carried out positive investigation and application work.But while practical application, also there are some shortcomings.As comparatively common polymer impregnated pyrolysis method (PIP); first must utilize expensive Polycarbosilane (PCS) resin-coating carbon fiber surface; carrying out high temperature pyrolysis again, is carborundum (SiC) protective layer by outer field Polycarbosilane (PCS) resin transfer.The component loss of this method in pyrolytic process, makes inevitably to produce more hole in SiC shell; And the difference of hot expansion property, also can cause in conjunction with bad between SiC shell and carbon fiber core, even peel off and further deteriorated protected effect.
Be prepare the common method of film or coating based on chemical vapour deposition (CVD) (CVD) technology, the coaxial fiber of carbon/carborundum (C/SiC) fine and close continuously can be acquired.But it is long to there is the reaction time in method, the high restriction of technological requirement.Although some methods improved contribute to the structure and the application characteristic that improve (C/SiC) coaxial fiber, the deficiencies such as process complexity is tediously long still make said method be subject to many limitations in Promotion practice.As Li Hejun (the Hejun Li of Northwestern Polytechnical University, Haibo Ouyang, LehuaQi, Yulei Zhang, Zhengjia Li, Jianfeng Wei.Effect of Temperature on the Synthesis of SiC Coating on CarbonFibers by the Reaction of SiO with the Deposited Pyrolytic Carbon Layer, J.Mater.Sci.Technol., 2010, 26 (3), 211-216.) etc. cut polyacrylonitrile (PAN) base carbon fibre surface short to achieve the coating of SiC coated, the coaxial fiber of the carbon/carborundum (C/SiC) acquired, ideal result is achieved at the anti-oxidation characteristics improving carbon fiber.But this process is complicated, based on waiting on the basis of thermal chemical vapor infiltration deposition 1h RESEARCH OF PYROCARBON, also must under 1400 ~ 1600 DEG C of high temperature successive reaction 1h, also have certain dependence to equipment.
In addition, (Sun Liangkui, Cheng Haifeng, Chu Zengyong, Zhou Yongjiang, Sun Guoliang, the C/SiO such as the Sun Liangkui of the National University of Defense technology
2the preparation and property research of coaxial composite fibre, Journal of Inorganic Materials, 02 phase in 2009), with SiO
2colloidal sol is shell, and polyacrylonitrile (PAN) solution is sandwich layer, adopts coaxial electrostatic spinning legal system for PAN/SiO
2coaxial fiber.Then to PAN/SiO
2coaxial fiber carries out the process such as follow-up pre-oxidation, charing, can obtain the C/SiO of diameter 1 μm
2coaxial fiber (has thickness to be about the SiO of 20nm on carbon fiber
2coating).But the top layer of this coaxial fiber is silica (SiO
2), the modified effect of its carbon-fiber high-temperature antioxygenic property, obviously not as SiC protects shell; And the carbon fiber diameter of the method is meticulous, fields such as inhaling ripple can only be applied to.Therefore, continue the preparation method exploring and optimize simple and effective, the coaxial fiber of carbon/carborundum (C/SiC) that quick obtaining is continuously fine and close, to improve the application reliability of carbon fiber under high-temperature oxidation environment and durability etc., remains very important practice demand.
Summary of the invention
Technical problem to be solved by this invention, based on Microwave Induced Plasma treatment technology, provides a kind of simple, efficient, low cost, is convenient to the method that industrialization prepares the coaxial fiber of C/SiC on a large scale fast.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of method based on the coaxial fiber of Microwave Induced Plasma quick obtaining carbon/carborundum (C/SiC), the steps include:
1) raw material mixing: commercially available carbon fiber, silica flour, silicon dioxide powder are mixed, and adds in ceramic crucible;
Described carbon and the mol ratio of element silicon are 2 ~ 5:1; Described silicon and silica mol ratio are 0.5 ~ 2:1;
2) cleaning activity environment: after crucible is placed in microwave cavity, can be evacuated to 10 ~ 50kPa by resonator, or passes into nitrogen or argon gas, forms nitrogen or argon gas atmosphere in resonator, with impact that is clean or reduction partial pressure of oxygen;
3) Microwave Induced Plasma process: open microwave, adjustment microwave power is 2 ~ 6kW, by raw material within the several seconds, even transient heating to 1100 ~ 1250 DEG C, in the plasma that microwave and induction thereof are produced, excite activation synthetic reaction 10 ~ 60 seconds.
4) product-collecting: after the Microwave Induced Plasma process of 10 ~ 60 seconds, namely obtains the coaxial fiber of C/SiC; Product can directly be collected, without the need to post processings such as purifications.
For the type of carbon fiber, because its basic composition is identical, to the response of Microwave Induced Plasma without significant difference, therefore the type of carbon fiber is unrestricted.According to the requirement of Application Areas, step 1) described in carbon fiber be polyacrylonitrile (PAN) base carbon fibre, viscose-based carbon fiber, asphalt base carbon fiber or phenolic resins base carbon fibre.The key of the coaxial fiber of preparation C/SiC is the top layer carbon atom of carbon fiber and the reaction in-situ of silicon monoxide, silica flour, silicon dioxide powder etc. are only the silicon sources producing silicon monoxide intermediate, therefore also unrestricted to the type of silica flour, silicon dioxide powder etc., namely silica flour, the silicon dioxide powder of various granularity, purity etc., all can be applicable to the present invention.
Step 3) middle optimum configurations explanation: control operating power is 2 ~ 6kW; Too low irradiation power, be not enough to induction and produce plasma, unstable state accelerated speed and activation degree will be restricted.But too high operating power, will cause energy exchange too violent, produce plasma ablation.The control treatment time was at 10 ~ 60 seconds.In the too short processing time, the SiC of formation is abundant not, can not ensure that forming continuous whole SiC protects shell.In the long reaction time, by making, the SiC containment vessel layer thickness on top layer is excessive, reduces the diameter of carbon fiber core, affects the combination property of the coaxial fiber of C/SiC.
Second technical problem to be solved by this invention, provides that a kind of antioxidant effect prepared based on the method for the coaxial fiber of Microwave Induced Plasma quick obtaining carbon/carborundum (C/SiC) is good, initial oxidation temperature is high, the coaxial fiber of carbon/carborundum that residual rate after high temperature continued oxidation is high.
For solving second technical problem, the technical solution adopted in the present invention is: the coaxial fiber of a kind of carbon/carborundum: take carbon fiber as core body, covering one deck carborundum protective layer of carbon fiber surface continuous uniform, carborundum protective layer and carbon fiber core be combined in amplification 100,000 times time fine and close zero defect; Described carborundum protective layer thickness is 50 ~ 600nm.
Know-why: difference and traditional processing mode such as conduction, convection current, microwave is while realizing penetration body heat phase, also generating an electromagnetic field, to being paired into the chemical reaction of key with atomic nucleus outer-shell electron by producing special coupling intervention effect, even can change response path.And High-Power Microwave radiation-induced under, can form low temperature plasma on surface, not only can realize the intensification of moment, and the atom on material top layer also will be activated.Under more high-power microwave, also can cause air ionization, or the distillation of surface of solids atom, strong plasma sparking even can cause plasma ablation.
The basic composition of carbon fiber is carbon, and the class graphite microcrystalline structure that its random layer is piled up makes carbon fiber have excellent electromagnetic property, has good response to microwave electromagnetic field.The present invention is according to the quick features of response between carbon fiber and microwave field, based on the plasma heating reaction system that the induction of High-Power Microwave electromagnetic field produces, form silicon source by silica flour and silicon dioxide powder, by redox reaction, produce and silicon monoxide (SiO) is provided fast; And the carbon atom on plasma exciatiaon activated carbon fiber top layer by microwave induced generation, form carborundum (SiC) with SiO reaction in-situ and protect shell, thus acquire the coaxial fiber of C/SiC.Owing to there is violent energy exchange in Microwave Induced Plasma processing procedure, and excite activation process, astable processing procedure, by breaking through the restriction of molecular balance, is conducive within the extremely short time, acquire the coaxial fiber of C/SiC.
It is to be noted, for the electromagnetic techniques such as microwave, for preventing the electromagnetic mutual interference of each wave band, particularly prevent microwave to the interference of radio communication, broadcast, radar etc., clear stipulaties can be used as heating or dry in the world, and the frequency range being applied to the application such as industry, scientific research and medical science only has four sections, is namely respectively: L section, frequency is 890 ~ 940MHz, and centre wavelength is 0.330m; S section, frequency is 2.40 ~ 2.50GHz, and centre wavelength is 0.122m; C section, frequency is 5.725 ~ 5.875GMHz, and centre wavelength is 0.052m; K section, frequency is 22.0 ~ 22.25GHz, and centre wavelength is 0.008m.Namely centre frequency lays respectively at 433MHz, 915MHz, 2.45GHz, 28GHz.What the present invention adopted the is magnetron that generally uses, as microwave source, processes under current 2.45GHz center bin.
According to the operation principle of electromagnetic wave and electromagnetic field, with the microwave source of the other types such as klystron, travelling-wave tubes, the superposition that also can generate an electromagnetic field in other frequency ranges collects, thus induction produces plasma.Therefore, the present invention may extend to the general principle based on Microwave Induced Plasma process, use the microwave source of the other types such as klystron, travelling-wave tubes, or centre frequency is positioned at the process of its all band such as 433MHz, 915MHz, 28GHz, can acquire the coaxial fiber of C/SiC fast equally, therefore similar with the present invention operation also should belong to related content of the present invention.
Beneficial effect of the present invention:
1) process is simple, easy to operate.Non-environmental-pollution in preparation process, technique environmental protection, except power consumption in preparation process, does not produce waste gas, waste liquid, waste residue etc.;
2) cost of material is low, strong adaptability.Various carbon fiber all can be generated the C/SiC composite fibre of coaxial configuration by Microwave Induced Plasma process; Utilize the industrial goods such as commercially available silica flour, silica namely to can be used as silicon source, carry out the preparation of the coaxial fiber of C/SiC, and without the need to carrying out preliminary treatment in early stage to raw material;
3) speed preparing the coaxial fiber of carbon/carborundum (C/SiC) is fast, and efficiency is high, the processing procedure of Microwave Induced Plasma, only needs 10 ~ 60 seconds;
4) the coaxial fiber of the C/SiC acquired, structure is desirable.Carborundum (SiC) the protective layer continuous uniform that surface is formed, zero defect fine and close in the combination of carbon fiber core;
5) vacuum level requirements is low, can in the low vacuum of 10 ~ 50kPa, or the condition of normal pressure of nitrogen/argon gas shielded processes, and utilizes common mechanical pump or water ring pump just can reduce the impact of oxidizing atmosphere in furnace chamber; Accurate vacuum meter etc. is not needed to carry out the detection and control of reaction compartment condition yet;
6) product form size is controlled, and by the mol ratio in carbon source and silicon source in adjustment raw material, the processing power of Microwave Induced Plasma, and the technological parameter such as processing time, can obtain the coaxial fiber of C/SiC that SiC containment vessel layer thickness is different;
7) the coaxial fiber of the carbon/carborundum (C/SiC) acquired, have excellent antioxidant effect, initial oxidation temperature is increased to more than 760 DEG C, and this oxidation can be summed up as the oxidation of surface carborundum; Residual rate after more than 1100 ~ 1420 DEG C high temperature continued oxidation can reach more than 40%.
Accompanying drawing explanation
Fig. 1 is Kim etc. synthesizes on the coaxial fiber surface of C/SiC that obtains peeling based on VS mechanism;
Fig. 2 is the coaxial fiber surface SiC protection shell of C/SiC of the synthesis such as Kim and the combination interface pattern of carbon fiber core;
Fig. 3 is the coaxial fiber (diametric plane) of carbon/carborundum (C/SiC);
Fig. 4 is the coaxial fiber (axis) of carbon/carborundum (C/SiC);
Fig. 5 is the C/SiO utilizing electrospinning process to obtain
2coaxial fiber;
Fig. 6 is that compound use radio frequency directly-heated method and chemical gaseous phase depositing process prepare the coaxial fiber of C/SiC;
Fig. 7 is the coaxial fiber of C/SiC (3kW/55 second) that Microwave Induced Plasma process obtains;
Fig. 8 is the coaxial fiber of C/SiC (3.0kW/20 second) that Microwave Induced Plasma process obtains;
Fig. 9 is the coaxial fiber of C/SiC (2.0kW/30 second) that Microwave Induced Plasma process obtains;
Figure 10 is the coaxial fiber of C/SiC (4.0kW/15 second) that Microwave Induced Plasma process obtains;
Figure 11 is the coaxial fiber of C/SiC (5.5kW/10 second) that Microwave Induced Plasma process obtains;
Figure 12 is the coaxial fiber of C/SiC (3.5kW/40 second) that Microwave Induced Plasma process obtains.
Detailed description of the invention
Specific embodiment of the invention scheme is described below in detail.
Comparative example 1
Conventional chemical vapor sedimentation is used to prepare SiC coating
At present, the example using chemical vapour deposition technique to be prepared SiC coating has a lot.As document " CVD prepares SiC advanced ceramics material progress " (material engineering, 2002 (7): 46-48) relate to one methyl trichlorosilane (MTS) is precursor, pyrolysis is there is at 900 ~ 1600 DEG C, the SiC gas produced is deposited on matrix surface by cooling solidification, forms SiC coating.Although the SiC purity prepared by the method is high, deposition temperature range is wide, and can release a large amount of HCl gas when MTS decomposes, HCl gas not only has toxicity, and has stronger corrosivity to equipment, inadequate environmental protection.For another example document " with liquid carbon silane for precursor is for CVD SiC coating " (material science and technique, 2007,15 (6): 848-850) also using CVD in, it is characterized in that, with the monocrystalline silicon piece of cleaning and graphite flake for base substrate, to pioneer body with liquid carbon silane, H
2for carrier gas and protective gas, adopt the mode of bubbling to bring in cvd reactive chamber by precursor, continue the low pressure vacuumizing to keep about 1kPa.Control depositing temperature between 800 ~ 900 DEG C, lower the temperature after a period of time, monocrystalline silicon piece obtains SiC coating.Although the coating that the method is prepared is comparatively bright and clean, SiC purity is also higher, and sedimentation rate can reach 40nm/min (2.4 μm/hr), but deposited coatings is in uneven thickness, higher to the requirement of process equipment and experiment condition, course of reaction is difficult to obtain control, and cost is also higher.
Can find the analysis of chemical vapour deposition technique; this legal system needs the special equipment used comparatively complicated for SiC coating; and need a large amount of hydrogen that uses as protective gas; course of reaction expends time in length, and the cost of raw material is high, and higher to the requirement of process equipment and experiment condition; course of reaction is difficult to obtain control; carrying out for block or flaky matrix, SiC is relatively general, but for the such ad hoc structure of the coaxial fiber of C/SiC, in preparation, then has obvious difficulty.
Comparative example 2:
Sol-gel process (Sol-Gel) is used to prepare the coaxial fiber of C/SiC.
At present, the example using sol-gel process to prepare SiC coating also has a lot.As document " carbon fiber surface SiC/SiO
2the sol-gal process preparation of ORC " (novel charcoal material, 2013,28 (3): 208-214) described in, at room temperature mix with ethanol, MTES (MTES) with hydrochloric acid solution, after airtight stirring 2h, obtain the collosol and gel precursor of stable transparent.Again by impregnated carbon fiber dry process in sol solution, 1500 DEG C of heat treatment 2h under high-purity argon gas protection, synthesize uniform SiC/SiO in carbon fiber surface
2coating.
But the defect utilizing sol-gel process is comparatively obvious, and particularly precursor preparation technology is comparatively complicated, the course of reaction length that expends time in is the intrinsic drawback of this method; And containing corrosive elements in reactant, there is a large amount of volatile contaminants in building-up process, inadequate environmental protection, make the product obtained also need to do further purifying process.
Comparative example 3
With the contrast using solid sintering technology to prepare SiC coating in carbon fiber surface
Solid sintering technology is applied to one of method of preparing SiC coating very early.If Kim etc. is based on solid and gas (VS) mechanism, 7 μm of diameter carbon fibers that Univ Cambridge Tech (Goodfellow Cambridge Limited) provides are taken with Gu Te, and silicon dioxide powder, silica flour mixture be presoma, be the argon gas/hydrogen (Ar/H of 80/20 by flow-rate ratio
2) mixed flow gas protection under, in 1350 ~ 1400 DEG C reaction 5h, namely obtain the coaxial fiber of C/SiC.Thermal oxide contrast in air is carried out to the coaxial fiber of gained C/SiC, can find that unprotected carbon fiber is comparatively stable below 500 DEG C, 600 DEG C of dangerous cinders that namely burn.The oxidation initial temperature of the coaxial fiber of C/SiC is increased to 600 DEG C, and 700 ~ 800 DEG C just rapid oxidation are weightless, but 700 DEG C of continuous oxidation 2h then carbon fiber core oxidation is totally.Fig. 1 amplifies the photo display of 5,000 times, and the surperficial SiC pipe of formation is also imperfect, is difficult to completely to the protection of carbon fiber core; Fig. 2 pattern also shows, the inner surface of SiC pipe and the combination of carbon fiber core also not ideal enough.[information contrast source: J W, Lee S S, Jung Y G, et al.Synthesis of SiC microtube with villus-like morphology and SiC fiber [J] .Journal ofMaterials Reseauch, 2005,20 (2): 409-416Kim]
And for example described in patent CN 101003942 " a kind of method preparing coat of silicon carbide at carbon fiber surface ", by silica flour and carbon dust mixing, load in vacuum sphere grinding jar and grind to form mixed powder, be prepared into slurry; Again carbon fiber is put into slurry, after mixing, carry out drying, sintering, obtain the carbon fiber that surface has SiC coating.
Although simple with solid sintering technology equipment when carbon fiber surface prepares SiC coating, harsh to the requirement of experiment condition, need circulation to pass into Ar/H in building-up process
2protective atmosphere in, otherwise in like this for a long time high-temperature sintering process, carbon fiber is easy to be burnt, and also causes the raising of cost simultaneously.
Comparative example 4
With the contrast using precursor infiltration and pyrolysis method (PIP) to prepare carbon fiber surface SiC ORC
The precursor of SiC coating is prepared, using dimethylbenzene as solvent using the Polycarbosilane (PCS) of average molecular mass about 1500 as cracking process.By PCS grind into powder, be dissolved in dimethylbenzene, ultrasonic disperse prepares the PCS/ xylene solution that PCS mass fraction is 5 ~ 15%.Be under the condition of 1MPa respectively in a vacuum with pressure by carbon fiber, with PCS/ xylene solution dipping 1h; Then dry at 100 DEG C, then in the tube type resistance furnace of inert atmosphere protection in 950 DEG C of cracking to form SiC coating.Be cycled to repeat aforesaid operations repeatedly, to obtain the coaxial fiber of C/SiC.Carry out antioxygenic property to carbon fiber with the coaxial fiber of C/SiC utilizing PIP method to obtain to compare and can find, namely unprotected carbon fiber starts weightlessness at 400 DEG C, and 550 DEG C of oxidations completely.And the coaxial fiber of C/SiC containing SiC coating, oxidation initial temperature is increased to about 600 DEG C, and the residual mass mark after 950 DEG C of heat treatments is still about 30%.[information contrast source: Xiao Hanning, Chen Gangjun, Gao Pengzhao, Wang Chao, SiC preparation technology of coating on the impact of carbon fiber non-oxidizability, Hunan University's journal, 2007,34 (8), 41-44]
And for example in patent CN 103266470 A " a kind of carbon fiber ORC and preparation method thereof ", Polycarbosilane (PCS) and ethyl orthosilicate are added stirring and dissolving in dimethylbenzene and obtains precursor solution, pressure impregnation is with the carbon fabric perform of pyrocarbon coating again, in 160 ~ 220 DEG C time, solidify 1 ~ 2h in atmosphere, then in vacuum environment, at the temperature of 1000 ~ 1300 DEG C, cracking 1 ~ 2h also can prepare SiO at carbon fiber surface
2the SiC coating of doping.
But the raw material Polycarbosilane involved by the method is expensive, and organic solvent dimethylbenzene also has hypertoxicity, considerably increases preparation cost and danger.The cycle of whole building-up process is longer simultaneously, relates to the operations such as raw material dipping, solidification, Pintsch process, combined coefficient is reduced.In addition, because in high temperature pyrolysis process, the degraded of organic resin and micromolecular volatilization escape, although by repeated multiple times circulation dipping and pyrolysis processing, but still be difficult to eliminate the defects such as hole.And gained SiC coating is completed by repeatedly intermittent operation, in coutinuity of coating, uniformity etc. are Shortcomings all, is at high temperature easy to cause interfacial separation, and antioxygenic property deterioration was even lost efficacy.
Comparative example 5
With the contrast of the method for use generating silicon carbide coating by using silicon thermal evaporation method
Thermal evaporation silicon process synthesis SiC coating is also more common.As in patent CN 102477694 A " method of generating silicon carbide coating by using silicon thermal evaporation method ", silica flour or silico briquette fragment are put into bottom graphite crucible, be horizontally placed on crucible top using carbon fiber as carbon source, and be inverted onesize crucible thereon to fix carbon fiber.This device is put into high-temperature vacuum sintering furnace, is evacuated to 1 ~ 5Pa, under the protection of argon gas, be warming up to more than the fusing point of silicon, cool after insulation 1 ~ 9h, namely generate one deck coat of silicon carbide at carbon fiber surface.
Compared with conventional method, although the method has, equipment is simple, without the need to chlorosilane or polycarbosilane precusor gas and hydrogen, do not need the preliminary treatment carrying out raw material, the advantages such as the products pure obtained, preparation time is longer, at least needs more than 1h.A large amount of uses of protective gas argon gas simultaneously also result in cost and improve.
Comparative example 6
The thermal chemical vapor infiltrations such as compound use and pyrocarbon thermal response prepare the coaxial fiber of C/SiC
First by short for polypropylene-base (PAN) the carbon fiber staple fibre being cut to length 3 ~ 5mm.Then utilization waits thermal chemical vapor infiltration (ICVI) technology, take methane as presoma, take nitrogen as diluent gas, at the hot conditions of methane partial pressure 30kPa and 1100 DEG C and lower continuous pyrolysis 1 hour, deposit the thick RESEARCH OF PYROCARBON of coated 200nm (PyC) at carbon fiber surface.And then in vacuum sintering furnace, in graphite crucible, hold silicon dioxide powder (SiO
2) and silica flour (Si), and the mixture of chopped carbon fiber is (by SiO
2be placed on bottom graphite crucible with Si powder), successive reaction 1 hour under 1400 ~ 1600 DEG C of high temperature and 20Pa vacuum condition, namely respectively by silicon dioxide powder (SiO
2) and silica flour (Si) reaction first formed and discharge silicon monoxide (SiO) gas; continue to react with the RESEARCH OF PYROCARBON (PyC) of carbon fiber surface again and obtain carborundum (SiC) containment vessel, thus acquiring the coaxial fiber of C/SiC.
Fig. 3 illustrates in " diametric plane " of the coaxial fiber of carbon/carborundum (C/SiC) visible; the SiC of fiber sheath protects shell to be about 160nm, visible comparatively significantly interface between RESEARCH OF PYROCARBON (PyC) and carbon fiber core and carborundum protective layer.The microstructure being illustrated " axis " of the coaxial fiber of carbon/carborundum (C/SiC) by Fig. 4 also can find, due to the difference of thermal coefficient of expansion etc., the protective layer of the coaxial fiber of gained C/SiC has obvious crackle.[information contrast source: Hejun Li, Haibo Ouyang, LehuaQi, Yulei Zhang, Zhengjia Li and Jianfeng Wei.Effect of Temperature on the Synthesis of SiCCoating on Carbon Fibers by the Reaction of SiO with the Deposited PyrolyticCarbon Layer, J.Mater.Sci.Technol., 2010,26 (3), 211-216.]
Contrast 7
C/SiO prepared by method of electrostatic spinning
2coaxial composite fibre
First ethyl orthosilicate (TEOS), water, hydrochloric acid (HCl) are mixed according to mol ratio 1:2:0.01, join strong agitation 2h in ethanol in proper amount solvent, in time there is Tyndall phenomenon in colloidal sol, colloidal sol is placed in the insulation of 60 DEG C, baking oven, is hydrolyzed to promote TEOS and ethanol volatilization.To SiO
2dissolved adhesiveness takes out when increasing to 100mPas.The spinning nozzle of another transformation electrostatic spinning, makes coaxial two spinning nozzle by it.Then with SiO
2colloidal sol is shell, and polyacrylonitrile (PAN) solution is sandwich layer, has adopted coaxial electrostatic spinning legal system for PAN/SiO under the driving voltage of 15 ~ 18kV
2coaxial fiber.To gained PAN/SiO
2coaxial fiber carries out the process such as follow-up pre-oxidation, charing, can obtain C/SiO
2coaxial fiber.[information contrast source: Sun Liangkui, Cheng Haifeng, Chu Zengyong, Zhou Yongjiang, Sun Guoliang, C/SiO
2the preparation and property research of coaxial composite fibre, Journal of Inorganic Materials, 2009,24 (2), 310-314]
But the modified effect of this carbon-fiber high-temperature antioxygenic property, obviously not as SiC protects shell.Fig. 5 is the C/SiO utilizing electrospinning process to obtain
2coaxial fiber.Pattern shows, and coaxial fibre diameter is about 1 μm, carbon fiber has thickness be about the SiO of 20nm
2coating.
Comparative example 8
Compound use radio frequency directly-heated method and chemical gaseous phase depositing process prepare the coaxial fiber of C/SiC
Using carbon fiber as coated matrix, carbon fiber is positioned in RF-coupled chamber, under the radio-frequency electromagnetic field action produced utilizing radio-frequency signal generator, carbon fiber inside produces induced-current, absorbs RF energy because carbon fiber has certain resistance and forms ohm heat.When belt current intensity is enough large, carbon fiber body temperature can be increased to the required temperature of deposition.Adopt chemical vapour deposition (CVD) (CVD) method again, with methyl trichlorosilane (CH
3siCl
3) be precursor raw material, with hydrogen (H
2) be carrier gas, argon gas (Ar) is dilution and protective gas, under the depositing temperature of 700 ~ 780 DEG C, applies one deck SiC protective layer in carbon fiber surface low temperature.Wang Cheng states of Tu6Shi Shandong University etc. use radio frequency directly-heated method and chemical gaseous phase depositing process to prepare the pattern of the coaxial fiber of C/SiC.Photo shows, the coaxial fiber of the C/SiC that the method obtains, and by restrictions such as depositing temperature are lower, the SiC protective layer obtained is coarse, and fine and close not continuously, distribution and thickness etc. are also even not.[information contrast source: well is quick, Wang Chengguo, Zhu Bo, and white jade is pretty, Wang Yanxiang, Chen Xinmou, radio frequency directly-heated method in the research of carbon fiber surface low temperature SiC Coating, material engineering, 2005, (8), 53-58]; And for example in patent CN1461821A " technique of carbon fiber surface coating silicon carbide and device ", by radio frequency method fields focus device, 1100 ~ 1300 DEG C are heated to the graphitized carbon fibre in motion, the reaction environment that a chlorosilane adds high-purity hydrogen is manufactured while heating, chlorosilane cracking, achieves SiC and is deposited on carbon fiber surface formation coating.
But radio frequency method prepares the device of SiC and technique is all comparatively complicated, the speed of wire, reaction temperature and to be filled with the controllability of amount of reactant gases not high, directly affect the thickness of coating.Can produce pollution gas in simultaneous reactions process, the product obtained is impure.
Application example 1
With T300 type polypropylene (PAN) base carbon fibre, and silica (SiO
2) and silica flour (Si) be raw material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=2:1, the mol ratio Si:SiO of silicon/silicon dioxide in silicon source
2the ratio batching of=1:1, mixing is placed in the resonator of micro-wave oven.First be evacuated to about 15kPa, then apply the microwave of 3kW.Utilize the conductive characteristic of carbon fiber excellence and realize absorbing fast microwave energy, being warming up to about 1100 DEG C by the body of uniqueness instantaneously from heating.Meanwhile, the plasma of microwave induced generation will excite and the carbon atom on activated carbon fiber surface.Silica (SiO
2) and silica flour (Si) at high temperature react gaseous state silicon monoxide (SiO) intermediate of formation, the carbon atom activated with carbon fiber surface, the Formed SiClx (SiC) by reaction in-situ.Through the continuous irradiation of 55 seconds, namely obtain the SiC protective layer that thickness is about 565nm.
Take air as oxidizing atmosphere, respectively dynamic high temperature oxidation test comparison is carried out to PAN base carbon fibre and the coaxial fiber of C/SiC.Result shows, and the initial oxidation temperature of PAN base carbon fibre is about 410 DEG C, is rapid weight loss between 625 ~ 788 DEG C, more than 823 DEG C thermal oxide noresidues.The initial oxidation temperature of the coaxial fiber of C/SiC is then increased to 790 DEG C, and ironically, because carborundum is to the conversion of silica, does not present weightlessness time initial, but along with silica glass phase diaphragm continue thicken, coaxial fiber slightly increases weight; The temperature range that in the coaxial fiber of C/SiC, carbon fiber core is obviously oxidized is delayed to 825 ~ 980 DEG C.After more than 1100 ~ 1460 DEG C lasting thermal oxides, the residual rate of coaxial fiber is still up to 46%.
Fig. 7 is the coaxial fiber of C/SiC that Microwave Induced Plasma process obtained after 55 seconds.Amplify in the photo of 100,000 times visible, the SiC protective layer of carbon fiber surface is coated continuous uniform.Compared with the coaxial fiber of C/SiC obtained with various methods such as utilizing PIP method, CVD in comparative example; the SiC that the present invention obtains with Microwave Induced Plasma process protects shell to be obviously a continuous whole overall structure; surperficial without the defect such as hole or crackle, and fine and close with the combination of carbon fiber core.
Application example 2
By asphalt base carbon fiber and silica (SiO
2) and silica flour (Si) be raw material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=5:1, the mol ratio Si:SiO of silicon/silicon dioxide in silicon source
2the ratio batching of=2:1, mixing is placed in the resonator of micro-wave oven.First in resonator, pass into nitrogen (N
2) as protective atmosphere, then apply the microwave of 3kW, about sample rapid temperature increases to 1173 DEG C.Through the continuous irradiation of 20 seconds, namely obtain the SiC protective layer that thickness is about 260nm.
Carry out test display to the high-temperature thermal oxidation characteristic of the coaxial fiber of C/SiC, initial oxidation temperature is about 771 DEG C, and slightly increases weight; The fiber thermal weight loss of 805 ~ 940 DEG C of scopes is comparatively obvious; After more than 1100 ~ 1493 DEG C lasting thermal oxides, the residual rate of coaxial fiber is about 43%.
Fig. 8 is the coaxial fiber of C/SiC that Microwave Induced Plasma 3.0kW process obtained after 20 seconds.Amplify the pattern display of 100,000 times, the SiC protective layer of carbon fiber surface is coated continuous uniform, and the combination of SiC shell and carbon fiber core is fine and close.With implement compared with the coaxial fiber of C/SiC that additive method obtains in comparative example; SiC containment vessel continuous uniform surface is obtained without the defect such as hole or crackle with Microwave Induced Plasma process in the present invention; and it is fine and close with the combination of carbon fiber core; good overall structure is combined into carbon fiber core layer
Application example 3
With viscose-based carbon fiber and silica (SiO
2) and silica flour (Si) be raw material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=3:1, the mol ratio Si:SiO of silicon/silicon dioxide in silicon source
2the ratio batching of=0.5:1, mixing is placed in the resonator of micro-wave oven.Pass into argon gas (Ar) as protective atmosphere, then apply the microwave irradiation of 2.0kW, about sample rapid temperature increases to 1130 DEG C.Through the continuous process of the microwaves of 30 seconds and induced plasma, namely obtain the coaxial fiber of C/SiC.
Carry out test display to the high-temperature thermal oxidation characteristic of the coaxial fiber of C/SiC, initial oxidation temperature is about 762 DEG C, and slightly increases weight; 800 ~ 928 DEG C of interval thermal weight losses are rapider; After more than 1105 ~ 1420 DEG C lasting thermal oxides, the residual rate of coaxial fiber is about 41%.
Fig. 9 is the coaxial fiber of C/SiC that Microwave Induced Plasma 2.0kW process obtained after 30 seconds.Amplify the pattern display of 100,000 times, the SiC protective layer of carbon fiber surface is coated continuous uniform, thickness is about 51nm.Compared with the coaxial fiber of C/SiC obtained with various methods such as utilizing PIP method, CVD in comparative example; the SiC that the present invention obtains with Microwave Induced Plasma process protects shell; structural integrity is even; surface is without the defect such as hole or crackle; and fine and close with the combination of carbon fiber core, form desirable interface cohesion with carbon fiber.
Application example 4
With T700 type polypropylene-base carbon fiber (PAN-CF) and silica flour (Si) and silicon dioxide powder (SiO
2) be raw material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=4:1, the mol ratio Si:SiO of silicon/silicon dioxide in silicon source
2the ratio batching of=1.5:1, is positioned in the resonator of micro-wave oven after mixing.First be evacuated to about 35kPa, then apply the microwave of 4.0kW, about sample rapid temperature increases to 1220 DEG C.Through the continuous irradiation of 15 seconds, namely obtain the coaxial fiber of C/SiC.
Carry out test display to the high-temperature thermal oxidation characteristic of the coaxial fiber of C/SiC, initial oxidation temperature is about 806 DEG C, and slightly increases weight; The fiber thermal weight loss of 817 ~ 953 DEG C of scopes is relatively very fast, good to the protected effect of carbon fiber core.The high temperature of more than 1117 ~ 1439 DEG C continues thermal oxide, and the residual rate of coaxial fiber is still about 47%.
Figure 10 is the coaxial fiber of C/SiC that Microwave Induced Plasma 4.0kW process obtained after 15 seconds.Amplify the pattern display of 100,000 times, the SiC protective layer of carbon fiber surface is coated continuous uniform, thickness is about 265nm.Compared with the coaxial fiber of C/SiC obtained with additive methods such as utilizing PIP method, CVD in comparative example; the SiC utilizing Microwave Induced Plasma process to obtain in the present invention protects the combination of shell and carbon fiber core fine and close; interface zero defect, defines the overall structure that morphosis is ideal.
Embodiment 5
With gas-phase growth of carbon fibre and silica flour (Si) and silicon dioxide powder (SiO
2) be raw material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=5:1, the mol ratio Si:SiO of silicon/silicon dioxide in silicon source
2the ratio batching of=2:1, is positioned in the resonator of micro-wave oven after mixing.First be evacuated to about 25KPa, then apply the microwave of 5.5kW, about sample rapid temperature increases to 1245 DEG C.Through the continuous irradiation of 10 seconds, namely obtain the coaxial fiber of C/SiC.
Carry out test display to the high-temperature thermal oxidation characteristic of the coaxial fiber of C/SiC, initial oxidation temperature is about 781 DEG C; The fiber thermal weight loss change of 810 ~ 915 DEG C of scopes is relatively very fast, but still has comparatively significantly protected effect to carbon fiber core.The high temperature of more than 1105 ~ 1436 DEG C continues thermal oxide, deteriorated to some extent to the protective capability of carbon fiber core, and the oxidation of carbon fiber is comparatively serious, and the residual rate of coaxial fiber is about 42%.
Figure 11 is the coaxial fiber of C/SiC that Microwave Induced Plasma 5.5kW process obtained after 10 seconds.Amplify the pattern display of 100,000 times, the SiC protective layer of carbon fiber surface is coated continuous uniform, thickness is about 70.3nm.Compared with the coaxial fiber of the C/SiC obtained with additive method in comparative example; the SiC that the present invention obtains with Microwave Induced Plasma process protects shell to be obviously a continuous whole overall structure; surperficial without the defect such as hole or crackle, and fine and close with the combination of carbon fiber core.
Embodiment 6
With T800 type polyacrylonitrile (PAN) base carbon fibre and silica flour (Si) and silicon dioxide powder (SiO
2) be raw material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=4:1, the mol ratio Si:SiO of silicon/silicon dioxide in silicon source
2the ratio batching of=1:1, is positioned in the resonator of micro-wave oven after mixing.First be evacuated to about 30Pa, then apply the microwave of 3.5kW, about sample rapid temperature increases to 1190 DEG C.Through the continuous irradiation of 40 seconds, namely obtain the coaxial fiber of C/SiC.
Carry out test display to the high-temperature thermal oxidation characteristic of the coaxial fiber of C/SiC, initial oxidation temperature improves most 781 DEG C, and slightly increases weight; Rapid Thermal weightless temperature interval is delayed to 827 ~ 945 DEG C of scopes; The high temperature of more than 1117 ~ 1435 DEG C continues thermal oxide, and the oxidation of carbon fiber is relative, and the residual rate of coaxial fiber is about 44%.
Figure 12 is the coaxial fiber of C/SiC that Microwave Induced Plasma 3.5kW process obtained after 40 seconds.Amplify the pattern display of 100,000 times, the SiC protective layer of carbon fiber surface is coated continuous uniform, thickness is about 131nm.Compared with the coaxial fiber of the C/SiC obtained with additive method in comparative example, the SiC that the present invention obtains with Microwave Induced Plasma process protects shell more evenly complete, without the defect such as hole or crackle in structure, and with carbon fiber core in conjunction with ideal.
Claims (8)
1. a preparation method for the coaxial fiber of carbon/carborundum, forms mixture after the steps include: carbon fiber, silica flour, silicon dioxide powder fully to mix, and under being placed in vacuum or inert gas normal pressure protective condition; Utilize microwave to heat mixture, carbon fiber surface is activated and excites pyroreaction, obtain the coaxial fiber of carbon/carborundum.
2. the preparation method of the coaxial fiber of a kind of carbon/carborundum according to claim 1, it is characterized in that: described carbon and element silicon mol ratio are 2 ~ 5:1, described silica flour and the mol ratio of silica are 0.5 ~ 2:1.
3. the preparation method of the coaxial fiber of a kind of carbon/carborundum according to claim 1 and 2, is characterized in that: described vacuum condition pressure is 10 ~ 50kPa; Described inert gas is argon gas or nitrogen.
4. the preparation method of the coaxial fiber of a kind of carbon/carborundum according to claim 1 and 2, it is characterized in that: described heating using microwave frequency is 433MHz, 915MHz or 2.45GHz, heating power is 2 ~ 6kW.
5. the preparation method of the coaxial fiber of a kind of carbon/carborundum according to claim 1 and 2, is characterized in that: the described pyroreaction time is 10 ~ 60 seconds.
6. the preparation method of the coaxial fiber of a kind of carbon/carborundum according to claim 1 and 2, is characterized in that: described pyroreaction temperature is 1100 ~ 1250 DEG C.
7. the preparation method of the coaxial fiber of a kind of carbon/carborundum according to claim 1 and 2, is characterized in that: described carbon fiber is polyacrylonitrile-based carbon fibre, viscose-based carbon fiber, asphalt base carbon fiber or phenolic resins base carbon fibre.
8. utilize the coaxial fiber of carbon/carborundum prepared by the preparation method of the coaxial fiber of a kind of carbon/carborundum described in claim 1 or 2, it is characterized in that: the described coaxial fiber of carbon/carborundum take carbon fiber as core body, covering one deck carborundum protective layer of carbon fiber surface continuous uniform, carborundum protective layer and carbon fiber core be combined in amplification 100,000 times time fine and close zero defect; Carborundum protective layer thickness is 50 ~ 600nm.
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